CN117778728A - Method for recycling heavy metal elements in waste ternary lithium batteries - Google Patents
Method for recycling heavy metal elements in waste ternary lithium batteries Download PDFInfo
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- CN117778728A CN117778728A CN202410007445.6A CN202410007445A CN117778728A CN 117778728 A CN117778728 A CN 117778728A CN 202410007445 A CN202410007445 A CN 202410007445A CN 117778728 A CN117778728 A CN 117778728A
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- active material
- ternary lithium
- acid leaching
- heavy metal
- acid
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 25
- 238000004064 recycling Methods 0.000 title claims description 10
- 238000002386 leaching Methods 0.000 claims abstract description 75
- 239000002253 acid Substances 0.000 claims abstract description 67
- 239000011149 active material Substances 0.000 claims abstract description 59
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000011780 sodium chloride Substances 0.000 claims abstract description 14
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000007599 discharging Methods 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 13
- 229930003268 Vitamin C Natural products 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 13
- 235000019154 vitamin C Nutrition 0.000 claims description 13
- 239000011718 vitamin C Substances 0.000 claims description 13
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 11
- 239000001630 malic acid Substances 0.000 claims description 11
- 235000011090 malic acid Nutrition 0.000 claims description 11
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 150000007522 mineralic acids Chemical class 0.000 abstract description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 abstract description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 abstract description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 2
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 2
- 239000004571 lime Substances 0.000 abstract description 2
- 239000008267 milk Substances 0.000 abstract description 2
- 210000004080 milk Anatomy 0.000 abstract description 2
- 235000013336 milk Nutrition 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 208000028659 discharge Diseases 0.000 description 15
- 239000011812 mixed powder Substances 0.000 description 9
- 150000007524 organic acids Chemical class 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000010405 anode material Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- NFDFQCUYFHCNBW-SCGPFSFSSA-N dienestrol Chemical group C=1C=C(O)C=CC=1\C(=C/C)\C(=C\C)\C1=CC=C(O)C=C1 NFDFQCUYFHCNBW-SCGPFSFSSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- -1 organic acid malic acid compound Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for recovering heavy metal elements in waste ternary lithium batteries, which comprises the following specific process flows: the preparation method comprises the steps of disassembling a ternary lithium battery, discharging in a NaCl solution, dividing the ternary lithium battery into mechanical crushing in an inert gas, mixing the mechanical crushing with the inert gas, performing high-temperature heat treatment to obtain a pretreated active material, placing the pretreated active material into a reaction kettle, performing primary acid leaching by dilute sulfuric acid to obtain a primary acid leached active material, granulating the primary acid leached active material, performing medium-temperature sintering, selecting inorganic acid and disulfide according to a certain proportion, constructing an acid leaching system, performing secondary acid leaching to obtain a secondary acid leached active material, adding lime milk into the secondary acid leached active material, filtering, evaporating and crystallizing to obtain the battery-level lithium sulfate.
Description
Technical Field
The invention relates to the technical field of lithium battery recovery, in particular to a method for recovering heavy metal elements in waste ternary lithium batteries.
Background
The ternary lithium battery material has the advantages of large discharge capacity, good cycle performance, good thermal stability, stable structure and the like, is one of the novel lithium ion battery positive electrode materials with the most development prospect at present, and the recovery of the waste ternary lithium battery material has great significance for environmental protection, and the heavy metal elements in the waste ternary lithium battery have higher recovery value, and the main methods of the current recovery comprise a dry method, a wet method and a biological method;
the dry recovery is to crush, screen and separate the waste lithium ion battery by a physical method, calcine the anode and cathode mixed powder at high temperature under high temperature, but the disadvantage is that the charge and discharge performance of the regenerated mixed material is obviously reduced after calcination, the wet recovery mainly adopts an acid leaching method, after acid leaching, cobalt and lithium in solution exist in ion form, but the higher concentration inorganic acid is leached, corresponding operation equipment is easy to corrode and acid liquid polluting the environment is easy to obtain, the biological method is to separate valuable metal elements from solid matters by utilizing microorganisms, but the microorganism leaching method has the disadvantages of difficult strain culture, difficult leaching solution separation and the like;
how to recycle heavy metal elements in waste ternary lithium batteries at high concentration is a technical problem to be solved.
Disclosure of Invention
The invention aims to provide a method for recovering heavy metal elements in waste ternary lithium batteries, which is characterized in that the pretreated positive and negative electrode materials are fully crushed and redundant materials in the batteries are removed through continuous pretreatment, and then continuous processes such as primary acid leaching, medium-temperature sintering, secondary acid leaching, evaporative crystallization and the like are carried out to construct different kinds of pickle liquor, so that heavy metal recovery liquid with higher purity is obtained, and the heavy metal recovery liquid can be used as other raw materials.
