CN117080600A - Method for treating, repairing and regenerating waste lithium secondary battery anode material - Google Patents
Method for treating, repairing and regenerating waste lithium secondary battery anode material Download PDFInfo
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- CN117080600A CN117080600A CN202311026567.1A CN202311026567A CN117080600A CN 117080600 A CN117080600 A CN 117080600A CN 202311026567 A CN202311026567 A CN 202311026567A CN 117080600 A CN117080600 A CN 117080600A
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- positive electrode
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- borohydride
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- 239000002699 waste material Substances 0.000 title claims abstract description 75
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000010405 anode material Substances 0.000 title claims description 14
- 230000001172 regenerating effect Effects 0.000 title claims description 8
- 239000007774 positive electrode material Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 20
- 150000003624 transition metals Chemical class 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000002386 leaching Methods 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000002893 slag Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000006183 anode active material Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 238000011084 recovery Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 13
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 239000010926 waste battery Substances 0.000 abstract 1
- 239000011149 active material Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 9
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- -1 aluminum ions Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention belongs to the field of recovery of waste battery materials, and in particular relates to a treatment method of a waste lithium secondary battery positive electrode material, which is characterized in that the waste positive electrode material is obtained from a waste lithium secondary battery, the waste positive electrode material and borohydride are arranged in a reaction kettle, and the first-stage heat treatment is performed in advance at the temperature of 400-500 ℃, and then the second-stage heat treatment is performed at the temperature of 500-600 ℃ in a steam atmosphere; then carrying out water leaching treatment, and carrying out solid-liquid separation to obtain lithium liquid and transition metal slag. The process can effectively realize the recovery and regeneration of the anode, can refine the structure and modify the anode, and is beneficial to improving the performance of regenerated materials.
Description
Technical Field
The invention belongs to the field of battery waste recovery, and particularly relates to the field of waste lithium battery material recovery.
Background
Waste lithium ion batteries such as mainstream waste ternary batteries (positive electrode active material is mainly NCM ternary material, liNi x Co y Mn z O 2 It has higher potential value and higher recovery and regeneration value.
In the prior art, the main recovery process of the main stream waste lithium ion battery mainly comprises the processes of full acid leaching, lithium pre-extraction and the like:
the Chinese patent document with publication number of CN116417704A discloses a method for recycling ternary lithium battery anode materials based on supercritical hydrothermal reaction, which comprises the following steps: firstly, mixing a positive electrode piece of a waste ternary lithium battery with a first oxidant and deionized water, performing hydrothermal oxidation reaction in a supercritical state, and filtering to obtain filter residues after the reaction is completed; then, acid leaching is carried out on filter residues by using inorganic acid liquor containing a reducing agent, and precipitation removal is carried out on aluminum ions; adding nickel salt, manganese salt and cobalt salt into the aluminum removal filtrate, adjusting the proportion, and then adding a complexing agent and a precipitator for coprecipitation reaction to obtain a ternary precursor; and finally, carrying out hydrothermal crystallization reaction on the ternary precursor, mixing the ternary precursor with a lithium source and a second oxidant, and carrying out hydrothermal synthesis reaction in a supercritical state to obtain the regenerated ternary anode material.
Then, as disclosed in Chinese patent document with publication number of CN114956130A, a subcritical lithium pre-extraction method of a waste lithium battery positive electrode material is disclosed, a mixed solution containing waste lithium battery positive electrode powder, water and polyhydroxy alcohol is heated, so that the water in the mixed solution is in a subcritical state, the water is maintained in the subcritical state, the pre-extraction lithium treatment is carried out, and after the treatment is finished, solid-liquid separation is carried out, so as to obtain a lithium extraction liquid; the number of the hydroxyl groups of the alcohols in the polyhydroxy alcohol is more than or equal to 2; in the water and the polyhydroxy alcohol, the volume fraction of the polyhydroxy alcohol is more than or equal to 30 percent.
Although the prior art reports that a plurality of recovery modes of waste positive electrode materials bring good recovery effect, the problems that the element separation selectivity is not ideal, high-performance materials are difficult to regenerate conveniently, the three wastes are high in output and the like are also common.
Disclosure of Invention
Aiming at the problems faced by the recovery of the positive electrode of the existing waste lithium ion battery, the invention aims to provide a treatment method of the positive electrode material of the waste lithium secondary battery, which aims at efficiently recovering and separating lithium and transition metals from the waste positive electrode material.
