CN117117165A - Method for repairing ternary positive electrode material by wet method - Google Patents
Method for repairing ternary positive electrode material by wet method Download PDFInfo
- Publication number
- CN117117165A CN117117165A CN202211595337.2A CN202211595337A CN117117165A CN 117117165 A CN117117165 A CN 117117165A CN 202211595337 A CN202211595337 A CN 202211595337A CN 117117165 A CN117117165 A CN 117117165A
- Authority
- CN
- China
- Prior art keywords
- lithium
- powder
- inorganic salt
- ternary
- positive electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 80
- 239000000843 powder Substances 0.000 claims abstract description 56
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 35
- 239000011343 solid material Substances 0.000 claims abstract description 29
- 239000012266 salt solution Substances 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 17
- 239000011888 foil Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000007873 sieving Methods 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 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
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 11
- 230000008439 repair process Effects 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- 238000011068 loading method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 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
- 238000005470 impregnation Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005303 weighing 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
- 230000006978 adaptation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000006229 carbon black Substances 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
- 239000012535 impurity Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910004761 HSV 900 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229940008015 lithium carbonate Drugs 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 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 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002351 wastewater Substances 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
-
- 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
Abstract
The invention provides a method for repairing ternary positive electrode materials by a wet 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 and electromagnetic iron removal treatment on the powder to obtain recovered powder; b) Stirring and mixing the reclaimed powder and an inorganic salt solution to obtain a mixed solution; then carrying out solid-liquid separation and drying on the mixed liquid to obtain a solid material; c) Roasting the solid material to obtain a sintered material; d) Crushing, sieving, demagnetizing, washing and drying the sintered material to obtain a repaired ternary anode material; wherein the concentration of the inorganic salt solution is 1-5 mol/L; the inorganic salt in the inorganic salt is Na 2 CO 3 、MgCO 3 、CaCO 3 、MgSO 4 And CaSO 4 At least one of them. The method provided by the invention can effectively recover and repair the ternary positive electrode material, and has the advantages of simple process and low cost.
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 wet method.
Background
The ternary lithium ion battery is widely applied to domestic and foreign portable electronic equipment and new energy automobiles due to the excellent performance. With the increasing demand for lithium ion batteries, a large number of lithium ion batteries will come out of service during peak hours. The lithium ion battery anode material contains Li, ni, co, mn and other valuable metals, has huge resource value, and the Li and Co prices are increased sharply in recent years, so that the cost of the ternary anode material is increased, and the recycling of the ternary anode material is greatly focused on reducing the influence of solid waste treatment on the environment.
At present, the method for recycling the ternary lithium ion battery anode material is mainly a wet process, valuable metals in the anode material are transferred into a solution in an ionic form through acid leaching or alkali leaching, then salts or oxides of nickel sulfate, cobalt sulfate, manganese sulfate, lithium carbonate, cobalt oxide, nickel oxide and the like are obtained through separation, purification and multi-step precipitation, a precursor is prepared again, and Li salt is added for roasting to prepare the ternary anode material. However, the recovery process is complex, the cost is high, and the recovery rate is low. In addition, in the prior art, elements such as nickel, cobalt, manganese, lithium and the like in the waste ternary lithium ion battery are utilized to prepare the ternary lithium ion battery anode material again, the nickel, cobalt, manganese and the lithium in the leaching solution are separated to prepare a nickel, cobalt, manganese hydroxide precursor and lithium carbonate or lithium hydroxide respectively, and then the ternary material is synthesized, so that the process flow is long. Thus, there is a need for a recovery process that is simpler, less costly, and more efficient.
Disclosure of Invention
In view of this, the present invention provides a method for wet repairing ternary positive electrode materials. The method provided by the invention can effectively recover and repair the ternary positive electrode material, and has the advantages of simple process and low cost.
The invention provides a method for repairing ternary positive electrode materials by a wet 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 and electromagnetic iron removal treatment on the powder to obtain recovered powder;
b) Stirring and mixing the reclaimed powder and an inorganic salt solution to obtain a mixed solution; then carrying out solid-liquid separation and drying on the mixed liquid to obtain a solid material;
c) Roasting the solid material to obtain a sintered material;
d) Crushing, sieving, demagnetizing, washing and drying the sintered material to obtain a repaired ternary anode material;
wherein,
the concentration of the inorganic salt solution is 1-5 mol/L;
the inorganic salt in the inorganic salt is Na 2 CO 3 、MgCO 3 、CaCO 3 、MgSO 4 And CaSO 4 At least one of them.