The aim of the invention can be achieved by the following technical scheme: a method for recycling heavy metal elements in waste ternary lithium batteries comprises the following steps:
a1, disassembling the ternary lithium battery, soaking the ternary lithium battery in NaCl solution for discharging and shearing to obtain a positive plate and a negative plate; then under the inert gas atmosphere, the positive plate and the negative plate are separated to be mechanically stirred, crushed and subjected to high-temperature heat treatment to obtain a pretreated active material;
the waste ternary lithium battery is placed in an inert gas atmosphere for mechanical crushing, so that not only can the toxic byproducts generated by electrolyte hydrolysis be effectively avoided, but also the waste ternary lithium battery and O can be prevented 2 The reaction takes place so that the risk of internal short-circuits is avoided. The anode and cathode materials of the waste ternary lithium battery are mixed, and the separation of the anode and cathode raw materials is not needed, so that the process is simplified.
A2, placing the pretreated active material into a reaction kettle, mixing and stirring with dilute sulfuric acid, and reacting to obtain an acid-mixed active material;
because the anode material and the cathode material are not separated, the anode material is a carbon material mainly comprising graphite, carbon dioxide gas is released, and the carbon dioxide gas is discharged through an exhaust pipeline of the reaction kettle, so that gas pollution is avoided.
A3, granulating the active material subjected to primary acid leaching, standing for aging, sintering at medium temperature, taking out, and cooling to room temperature in a nitrogen atmosphere. PVDF and graphite in the anode material can be removed through medium-temperature sintering, and the cathode graphite material can be further removed, so that the purity of the active material after primary acid leaching is improved.
A4, mixing, soaking and filtering the active material mixed by the acid and the acid leaching system to obtain acid leaching solution;
a5, adding lime milk into the pickle liquor, filtering to obtain filtrate, and evaporating and crystallizing to obtain battery-grade lithium sulfate;
the acid leaching system comprises the following steps: the vitamin C-containing beverage is prepared by mixing, by weight, 2-10 parts of vitamin C, 2-10 parts of malic acid, 1-3 parts of disulfide and 20 parts of ethanol.
The acid leaching system consists of an organic acid and a disulfide with a reducing disulfide bond. The organic acid is obtained by mixing malic acid with small molecular weight, organic acid vitamin C with reducibility and aliphatic disulfide with dynamic covalent bonds. The organic acid vitamin C is taken as an acidic polyhydroxy compound, and adjacent enol hydroxy groups are easy to be dissociated to release H+, so that the vitamin C has an acid form. The dienol structure of the catalyst is easily oxidized into a diketone structure, so that Co after high-temperature calcination is obtained 3+ Reduction to Co 2+ The organic acid is more easily complexed, so that the acid leaching rate of each metal element is improved.
Further, the discharging step specifically includes: and immersing the disassembled ternary lithium battery in 20g/L NaCl solution to discharge for 6-10h.
The waste ternary lithium battery is scrapped, but still a part of electric quantity remains, if the waste ternary lithium battery is directly disassembled without releasing the residual electric quantity, the explosion risk exists, and the ternary lithium battery is subjected to discharge treatment in advance. The sodium chloride conductive solution is utilized to carry out short-circuit discharge, so that a large amount of heat generated in the discharge process can be absorbed by the salt solution at the same time, and the danger caused by high temperature is avoided.
Further, the concentration of the dilute sulfuric acid in the A2 is 10-20%wt, and the mass ratio of the pretreated active material to the dilute sulfuric acid is 0.1:1.
Further, in A3, the medium temperature sintering temperature is 500-600 ℃ and the sintering time is 100-200min. In the middle-temperature sintering process, impurities in the anode material and the cathode material, including carbon materials such as graphite and the like, can be further removed. In this process, valuable metal elements are also all oxidized to the highest value.
Further, in the A4, the concentration of the acid leaching system is 2-5mol/L, and the active material after primary acid leaching and the acid leaching system are mixed according to the solid-to-liquid ratio of 5 g/L.
Further, the leaching temperature is 70-80 ℃ and the leaching time is 70-90min.