The second aim of the invention is to provide a repairing and regenerating method of the waste positive electrode material, which aims at regenerating the waste positive electrode material to obtain the high-performance positive electrode active material.
The method for processing the waste lithium secondary battery positive electrode material comprises the steps of obtaining the waste positive electrode material from the waste lithium secondary battery, arranging the waste positive electrode material and borohydride in a reaction kettle, carrying out first-stage heat treatment at 400-500 ℃ in advance, and carrying out second-stage heat treatment at 500-600 ℃ in a steam atmosphere; then carrying out water leaching treatment, and carrying out solid-liquid separation to obtain lithium liquid and transition metal slag.
The innovative research of the invention shows that the first section of heat treatment assisted by borohydride and the second section of heat treatment assisted by steam are further matched with the joint control of the temperature of the heat treatment, so that the lattice structure of the waste anode material can be effectively destroyed, lithium and transition metal in the waste anode material can be effectively separated, and the method is not only beneficial to modifying and modifying the separated components, but also beneficial to improving the electrochemical performance of the regenerated material.
In the invention, the waste lithium secondary battery can be a waste lithium ion battery.
In the invention, the waste positive electrode material can be stripped from the waste lithium secondary battery based on a known method. For example, the waste lithium ion battery is discharged, disassembled and stripped (such as organic solvent NMP stripping) to obtain waste positive electrode powder. In the invention, considering the simplicity of the process, the waste lithium ion battery anode material is allowed to contain at least one of a conductive agent, a binder and an electrolyte.
In the present invention, the content of the waste positive electrode material is not particularly required, and the content of the active material is preferably 50wt% or more, more preferably 80wt% or more, and still more preferably 80 to 95 wt% in view of process economy.
In the invention, the borohydride is at least one of sodium borohydride and potassium borohydride.
In the invention, the weight ratio of the borohydride to the positive electrode active material in the waste positive electrode material is 5-10: 1.
in the invention, the waste anode material and the borohydride are arranged in the reaction kettle in a single-layer mixing or double-layer stacking mode.
The monolayer mixing mode means that the waste anode material and the borohydride are arranged in the reaction kettle in a monolayer mode in a mixture mode.
The double-layer superposition comprises a bottom layer and an upper layer arranged on the bottom layer, wherein copper nets are arranged on the bottom layer and the upper layer (the copper net holes can be ventilated and can intercept upper layer particles); the bottom layer is a borohydride layer, the upper layer is a mixed layer of waste anode material and borohydride, and the borohydride content in the upper layer accounts for 10-20% of the total borohydride content.
According to the research of the invention, the components are arranged in a double-layer superposed manner, and the reaction is carried out, so that the separation effect of lithium and transition metal can be further improved, the modification effect of the material can be further improved, and the electrochemical performance of the regenerated material can be further improved.
In the invention, the pressure in the initial stage of the first heat treatment can be normal pressure or can be pressurized by protective atmosphere; the preferred pressurization pressure is 1 to 3MPa.
It has been unexpectedly found that the pressurization by the protective atmosphere at the initial stage, in combination with the subsequent two-stage treatment, helps to further improve the separation of lithium and transition metal and the modification effect, and can further facilitate regeneration to obtain a material with high electrochemical performance.
Preferably, the first heat treatment is carried out for a period of 1 to 3 hours.
In the present invention, in the second stage of treatment, other water vapor may be introduced directly into the treatment system, or water may be introduced into the system.
In the invention, the water vapor is introduced into the waste anode material in a weight ratio of 10-20: 1, a step of;
preferably, the second heat treatment is carried out for a period of 1 to 3 hours.
The invention also provides a repairing and regenerating method of the waste anode material, and the method is adopted to obtain lithium liquid and transition metal slag; and (3) obtaining a lithium source from the lithium liquid, and then mixing the lithium source with the transition metal slag to perform oxidation roasting to obtain the regenerated anode active material.
According to the invention, the research discovers that the separation of lithium and transition metal can be realized and the repair modification can be realized thanks to the treatment method, and the obtained lithium source and transition metal source are subjected to oxidative roasting, so that the electrochemical performance of the repaired material can be improved.