Preferably, in the step b), the solid content of the mixed solution is 30% -60%.
Preferably, in the step b), the stirring speed of the stirring and mixing is 100-300 rpm, and the time is 5-20 min.
Preferably, in step c), the roasting conditions are: the temperature rising rate is less than or equal to 20 ℃/min, the roasting temperature is 600-1000 ℃, and the heat preservation time is 5-20 h.
Preferably, in step a), the temperature of the heat treatment is 150 to 300 ℃ and the time is 1 to 10 hours.
Preferably, in step d), the solid content in the water washing is controlled to be 10% -40%.
Preferably, in step b), the drying temperature is 0 to 300 ℃; in step d), the drying temperature is 0-500 ℃.
Preferably, step c) specifically comprises: and mixing the solid material with a lithium source, and roasting to obtain a sintered material.
Preferably, the lithium source is at least one of lithium carbonate, lithium hydroxide, lithium ethoxide, lithium methoxide, lithium isopropoxide and lithium butoxide.
Preferably, the content of Li element in the lithium source is 100-20000 ppm in the mixture obtained after adding the lithium source.
According to the method provided by the invention, the used waste positive plate is subjected to 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; stirring and mixing the reclaimed powder with an inorganic salt solution to obtain a mixed solution; then carrying out solid-liquid separation and drying on the mixed liquid to obtain a solid material; roasting the solid material to obtain a sintered material; and finally, crushing, sieving, demagnetizing, washing and drying the sintered material to obtain the repaired ternary anode material. According to the invention, inorganic salt solution is used for impregnating and recycling powder, inorganic salt is introduced, corrosion damage of HF generated by high-temperature decomposition of a binder to a material is reduced, then roasting is carried out to obtain a ternary material, and then crushing, sieving, demagnetizing, washing and drying are carried out to obtain a pure ternary anode material; if necessary, a small amount of lithium source can be introduced in the roasting process, so that the surface of the material is further subjected to structural repair. The wet process of the invention is simple and convenient, environment-friendly and safe, has lower cost, and the repaired ternary positive electrode material has excellent performance, is equivalent to the electrochemical performance and the processing performance of the unused initial ternary positive electrode material, and has more time development significance in the time of the surge of lithium.
The test result shows that the discharge capacity of the repaired ternary positive electrode material obtained by the method reaches more than 120mAh/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 charge-discharge graph of a battery assembled from the materials obtained in example 1 and comparative example 1;
fig. 4 is a charge-discharge graph of the assembled battery 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 wet 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 and electromagnetic iron removal treatment on the powder to obtain recovered powder;
b) Stirring and mixing the reclaimed powder and an inorganic salt solution to obtain a mixed solution; then carrying out solid-liquid separation and drying on the mixed liquid to obtain a solid material;
c) Roasting the solid material to obtain a sintered material;
d) Crushing, sieving, demagnetizing, washing and drying the sintered material to obtain a repaired ternary anode material;
wherein,
the concentration of the inorganic salt solution is 1-5 mol/L;
the inorganic salt in the inorganic salt is Na 2 CO 3 、MgCO 3 、CaCO 3 、MgSO 4 And CaSO 4 At least one of them.
According to the method provided by the invention, the used waste positive plate is subjected to 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; stirring and mixing the reclaimed powder with an inorganic salt solution to obtain a mixed solution; then carrying out solid-liquid separation and drying on the mixed liquid to obtain a solid material; roasting the solid material to obtain a sintered material; and finally, crushing, sieving, demagnetizing, washing and drying the sintered material to obtain the repaired ternary anode material. The method provided by the invention can effectively recover and repair the ternary positive electrode material, and has the advantages of simple process and low cost.