The invention has the following beneficial effects:
1. according to the invention, firstly, the waste ternary lithium battery is subjected to pretreatment such as salt solution discharge, high-temperature heat treatment and the like, and then, the acid leaching process is adopted twice, so that the extraction efficiency of heavy metal elements in the ternary lithium battery is improved. The conventional pretreatment of ternary lithium batteries by concentrated sulfuric acid can cause corrosion to equipment due to overhigh concentration of inorganic acid and release SO at the same time 3 Toxic gas pollutants, and the leached waste liquid is difficult to treat, and can also form potential hazard to human bodies and the environment. The invention adopts dilute sulfuric acid with the concentration of 10-20%wt to carry out acid leaching, provides an acidification environment in advance, overcomes the defect of lower acidity of the mixed inorganic acid in the later stage, can oxidize the anode material, and can remove impurity materials by adopting only medium-temperature sintering in the later sintering process.
2. In the secondary acid leaching process, an acid leaching system with a certain proportion is adopted. The organic acid malic acid compound comprises small molecule organic acid malic acid, vitamin C with a reducing group and an aliphatic disulfide bond compound with a dynamic repair bond. Disulfide bonds act as dynamic covalent bonds, utilizing hydrogen bonding in organic acids, by reversibly forming thiols and thio groups, thereby forming disulfides. The acid leaching system of the invention is doped with a small amount of aliphatic disulfide bond compound, thus being capable of timely mixing Co 3+ Reduction to Co 2+ The organic acid is used for capturing the complex Co 2+ Thereby improving the leaching rate of each heavy metal element, and preparing the battery-grade lithium sulfate through a post-evaporation crystallization process.
Drawings
FIG. 1 shows the reduction of Co by C in the microorganism of the present invention 3+ Is a reaction schematic diagram of (2);
FIG. 2 is a diagram showing the reaction scheme of complex cyclization of heavy metal elements such as Li, co and Ni with malic acid in the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1. Removing plastic outer packages from waste ternary lithium batteries, placing the waste ternary lithium batteries in a container, adding 20g/L NaCl solution into the container, immersing the ternary lithium batteries in the NaCl solution, sealing a film on the container, and placing the container in a ventilation primary cabinet for discharge treatment; wherein the discharge time is 6-10h; shearing the anode and cathode links and overcharging protection devices in the inert gas atmosphere to obtain an anode plate and a cathode plate; then the positive plate and the negative plate are separated and mechanically stirred, crushed to 40 meshes and mixed to obtain mixed powder; and (3) carrying out high-temperature heat treatment on the mixed powder to separate the positive plate from the negative plate and the current collector aluminum foil, and simultaneously removing the binder and the conductive agent to obtain the pretreated active material.
2. The pretreated active material is put into a reaction kettle, and the pretreated active material and 10 percent by weight of dilute sulfuric acid are mixed according to the mass ratio of 0.1:1 at normal temperature, and are mixed and stirred at 300r/min for reaction for 2 hours to obtain the active material after primary acid leaching; wherein the generated CO 2 And discharging from an air outlet pipeline of the reaction kettle.
3. Granulating the active material subjected to primary acid leaching by using a granulating machine, wherein the average particle size of the active material is 2mm; standing and aging in a constant temperature and humidity environment, wherein the temperature is 25 ℃ and the aging time is 24 hours; aging, and then placing the mixture in a roasting furnace in a nitrogen atmosphere to perform a medium-temperature sintering reaction, wherein the sintering temperature is 500 ℃; and then taken out, and cooled to room temperature under a nitrogen atmosphere.
4. 2 parts of vitamin C, 2 parts of malic acid, 1 part of aromatic disulfide and 20 parts of ethanol are mixed according to parts by weight to construct an acid leaching system; mixing, impregnating and filtering the active material subjected to primary acid leaching and an acid leaching system according to a solid-to-liquid ratio of 1g/L to obtain an active material subjected to secondary acid leaching; wherein the leaching temperature is 75 ℃ and the leaching time is 70min.
5. Evaporating, concentrating and crystallizing the active material after the secondary acid leaching to obtain heavy metal concentrated solution.
Example 2
1. Removing plastic outer packages from waste ternary lithium batteries, placing the waste ternary lithium batteries in a container, adding 20g/L NaCl solution into the container, immersing the ternary lithium batteries in the NaCl solution, sealing a film on the container, and placing the container in a ventilation primary cabinet for discharge treatment; wherein the discharge time period is 8h. Then, under the atmosphere of inert gas, the ternary lithium battery is disassembled, and a positive plate and a negative plate are obtained by shearing, connecting an internal positive electrode and a negative electrode and overcharging the protective device; then the positive plate and the negative plate are separated and mechanically stirred, crushed to 50 meshes and mixed to obtain mixed powder; and (3) carrying out high-temperature heat treatment on the mixed powder to separate the positive plate from the negative plate and the current collector aluminum foil, and simultaneously removing the binder and the conductive agent to obtain the pretreated active material.