In the present invention, a lithium round and a transition metal source may be obtained using a known process, and then may be regenerated based on a known process to form a positive electrode active material.
In the invention, the lithium liquid is evaporated to obtain a lithium source, or the lithium liquid is carbonized and precipitated to obtain the lithium source. The research of the invention shows that the adoption of the carbonization precipitation mode to obtain the lithium source is beneficial to effectively retaining the modification advantage of the treatment method and further improving the electrochemical performance of the regenerated material.
In the invention, the transition metal slag is subjected to washing treatment in advance. Preferably, the washing process comprises a water washing and/or alkali washing process, and further preferably comprises alkali washing and water washing; more preferably, the washing is performed after the alkali washing. It is found that based on the process, the modification advantage of the recovery process of the invention can be further maintained, and the electrochemical properties of the regenerated material can be further improved.
In the present invention, the liquid-solid ratio in the water washing and alkaline washing stages is not particularly limited, and may be, for example, 5 to 50ml/g. In the present invention, the alkali liquor in the alkaline washing stage may be an aqueous alkali metal hydroxide solution of 0.1 to 5M.
In the present invention, the oxidative calcination stage is carried out under an oxygen-containing atmosphere. And the temperature of the oxidizing roasting is 600-800 ℃.
Preferably, the time of the oxidative calcination is 1 to 5 hours.
Advantageous effects
The innovative research of the invention shows that the first section of heat treatment assisted by borohydride and the second section of heat treatment assisted by steam are further matched with the joint control of the temperature of the heat treatment, so that the lattice structure of the waste anode material can be effectively destroyed, lithium and transition metal in the process of separation can be effectively separated, and the modification and modification of the separated components are facilitated, and the electrochemical performance of the regenerated material is further improved.
The invention adopts the two-layer superposition one-section heat treatment mode, further matches with the acquisition mode of a lithium source and a transition metal source, and can further synergistically improve the electrochemical performance of the regenerated active material.
Drawings
FIG. 1 is a cycle chart of example 1;
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
In the present invention, the content of the active material in the positive electrode material of the waste lithium ion battery is not particularly required, and in view of the economical efficiency of the process, the content is preferably 50wt.% or more, and in the following cases, the active content is 85 to 90wt.% unless specifically stated.
In the course of the operation of the invention, except for the particular restrictions, the temperatures are, for example, in the case of washing processes, all at room temperature, for example, in particular from 15 to 40 ℃.
Example 1:
step (1):
putting a waste power NCM111 nickel cobalt lithium manganate battery into 2mol/L saline water for 30h discharge treatment, drying the discharged battery at 85 ℃, disassembling and separating a positive plate and a negative plate, soaking the positive plate into N-methylpyrrolidone, separating a current collector in the positive plate, filtering, washing with water, and drying to obtain waste positive powder;
step (2): two-stage calcination
Waste positive electrode powder and sodium borohydride are treatedWherein NCM active material/NaBH 4 Uniformly mixing the materials in a weight ratio of 1:7), and then setting the mixture in a pressure-resistant reaction kettle, and performing first-stage roasting treatment, wherein the temperature of the first-stage roasting treatment (marked as T1) is 450 ℃ and the time is 2 hours;
then, steam (15 times of the weight of the active material of the waste anode powder) is introduced into the reaction system for the second stage of roasting treatment, the temperature (marked as T2) of the process is 550 ℃, the time is 1h, and the steam is introduced. After the reaction was completed, the reaction mixture was cooled to room temperature and taken out.
Step (3):
the reaction material of the step (2) is 10: adding pure water into the solution with the liquid-solid ratio of 1mL/g for leaching for 1h at 30 ℃, filtering to obtain filtrate A and filter residue, washing the filter residue (the liquid-solid ratio is 15 mL/g) to obtain a washing solution a and washing residues, washing the washing residues with alkali (washing with 0.5M sodium hydroxide alkali liquor, the liquid-solid ratio is 15 mL/g), and washing the washing residues with water until the filtrate is neutral to obtain a transition metal source;
combining the water washing liquid a and the filtrate A to obtain lithium liquid; and evaporating the lithium liquid to obtain a lithium source.
In the waste nickel cobalt lithium manganate anode, the recovery rate of lithium is Li99.1%.