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 and electromagnetic iron removal 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 NCM ternary positive electrode material, i.e. the treatment method is more suitable for NCM ternary positive electrode material, i.e. LiNi x Co y Mn 1-x-y O 2 More preferably, at least one of an NCM5 ternary positive electrode material (i.e., x=0.50 to 0.59 in the above general formula), an NCM6 ternary positive electrode material (i.e., x=0.60 to 0.69 in the above general formula), and an NCM7 ternary positive electrode material (i.e., x=0.70 to 0.79 in the above general 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 separated powder is subjected to ultrasonic vibration screen treatment. In the invention, the screen mesh size of the ultrasonic vibration screen is preferably 325 meshes, namely, 325 mesh powder is obtained. In the invention, after the ultrasonic vibration sieve treatment, electromagnetic iron removal treatment is carried out, and the electromagnetic iron remover can be used for treatment, the process of the electromagnetic iron remover is not particularly limited, the electromagnetic iron remover is carried out according to the conventional electromagnetic iron removal operation, and the reclaimed powder is obtained after the treatment.
Regarding step b)：
b) Stirring and mixing the reclaimed powder and an inorganic salt solution to obtain a mixed solution; and then carrying out solid-liquid separation and drying on the mixed liquid to obtain a solid material.
In the invention, the inorganic salt solution is an aqueous solution of inorganic salt. The inorganic salt in the inorganic salt solution is Na 2 CO 3 、MgCO 3 、CaCO 3 、MgSO 4 And CaSO 4 At least one of them. In the present invention, the concentration of the inorganic salt solution is 1 to 5mol/L, and specifically may be 1mol/L, 2mol/L, 3mol/L, 4mol/L, or 5mol/L. In the present invention, the relation between the amount of the reclaimed powder and the amount of the inorganic salt solution is preferably such that the solid content of the obtained mixed solution is 30% to 60%, that is, the mass ratio of the reclaimed powder to the mixed solution is (30 to 60): 100, and specifically, 30%, 35%, 40%, 45%, 50%, 55%, 60%. According to the invention, the reclaimed powder is placed in an inorganic salt solution for stirring and dipping, so that inorganic salt is doped in the inorganic powder, PVDF binder in the ternary pole piece material is decomposed to generate HF in the subsequent high-temperature treatment, so that the surface of the material is severely corroded, the material structure is destroyed, and the capacity of the material is reduced; the invention can effectively function only by controlling the concentration and the dosage of the inorganic salt solution, if the concentration of the inorganic salt is too high, the residual inactive substances and impurities in the material are increased, the material performance is affected, ifToo low a concentration of inorganic salts can result in HF not being adsorbed and reacted in time, which can corrode the material surface, resulting in reduced performance.
In the present invention, when the reclaimed powder and the inorganic salt solution are stirred and mixed, the stirring speed is preferably 100 to 300rpm, and specifically, 100rpm, 150rpm, 200rpm, 250rpm, 300rpm may be used. The stirring time is preferably 5-20 min, and specifically may be 5min, 10min, 15min, or 20min. Stirring and mixing to obtain a mixed solution which is uniformly mixed.
In the present invention, after the mixed liquid is obtained, solid-liquid separation is performed. The solid-liquid separation mode is not particularly limited, and is a conventional separation mode in the field, such as filtration and the like. After solid-liquid separation, the obtained solid was dried. In the present invention, the drying temperature is preferably 0 to 300 ℃, more preferably 120 ℃. The drying time is preferably 1 to 10 hours, specifically 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, more preferably 5 hours. After drying, a solid material was obtained.
Regarding step c)：
c) And roasting the solid material to obtain a sintered material.
In the present invention, the conditions for the calcination are preferably: the temperature rising rate is less than or equal to 20 ℃/min, the roasting temperature is 600-1000 ℃, and the heat preservation time is 5-20 h. Wherein the heating rate can be specifically 1 ℃/min, 5 ℃/min, 10 ℃/min, 15 ℃/min and 20 ℃/min. The baking 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 roasting, 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 (3) after the sintering treatment, obtaining a sintered material.