2. Placing the pretreated active material into a reaction kettle, mixing the pretreated active material with 14% by weight of dilute sulfuric acid according to the mass ratio of 0.1:1 at normal temperature, mixing and stirring at 304r/min, reversing for 3 hours, and filtering to obtain an active material after primary acid leaching; wherein the generated CO 2 And discharging from an air outlet pipeline of the reaction kettle.
3. Granulating the active material subjected to primary acid leaching by using a granulating machine, wherein the average particle size of the active material is 3mm; standing and aging in a constant temperature and humidity environment, wherein the temperature is 30 ℃ and the aging time is 24 hours; aging, and then placing the mixture in a roasting furnace in a nitrogen atmosphere to perform a medium-temperature sintering reaction, wherein the sintering temperature is 705 ℃; and then taken out, and cooled to room temperature under a nitrogen atmosphere.
4. According to the weight parts, 5 parts of vitamin C, 5 parts of malic acid, 1 part of aromatic disulfide and 20 parts of ethanol are mixed to obtain an acid leaching system; mixing, impregnating and filtering the active material subjected to primary acid leaching and an acid leaching system according to a solid-to-liquid ratio of 3g/L to obtain an active material subjected to secondary acid leaching; wherein the leaching temperature is 70-80deg.C, and the leaching time is 75min.
5. Evaporating, concentrating and crystallizing the active material after the secondary acid leaching to obtain heavy metal concentrated solution.
Example 3
1. Removing plastic outer packages from waste ternary lithium batteries, placing the waste ternary lithium batteries in a container, adding 20g/L NaCl solution into the container, immersing the ternary lithium batteries in the NaCl solution, sealing a film on the container, and placing the container in a ventilation primary cabinet for discharge treatment; wherein the discharge duration was 7h. Then, under the atmosphere of inert gas, the ternary lithium battery is disassembled, and a positive plate and a negative plate are obtained by shearing, connecting an internal positive electrode and a negative electrode and overcharging the protective device; then the positive plate and the negative plate are separated and mechanically stirred, crushed to 54 meshes and mixed to obtain mixed powder; and (3) carrying out high-temperature heat treatment on the mixed powder to separate the positive plate from the negative plate and the current collector aluminum foil, and simultaneously removing the binder and the conductive agent to obtain the pretreated active material.
2. The pretreated active material is put into a reaction kettle, the pretreated active material and 16 percent by weight of dilute sulfuric acid are mixed according to the mass ratio of 0.1:1 at normal temperature, mixed and stirred at 325r/min for reaction for 4 hours, and then the active material after primary acid leaching is obtained after filtration; wherein the generated CO 2 And discharging from an air outlet pipeline of the reaction kettle.
3. Granulating the active material subjected to primary acid leaching by using a granulating machine, wherein the average particle size of the active material is 3mm; standing and aging in a constant temperature and humidity environment, wherein the temperature is 32 ℃ and the aging time is 24 hours; aging, and then placing the mixture in a roasting furnace in a nitrogen atmosphere to perform a medium-temperature sintering reaction, wherein the sintering temperature is 750 ℃; and then taken out, and cooled to room temperature under a nitrogen atmosphere.
4. According to the weight parts, 7 parts of vitamin C, 7 parts of malic acid, 3 parts of aromatic disulfide, 3 parts of thiuram disulfide and 20 parts of ethanol are mixed to construct an acid leaching system; mixing, impregnating and filtering the active material subjected to primary acid leaching and an acid leaching system according to a solid-to-liquid ratio of 7g/L to obtain an active material subjected to secondary acid leaching; wherein the leaching temperature is 73 ℃ and the leaching time is 83min.
5. Evaporating, concentrating and crystallizing the active material after the secondary acid leaching to obtain heavy metal concentrated solution.
Example 4
1. Removing plastic outer packages from waste ternary lithium batteries, placing the waste ternary lithium batteries in a container, adding 20g/L NaCl solution into the container, immersing the ternary lithium batteries in the NaCl solution, sealing a film on the container, and placing the container in a ventilation primary cabinet for discharge treatment; wherein the discharge time period is 10h. Then, under the atmosphere of inert gas, the ternary lithium battery is disassembled, and a positive plate and a negative plate are obtained by shearing, connecting an internal positive electrode and a negative electrode and overcharging the protective device; then the positive plate and the negative plate are separated and mechanically stirred, crushed to 60 meshes and mixed to obtain mixed powder; and (3) carrying out high-temperature heat treatment on the mixed powder to separate the positive plate from the negative plate and the current collector aluminum foil, and simultaneously removing the binder and the conductive agent to obtain the pretreated active material.