Step (4): regeneration of
Mixing the lithium source and the transition metal source in the step (3), and controlling the molar ratio of NCM to be 1:1:1, and the molar ratio of Li to NCM is 1.05:1, and then roasting is carried out for 3 hours at the temperature of 700 ℃ under the air atmosphere, so as to obtain the regenerated positive electrode active material.
The regenerated material is subjected to electrochemical performance test, and the steps and conditions are as follows: in a glove box, under argon atmosphere, using aluminum foil as a current collector, coating a positive plate containing 90% of a positive electrode material regenerated by a positive electrode active material (regenerated positive electrode active material: conductive carbon black: PVDF (weight ratio: 90: 5)) and a negative electrode of lithium plate, wherein EC/EMC (volume ratio: 1) of 1mol/L LiPF6 is electrolyte, and the electrolyte shows 178mAh g at room temperature in 1C constant current circulation of 500 circles -1 Is a cyclic specific capacity of (c).
Example 2
Compared with the example 1, the difference is only that the proportion of the waste anode powder to the sodium borohydride in the step (2) is changed, and the experimental groups are as follows:
a: the ratio of active materials to sodium borohydride in the waste anode powder is 1:5;
b: the ratio of active materials to sodium borohydride in the waste anode powder is 1:10;
the test was performed as in example 1, with the following results:
group A: and (3) leaching rate of lithium is Li99.8%. A cycle specific capacity of 175mAh g-1 at room temperature in 500 cycles of constant current cycle of 1C;
group B: and (3) leaching rate of lithium is Li99.9%. The circulating specific capacity of 181mAh g-1 is shown in 500 circles of constant current circulation of 1C at room temperature;
example 3
The only difference compared with example 1 is that the two-stage treatment mechanism is changed, and the experimental groups are respectively as follows:
a: t1 is 400℃for 3h, T2 is 500℃for 3h.
B: t1 is 500℃for 1h, T2 is 600℃for 1h.
The test was performed as in example 1, with the following results:
group A: and (3) leaching rate of lithium is Li99.8%. The circulating specific capacity of 183mAh g-1 is shown in 500 circles of constant current circulation of 1C at room temperature;
group B: and (3) leaching rate of lithium is Li99.8%. The circulation specific capacity of 179mAh g-1 is shown at room temperature and in 500 circles of constant current circulation of 1C.
Example 4
The difference compared with example 1 is only that in step (2), the initial stage of the first stage firing is changed, and the firing is performed by pressurizing with Ar to 1MPa in advance and then heating to T1. The temperature of the water immersion process was 20℃and the subsequent stage was the same as in example 1.
The test was performed as in example 1, with the following results:
and (3) leaching rate of lithium is Li99.8%. The cycling specific capacity of 195mAh g-1 was exhibited at room temperature for 500 cycles of constant current at 1C.
Example 5
The difference compared with example 1 is only that in the modification step (2), the sample setting is performed by a double-layer stacking manner: setting 85% sodium borohydride at the bottom layer of the reaction kettle, setting the mixture of active material in the waste positive electrode powder and the rest 15% sodium borohydride at the upper layer of the stratum, and setting copper mesh at the bottom layer and the upper layer; the copper mesh hole can be breathable and can intercept upper particles. The temperature of the water immersion process was 20℃and the other operations and parameters were the same as in example 1.
The test was performed as in example 1, with the following results:
and (3) leaching rate of lithium is Li99.9%. The circulation specific capacity of 196mAh g-1 is shown at room temperature and in 500 circles of constant current circulation of 1C.
Example 6
Compared with the embodiment 5, the difference is that in the step (3), carbon dioxide is introduced into the lithium liquid until the precipitation is completed, and the lithium source is obtained by solid-liquid separation; the subsequent procedure is as in example 1.
The test was performed as in example 1, with the following results:
the circulation specific capacity of 197mAh g-1 is shown in 500 circles of constant current circulation of 1C at room temperature.
Comparative example 1
The difference compared to example 1 is only that the first heat treatment process is performed in a mixed gas containing 10v% of hydrogen-Ar. Other operations and parameters were the same as in example 1.
In the waste nickel cobalt lithium manganate anode, the recovery rate of lithium is 98.8%, and the regenerated active material circulates for 200 circles according to the condition of the example 1, and only 157mAh g-1 circulation specific capacity is left.