In the invention, a lithium source can be added before roasting, namely, the solid material and the lithium source are mixed for roasting, so that a sintered material is obtained. Wherein the lithium source is preferably at least one of lithium carbonate, lithium hydroxide, lithium ethoxide, lithium methoxide, lithium isopropoxide and lithium butoxide. In the invention, the content of Li element in the mixture obtained after adding the lithium source is preferably 100-20000 ppm, namely the mass ratio of Li in the lithium source to the mass of the mixture obtained after adding the lithium source is 100-20000 ppm, specifically can be 100ppm, 500ppm, 1000ppm, 5000ppm, 10000ppm, 15000ppm, 20000ppm. According to the invention, after the impregnation treatment by using the inorganic salt solution, a lithium source is added, and then the material is baked, so that the surface of the material can be subjected to structural repair, li lost on the surface is added, and the performance of the repaired ternary positive electrode material is ensured to be equivalent to that of an unused initial ternary positive electrode material. 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. Moreover, the control of the invention in the above dosage range is beneficial to achieving the best effect, if the lithium supplement 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 the normal ternary positive electrode material, and if the lithium supplement is too large, the residual alkali on the surface of the material is too much, and the processing performance and the high-temperature storage performance of the material are deteriorated.
In the invention, the materials are transferred into a sagger and then baked. Wherein, the bowl loading amount is preferably 1-7 kg/bowl, and can be specifically 1 kg/bowl, 2 kg/bowl, 3 kg/bowl, 4 kg/bowl, 5 kg/bowl, 6 kg/bowl and 7 kg/bowl; the dimensions of the interior of the sagger are preferably 330mm long by 330mm wide by 120mm high. And loading into a pot and roasting to obtain a sintered material.
Regarding step d)：
d) Crushing, sieving, demagnetizing, washing and drying the sintered 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.
In the invention, the solid content is preferably controlled to be 10% -40%, particularly 10%, 20%, 30% and 40% in the water washing process, and the solid content is controlled within the water washing solid content range, so that the water washing effect is ensured, the residual impurities are cleaned, the material performance is ensured, and the waste water amount is reduced. After washing with water, drying was performed. In the present invention, the drying temperature is preferably 0 to 500 ℃, more preferably 400 ℃. The drying time is preferably not more than 20 hours, more preferably 5 hours. And drying to obtain the repaired ternary positive electrode material.
According to the method provided by the invention, the used waste positive plate is subjected to 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; stirring and mixing the reclaimed powder with an inorganic salt solution to obtain a mixed solution; then carrying out solid-liquid separation and drying on the mixed liquid to obtain a solid material; roasting the solid material to obtain a sintered material; and finally, crushing, sieving, demagnetizing, washing and drying the sintered material to obtain the repaired ternary anode material. According to the invention, inorganic salt solution is used for impregnating and recycling powder, inorganic salt is introduced, corrosion damage of HF generated by high-temperature decomposition of a binder to a material is reduced, then roasting is carried out to obtain a ternary material, and then crushing, sieving, demagnetizing, washing and drying are carried out to obtain a pure ternary anode material; if necessary, a small amount of lithium source can be introduced in the roasting process, so that the surface of the material is further subjected to structural repair. The wet process of the invention is simple and convenient, environment-friendly and safe, has lower cost, and the repaired ternary positive electrode material has excellent performance, is equivalent to the electrochemical performance and the processing performance of the unused initial ternary positive electrode material, and has more time development significance in the time of the surge of lithium.
The test result shows that the discharge capacity of the repaired ternary positive electrode material obtained by the method reaches more than 120mAh/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 sintering the waste NCM5 ternary lithium ion battery positive plate at the low temperature of 250 ℃ for 3 hours, and separating powder from the foil. And (3) passing the stripped powder through an ultrasonic vibration sieve (325 meshes) and carrying out electromagnetic iron removal treatment to obtain recovered powder.
b) Placing the recovered powder material in Na 2 CO 3 The solution (concentration: 4 mol/L) was stirred at 200rpm for 30 minutes to obtain a mixed solution having a solid content of 30%. Then filtering and drying for 5 hours at 120 ℃ to obtain solid materials.
c) Weighing 5kg of solid materials, loading the solid materials into a sagger (the bowl loading amount is 5 kg/bowl), heating to 920 ℃ at the speed of 10 ℃/min, preserving heat, sintering for 5 hours, and then cooling to room temperature at the speed of 10 ℃/min to obtain the sintered materials.
d) Crushing, sieving (325 mesh of screen), demagnetizing, washing (solid content is 30% in washing), and drying at 400 ℃ for 5h to obtain the repaired ternary positive electrode material.
Comparative example 1
The procedure is as in example 1, except that step b) is not carried out, i.e. no impregnation with inorganic salt solution is carried out.