2. Placing the pretreated active material into a reaction kettle, mixing the pretreated active material with 20 wt% of dilute sulfuric acid according to the mass ratio of 0.1:1 at normal temperature, mixing and stirring at 300r/min, reacting for 4 hours, and filtering to obtain the active material after primary acid leaching; wherein the generated CO 2 And discharging from an air outlet pipeline of the reaction kettle.
3. Granulating the active material subjected to primary acid leaching by using a granulating machine, wherein the average particle size of the active material is 3mm; standing and aging in a constant temperature and humidity environment, wherein the temperature is 40 ℃ and the aging time is 24 hours; aging, and then placing the mixture in a roasting furnace in a nitrogen atmosphere to perform a medium-temperature sintering reaction, wherein the sintering temperature is 800 ℃; and then taken out, and cooled to room temperature under a nitrogen atmosphere.
4. 10 parts of vitamin C, 10 parts of malic acid, 3 parts of aromatic disulfide and 20 parts of ethanol are mixed according to parts by weight to construct an acid leaching system; mixing vitamin C, malic acid, aliphatic disulfide and ethanol to construct an acid leaching system, mixing and soaking the active material subjected to primary acid leaching and the acid leaching system according to a solid-to-liquid ratio of 10g/L, and filtering to obtain an active material subjected to secondary acid leaching; wherein the leaching temperature is 75 ℃ and the leaching time is 90min.
5. Evaporating, concentrating and crystallizing the active material after the secondary acid leaching to obtain heavy metal concentrated solution.
The foregoing is merely illustrative and explanatory of the invention, as it is well within the scope of the invention as claimed, as it relates to various modifications, additions and substitutions for those skilled in the art, without departing from the inventive concept and without departing from the scope of the invention as defined in the accompanying claims.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (7)
1. The method for recycling the heavy metal elements in the waste ternary lithium battery is characterized by comprising the following steps of:
a1, disassembling the ternary lithium battery, soaking the ternary lithium battery in NaCl solution for discharging and shearing to obtain a positive plate and a negative plate; then under the inert gas atmosphere, the positive plate and the negative plate are separated to be mechanically stirred, crushed and then mixed, and the active material after pretreatment is obtained through high-temperature heat treatment;
a2, placing the pretreated active material into a reaction kettle, mixing and stirring with dilute sulfuric acid, and reacting to obtain an active material subjected to primary acid leaching;
a3, granulating the active material subjected to primary acid leaching, standing for ageing, sintering at medium temperature, taking out, and cooling to room temperature in a nitrogen atmosphere.
A4, mixing, impregnating and filtering the active material subjected to the primary acid leaching with an acid leaching system to obtain an active material subjected to the secondary acid leaching;
a5, evaporating, concentrating and crystallizing the active material subjected to the secondary acid leaching to obtain heavy metal concentrated solution;
the acid leaching system comprises the following steps: the vitamin C is prepared by mixing 2-10 parts by weight of vitamin C, 2-10 parts by weight of malic acid, 1-3 parts by weight of disulfide and 20 parts by weight of ethanol.
2. The method for recycling heavy metal elements in waste ternary lithium batteries according to claim 1, wherein the discharging step is specifically: and immersing the disassembled ternary lithium battery in 20g/L NaCl solution to discharge for 6-10h.
3. The method for recycling heavy metal elements in waste ternary lithium batteries according to claim 1, wherein the concentration of dilute sulfuric acid in the A2 is 10-20% wt, and the mass ratio of the pretreated active material to the dilute sulfuric acid is 0.1:1.
4. The method for recycling heavy metal elements in waste ternary lithium batteries according to claim 1, wherein in the A3, the medium-temperature sintering temperature is 500-600 ℃, and the sintering time is 100-200min.
5. The method for recycling heavy metal elements in waste ternary lithium batteries according to claim 1, wherein in A4, the active material after primary acid leaching and the acid leaching system are mixed according to a solid-to-liquid ratio of 1-5 g/L.
6. The method for recycling heavy metal elements in waste ternary lithium batteries according to claim 1, wherein the leaching temperature is 70-80 ℃ and the leaching time is 70-90min.
7. The method for recycling heavy metal elements in waste ternary lithium batteries according to claim 1, wherein in the A5, disulfide is any one of aromatic disulfide, aliphatic disulfide or thiuram disulfide.
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