Comparative example 2
The only difference compared to example 1 is that no NaBH4 was added in the first firing stage and other operations and parameters were the same as in example 1.
The test was performed as in example 1, with the following results: the recovery of lithium was 47.9%, and the regenerated active material was cycled 200 times under the conditions of example 1 to leave only 113mAh g -1 Is a cyclic specific capacity of (c).
Comparative example 3
The only difference compared to example 1 is that no steam was introduced in the second calcination stage, and other operations and parameters are the same as in example 1.
The test was performed as in example 1, with the following results: the recovery of lithium was 98.5%, and the regenerated active material was cycled 200 times under the conditions of example 1 with only 166mAh g-1 of specific capacity.
Comparative example 4
The only difference compared to example 1 is that the temperature of the first stage firing was changed to 300℃and other operations and parameters were the same as in example 1.
In the waste nickel cobalt lithium manganate anode, the leaching rate of lithium is Li64.3%, and the regenerated active material circulates for 200 circles according to the condition of the example 1 to only leave 156mAh g-1 of circulating specific capacity.
Claims (10)
1. A method for processing a waste lithium secondary battery positive electrode material is characterized in that the waste lithium secondary battery positive electrode material is obtained, the waste positive electrode material and borohydride are arranged in a reaction kettle, the first-stage heat treatment is carried out in advance at the temperature of 400-500 ℃, and the second-stage heat treatment is carried out in the steam atmosphere at the temperature of 500-600 ℃; then carrying out water leaching treatment, and carrying out solid-liquid separation to obtain lithium liquid and transition metal slag.
2. The method for treating a waste positive electrode material according to claim 1, wherein the waste lithium secondary battery is a waste lithium ion battery;
preferably, the positive electrode active material in the waste positive electrode material comprises at least one of lithium cobaltate, lithium nickelate, lithium manganate and nickel cobalt manganese ternary;
preferably, the waste positive electrode also comprises at least one of a diaphragm, a conductive agent, a binder and an electrolyte;
preferably, in the waste positive electrode material, the content of the positive electrode active material is more than 50wt%, and further 80-95 wt%.
3. The method for treating waste positive electrode material according to claim 1, wherein the borohydride is at least one of sodium borohydride and potassium borohydride.
4. The method for treating a waste positive electrode material according to claim 1, wherein the weight ratio of the borohydride to the positive electrode active material in the waste positive electrode material is 5 to 10:1.
5. the method for treating a waste positive electrode material according to any one of claims 1 to 4, wherein the waste positive electrode material and the borohydride are arranged in a single-layer mixing or double-layer stacking manner in a reaction kettle;
the double-layer stack comprises a bottom layer and an upper layer arranged on the bottom layer, and copper nets are arranged on the bottom layer and the upper layer; the bottom layer is a borohydride layer, the upper layer is a mixed layer of waste anode material and borohydride, and the borohydride content in the upper layer accounts for 10-20% of the total borohydride content.
6. The method for treating a waste positive electrode material according to claim 1, wherein the initial stage of the first heat treatment is pressurized by a protective atmosphere;
preferably, the pressure of the first stage heat treatment is 1-3 MPa;
preferably, the first heat treatment is carried out for a period of 1 to 3 hours.
7. The method for treating waste positive electrode material according to claim 1, wherein in the second treatment stage, the amount of water vapor introduced and the weight ratio are 10-20% of the positive electrode active material in the waste positive electrode material: 1, a step of;
preferably, the second heat treatment is carried out for a period of 1 to 3 hours.
8. A method for repairing and regenerating a waste positive electrode material, which is characterized in that the method of any one of claims 1 to 7 is adopted to obtain lithium liquid and transition metal slag; and (3) obtaining a lithium source from the lithium liquid, and then mixing the lithium source with the transition metal slag to perform oxidation roasting to obtain the regenerated anode active material.
9. The method for repairing and regenerating a waste positive electrode material according to claim 8, wherein the lithium solution is subjected to evaporation treatment to obtain a lithium source, or the lithium solution is subjected to carbonization precipitation treatment to obtain the lithium source;
preferably, the transition metal slag is subjected to washing treatment in advance;
preferably, the washing process comprises a water washing and/or an alkaline washing process.
10. The method for repairing and regenerating a waste positive electrode material according to claim 9, wherein the temperature of the oxidizing and roasting stage is 600-800 ℃.
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