Example 2
a) And sintering the waste NCM6 ternary lithium ion battery positive plate at the low temperature of 250 ℃ for 3 hours, and separating powder from the foil. And (3) passing the stripped powder through an ultrasonic vibration sieve (325 meshes) and carrying out electromagnetic iron removal treatment to obtain recovered powder.
b) Placing the recovered powder material in Na 2 CO 3 The solution (concentration: 2 mol/L) was stirred at 300rpm for 10 minutes to obtain a mixed solution having a solid content of 30%. Then filtering and drying for 5 hours at 120 ℃ to obtain solid materials.
c) Weighing 5kg of solid materials, loading the solid materials into a sagger (the bowl loading amount is 5 kg/bowl), heating to 850 ℃ at the speed of 10 ℃/min, preserving heat, sintering for 5 hours, and cooling to room temperature at the speed of 10 ℃/min to obtain the sintered materials.
d) Crushing, sieving (325 mesh of screen), demagnetizing, washing (solid content is 30% in washing), and drying at 400 ℃ for 5h to obtain the repaired ternary positive electrode material.
Comparative example 2
The procedure is as in example 2, except that step b) is not carried out, i.e. no impregnation with inorganic salt solution is carried out.
Example 3: performance 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 is not significantly changed, but the binder on the surface reacts more thoroughly with substances such as carbon black, and the foreign matter residue is reduced, as compared with comparative example 2.
2. Electrochemical performance test
Assembling the battery:
9.0g of positive electrode active material, 0.5g of acetylene black (SP) conductive agent and 0.5g of PVDF (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. Positive electrode plate, metal lithium plate, negative electrode plate, ceramic diaphragm (thickness 16 μm), liPF 6 The electrolyte (concentration 1mol/L, solvent is mixed solvent of ethyl carbonate EC: dimethyl carbonate DMC: diethyl carbonate EMC volume ratio=1:1:1) is 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 charge and discharge of the battery assembled from the materials obtained in example 1 and comparative example 1, and fig. 4 is a graph of charge and discharge 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 84.84mAh/g, while the discharge capacity of example 1 can reach 120.79mAh/g, the gram capacity is increased by 35.95mAh/g, and the increase rate reaches 42%.
As can be seen from FIG. 4, the discharge capacity of comparative example 2 is brought into 89.85mAh/g, while the discharge capacity of example 2 can reach 160.79mAh/g, the gram capacity is increased by 70.94mAh/g, and the increase rate reaches 79%.
The test results of fig. 3-4 prove that the comparative example is directly sintered without being immersed in inorganic salt, which causes corrosion of HF on the surface of the material and lower discharge capacity, and after the treatment by the method of the embodiment, the material structure can be effectively repaired, and the discharge capacity of the material is obviously improved.
Example 4
a) And sintering the waste NCM6 ternary lithium ion battery positive plate at the low temperature of 250 ℃ for 3 hours, and separating powder from the foil. And (3) passing the stripped powder through an ultrasonic vibration sieve (325 meshes) and carrying out electromagnetic iron removal treatment to obtain recovered powder.
b) Placing the recovered powder material in Na 2 CO 3 The solution (concentration: 2 mol/L) was stirred at 200rpm for 15 minutes to obtain a mixed solution having a solid content of 30%. Then filtering and drying for 5 hours at 120 ℃ to obtain solid materials.
c) Weighing solid materials and lithium carbonate, uniformly mixing, loading the solid materials and the lithium carbonate into a sagger (the bowl loading amount is 5 kg/bowl, and the Li consumption in the lithium carbonate is 100 ppm), heating to 800 ℃ at the speed of 10 ℃/min, preserving heat and sintering for 6 hours, and then cooling to room temperature at the speed of 10 ℃/min to obtain the sintered materials.
d) Crushing, sieving (325 mesh of screen), demagnetizing, washing (solid content is 30% in washing), and drying at 400 ℃ for 5h to obtain the repaired ternary positive electrode material.
Example 5
According to example 2, except that Na in step b) is used 2 CO 3 Replacement of solution with CaSO 4 A solution.
Example 6: performance 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 | 120.79 |
| Example 2 | 160.79 |
| Example 4 | 161.2 |
| Example 5 | 160.3 |
| Comparative example 1 | 84.84 |
| Comparative example 2 | 89.85 |
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 120mAh/g or more, 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 discharge capacity is low because the material is directly sintered without being immersed by inorganic salt solution, and the surface of the material is corroded by HF. The discharge capacity of comparative example 3 is also significantly reduced compared to example 1, and it is proved that the performance of the material is reduced if the amount of the inorganic salt solution is too high, and the discharge capacity of the material can be effectively improved by controlling the amount of the inorganic salt solution to be a certain amount.
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 (10)
1. The method for repairing the ternary positive electrode material by the wet 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 and electromagnetic iron removal treatment on the powder to obtain recovered powder;
b) Stirring and mixing the reclaimed powder and an inorganic salt solution to obtain a mixed solution; then carrying out solid-liquid separation and drying on the mixed liquid to obtain a solid material;
c) Roasting the solid material to obtain a sintered material;
d) Crushing, sieving, demagnetizing, washing and drying the sintered material to obtain a repaired ternary anode material;
wherein,
the concentration of the inorganic salt solution is 1-5 mol/L;
the inorganic salt in the inorganic salt is Na 2 CO 3 、MgCO 3 、CaCO 3 、MgSO 4 And CaSO 4 At least one of them.
2. The method according to claim 1, wherein in step b) the solid content of the mixed liquor is 30-60%.
3. The method according to claim 1, wherein in the step b), the stirring rate of the stirring and mixing is 100 to 300rpm for 5 to 20 minutes.
4. The method according to claim 1, wherein in step c), the firing conditions are: the temperature rising rate is less than or equal to 20 ℃/min, the roasting temperature is 600-1000 ℃, and the heat preservation time is 5-20 h.
5. The method according to claim 1, wherein in step a), the heat treatment is performed at a temperature of 150 to 300 ℃ for a time of 1 to 10 hours.
6. The method according to claim 1, wherein in step d), the solids content in the water wash is controlled to be 10-40%.
7. The method according to claim 1, wherein in step b), the drying temperature is 0 to 300 ℃;
in step d), the drying temperature is 0-500 ℃.
8. The method according to claim 1, wherein step c) comprises in particular: and mixing the solid material with a lithium source, and roasting to obtain a sintered material.
9. The method of claim 8, wherein the lithium source is at least one of lithium carbonate, lithium hydroxide, lithium ethoxide, lithium methoxide, lithium isopropoxide, and lithium butoxide.
10. The method according to claim 1 or 8, wherein the Li element in the lithium source is present in an amount of 100 to 20000ppm in the resulting mixture after the addition of the lithium source.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211595337.2A CN117117165A (en) | 2022-12-13 | 2022-12-13 | Method for repairing ternary positive electrode material by wet method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211595337.2A CN117117165A (en) | 2022-12-13 | 2022-12-13 | Method for repairing ternary positive electrode material by wet method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117117165A true CN117117165A (en) | 2023-11-24 |
Family
ID=88797157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211595337.2A Pending CN117117165A (en) | 2022-12-13 | 2022-12-13 | Method for repairing ternary positive electrode material by wet method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117117165A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102738539A (en) * | 2011-04-08 | 2012-10-17 | 深圳市雄韬电源科技股份有限公司 | Method and apparatus for recovering lithium iron phosphate material from positive plates of waste lithium iron phosphate batteries |
| CN103370829A (en) * | 2011-02-15 | 2013-10-23 | 住友化学株式会社 | Method of recovering active material from scrap battery material |
| CN105244561A (en) * | 2015-08-28 | 2016-01-13 | 郭建 | Method for preparing high-voltage multi-component material by taking waste multi-component power lithium battery as a raw material |
| CN107008729A (en) * | 2017-04-18 | 2017-08-04 | 中科过程（北京）科技有限公司 | A kind of method of waste and old lithium ion battery roasting sorting |
| CN108336442A (en) * | 2018-03-01 | 2018-07-27 | 中国科学院过程工程研究所 | A method of detaching aluminium foil and anode waste from lithium ion battery positive plate |
| 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 |
| CN110311186A (en) * | 2019-03-06 | 2019-10-08 | 清华大学 | A method of recycling valuable element from waste and old lithium ion battery |
| WO2022055272A1 (en) * | 2020-09-11 | 2022-03-17 | 주식회사 엘지에너지솔루션 | Method for recovering cathode material |
| CN114597532A (en) * | 2022-03-15 | 2022-06-07 | 清华大学深圳国际研究生院 | Method for directly regenerating failed lithium cobaltate positive electrode into high-voltage lithium cobaltate positive electrode and product |
-
2022
- 2022-12-13 CN CN202211595337.2A patent/CN117117165A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103370829A (en) * | 2011-02-15 | 2013-10-23 | 住友化学株式会社 | Method of recovering active material from scrap battery material |
| CN102738539A (en) * | 2011-04-08 | 2012-10-17 | 深圳市雄韬电源科技股份有限公司 | Method and apparatus for recovering lithium iron phosphate material from positive plates of waste lithium iron phosphate batteries |
| CN105244561A (en) * | 2015-08-28 | 2016-01-13 | 郭建 | Method for preparing high-voltage multi-component material by taking waste multi-component power lithium battery as a raw material |
| CN107008729A (en) * | 2017-04-18 | 2017-08-04 | 中科过程（北京）科技有限公司 | A kind of method of waste and old lithium ion battery roasting sorting |
| 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 |
| CN108336442A (en) * | 2018-03-01 | 2018-07-27 | 中国科学院过程工程研究所 | A method of detaching aluminium foil and anode waste from lithium ion battery positive plate |
| CN110311186A (en) * | 2019-03-06 | 2019-10-08 | 清华大学 | A method of recycling valuable element from waste and old lithium ion battery |
| WO2022055272A1 (en) * | 2020-09-11 | 2022-03-17 | 주식회사 엘지에너지솔루션 | Method for recovering cathode material |
| CN114597532A (en) * | 2022-03-15 | 2022-06-07 | 清华大学深圳国际研究生院 | Method for directly regenerating failed lithium cobaltate positive electrode into high-voltage lithium cobaltate positive electrode and product |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5992016B2 (en) | Method for modifying lithium ion battery cathode material | |
| CN111653761B (en) | Preparation method of high-nickel positive electrode material with improved water washing | |
| JP7371263B2 (en) | How to reuse active materials using cathode scraps | |
| CN109904446B (en) | Regenerated positive electrode material, preparation method thereof and lithium ion battery containing regenerated positive electrode material | |
| CN109119711B (en) | Method for preparing high-voltage positive electrode material by adopting waste lithium cobalt oxide battery | |
| CN102651490A (en) | Regeneration method of positive active material of waste lithium battery | |
| CN104078719A (en) | Method for preparing nickel lithium manganate by using waste lithium manganate battery | |
| CN115064805A (en) | Method for recycling and regenerating anode material of waste ternary lithium ion battery | |
| CN114122552A (en) | LiAlO prepared by recycling retired lithium ion battery2Method for coating single crystal anode material | |
| CN111048862B (en) | Method for efficiently recovering lithium ion battery anode and cathode materials as supercapacitor electrode materials | |
| CN104953096A (en) | Surface-modified high-voltage lithium cobalt oxide positive material and preparation method thereof | |
| CN114134329B (en) | Method for recycling valuable metals in positive electrode material by utilizing aluminum foil of current collector of waste lithium ion battery | |
| CN104466293A (en) | Regeneration method of lithium ion battery anode material lithium cobalt oxide waste | |
| CN116706050B (en) | Medium-low nickel monocrystal ternary positive electrode material, preparation method thereof and battery | |
| US20230335817A1 (en) | Method for recycling lithium battery cathode material | |
| CN117096486A (en) | Repairing and regenerating method for waste lithium ion battery anode material | |
| CN104600284A (en) | Method for regenerating positive active material in spent lithium manganate lithium ion battery | |
| CN117117165A (en) | Method for repairing ternary positive electrode material by wet method | |
| CN111410239A (en) | Regeneration and recovery method of retired nickel cobalt lithium manganate battery positive electrode material | |
| CN113943021A (en) | Regenerated lithium cobaltate and repairing method and application thereof | |
| CN114447465A (en) | Method and material for synergistically regenerating anode material and cathode material of lithium ion battery and application of material | |
| CN117117166A (en) | Method for repairing ternary positive electrode material by dry method | |
| JP2005135849A (en) | Positive electrode activator for lithium battery | |
| CN114639889B (en) | Method for in-situ restoration of waste lithium battery anode material by supercritical water | |
| CN113943020A (en) | Regenerated lithium cobaltate and activation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |