CN111129634A - Method for separating and recovering anode material of failed ternary lithium ion battery - Google Patents
Method for separating and recovering anode material of failed ternary lithium ion battery Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000010405 anode material Substances 0.000 title description 7
- 238000003756 stirring Methods 0.000 claims abstract description 65
- 239000007787 solid Substances 0.000 claims abstract description 53
- 238000001914 filtration Methods 0.000 claims abstract description 43
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 35
- 239000011812 mixed powder Substances 0.000 claims abstract description 33
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000011084 recovery Methods 0.000 claims abstract description 29
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 21
- 208000028659 discharge Diseases 0.000 claims abstract description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 14
- KYHBEXRLFUIPGF-UHFFFAOYSA-N CC(C(=NO)C)=NO.N Chemical compound CC(C(=NO)C)=NO.N KYHBEXRLFUIPGF-UHFFFAOYSA-N 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims abstract description 11
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 10
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 124
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 62
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 46
- 229910021529 ammonia Inorganic materials 0.000 claims description 30
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 21
- 239000000706 filtrate Substances 0.000 claims description 20
- 238000012360 testing method Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000012267 brine Substances 0.000 claims description 15
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 239000001099 ammonium carbonate Substances 0.000 claims description 13
- 239000011888 foil Substances 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000011889 copper foil Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 4
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims description 2
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 claims description 2
- JGUQDUKBUKFFRO-GGWOSOGESA-N (NE)-N-[(3E)-3-hydroxyiminobutan-2-ylidene]hydroxylamine Chemical compound O\N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-GGWOSOGESA-N 0.000 claims 6
- 239000012670 alkaline solution Substances 0.000 claims 2
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 20
- UNMGLSGVXHBBPH-BVHINDLDSA-L nickel(2+) (NE)-N-[(3E)-3-oxidoiminobutan-2-ylidene]hydroxylamine Chemical compound [Ni++].C\C(=N/O)\C(\C)=N\[O-].C\C(=N/O)\C(\C)=N\[O-] UNMGLSGVXHBBPH-BVHINDLDSA-L 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 15
- 239000003446 ligand Substances 0.000 abstract description 11
- 239000011656 manganese carbonate Substances 0.000 abstract description 10
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000011780 sodium chloride Substances 0.000 abstract description 3
- PUQISMCZEMAJKQ-UHFFFAOYSA-N N-(3-hydroxyiminobutan-2-ylidene)hydroxylamine nickel Chemical compound [Ni].CC(C(=NO)C)=NO PUQISMCZEMAJKQ-UHFFFAOYSA-N 0.000 abstract 1
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000004064 recycling Methods 0.000 description 16
- 239000011572 manganese Substances 0.000 description 14
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- -1 ammonium ions Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 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 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- VRBPDNIPYNKRCU-UHFFFAOYSA-N nickel;oxalic acid;hydrate Chemical compound O.[Ni].OC(=O)C(O)=O VRBPDNIPYNKRCU-UHFFFAOYSA-N 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910005581 NiC2 Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
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
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for separating and recovering a positive electrode material of a failed ternary lithium ion battery, which comprises the following steps: performing saline discharge treatment on the failed ternary lithium ion battery under gradient concentration, mechanically crushing, and then sorting to obtain positive and negative electrode mixed powder; stirring the mixed powder in an alkali solution, removing residual Al element, and adding the mixture into H2SO4Adding hydrogen peroxide, heating, stirring and filtering to remove graphite solid to obtain Li-containing material+、Ni2+、Co2+And Mn2+Solution I of (1); adding concentrated ammonia water and carbonate, stirring and filtering to obtain MnCO3Solid and Li-containing+、Ni2+And Co2+Solution II of (1); adding the dimethylglyoxime ammonia water complex ligand solution into the solution II, stirring and filtering to obtain dimethylglyoxime nickel solid and Li+And Co2+Solution III of (2); dissolving nickel dimethylglyoxime solid in oxalic acid, and filtering to obtain hydrated nickel oxalate solid; mixing a carbonate saltAdding the solution into the solution III, heating at low temperature, stirring and filtering to obtain CoCO3Heating, stirring and filtering the solid to obtain Li2CO3And (3) a solid. The invention has simple process, less waste water discharge, low cost and high recovery rate.
Description
Technical Field
The invention belongs to the technical field of recovery of spent lithium ion batteries, and particularly relates to a method for separating and recovering a spent ternary lithium ion battery anode material with a silicon-carbon cathode.
Background
With the rapid development of new energy product technology, the demand of lithium ion batteries is increasing in particular in the electronic industry and the new energy automobile industry. According to the gasoline coordination data, the sales volume of new energy automobiles in 2018 in China all the year is up to 125.6 thousands of automobiles, which is 16.8 times of the sales volume in 2014, and the sales volume is expected to reach 230 thousands of automobiles in 2020. The power battery enters a scale scrapping period from 2019, and the scrapping amount of the power battery is expected to reach 126GWH by 2025. The scrapped and failed ternary lithium ion battery contains various recyclable resources, such as valuable metals like nickel, cobalt, manganese, copper, aluminum and lithium, and materials like graphite. If the dead batteries cannot be properly processed in time, resource waste is caused, serious environmental pollution is caused, and even the life safety of people is harmed. Therefore, the green recovery of the failed lithium ion battery can not only generate certain economic benefit, but also obtain good environmental protection benefit.
In recent years, resource recovery of valuable metals in spent lithium ion batteries is becoming a hot spot of research in the recovery field. In the current mainstream recycling process, wet processing is widely applied because the recycled products have the characteristics of high purity and high added value. However, it should be noted that, in the wet treatment process, the discharge of "three industrial wastes" is large, and secondary pollution is easily caused. In the wet treatment process, the separation of the metal elements of nickel, cobalt and manganese is mostly carried out by adopting an organic solvent extraction method. In the extraction process, the organic extractant is volatile, and is harmful to the life health of plant operators. And a large amount of acid liquor is consumed for back extraction, so that the wastewater treatment cost is high, and the recovery cost is high directly.
The Chinese patent office discloses some recovery processing methods for the failed lithium ion battery, but the recovery methods have the following problems: 1) the recovered electrolyte is filtered and precipitated for multiple times, and then the dimethylglyoxime is added, so that the dimethylglyoxime cannot be completely dissolved in the feed liquid, the waste of the dimethylglyoxime is caused, and the production wastewater containing the dimethylglyoxime is generated; 2) sodium carbonate is added as a precipitator of metal ion lithium, so that a large amount of production wastewater containing sodium ions can be generated; 3) the filtrate is separated by extraction and rectification methods, a large amount of back extraction waste acid and waste alkali can be generated, and the rectification energy consumption and the recovery cost are high.
Therefore, there is a need to address the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for separating and recovering the anode material of the failed ternary lithium ion battery, which has the advantages of simple process, short process flow, low cost, high recovery rate, less wastewater discharge and capability of realizing industrial production.
The invention provides a method for separating and recovering a failure ternary lithium ion battery anode material, which comprises the following steps:
s1, performing saline discharge treatment on the failed ternary lithium ion battery under gradient concentration, and then performing mechanical crushing and sorting to obtain a battery shell, a diaphragm, a copper foil, an aluminum foil, electrolyte, and positive and negative electrode mixed powder;
s2, adding the separated positive and negative electrode mixed powder into an alkali solution for stirring, and removing residual Al element;
s3 adding the mixed powder of the anode and the cathode after Al removal to H with a certain concentration2SO4Adding a certain amount of hydrogen peroxide, heating and stirring for reaction for a period of time, filtering to remove insoluble graphite solid to obtain the productLi+、Ni2+、Co2+And Mn2+Solution I of (1);
s4 test for Mn in solution I2+Adding concentrated ammonia water, adding carbonate solution, stirring for reaction for a period of time, and filtering to obtain MnCO3Solid and Li-containing+、Ni2+And Co2+Solution II of (1);
s5, dissolving a certain amount of dimethylglyoxime in 25-28% ammonia water to obtain dimethylglyoxime ammonia water complex ligand solution, and testing Ni in the solution II2+Adding the dimethylglyoxime ammonia water complex ligand solution into the solution II to ensure that dimethylglyoxime and Ni are mixed2+Is 1:1, stirring the mixture to react, and filtering the mixture to obtain the nickel dimethylglyoxime solid containing Li+And Co2+Solution III of (2);
s6, stirring and dissolving the nickel dimethylglyoxime solid in the oxalic acid solution with the concentration of 0.2-1 mol/L, filtering to obtain hydrated nickel dimethylglyoxime solid, and recycling the dimethylglyoxime in the filtrate;
s7 testing Co in solution III2+And CO3 2—Adding carbonate solution into the solution III, heating and stirring at low temperature for a period of time, and filtering to obtain CoCO3Heating the filtrate, stirring while replenishing carbonate solution, and filtering to obtain Li2CO3And (3) a solid.
The invention has the following technical effects:
(1) the invention adopts the brine with gradient concentration to discharge, has thorough discharge and low cost, and can ensure the safe crushing of follow-up substances.
(2) According to the invention, 5-28% of concentrated ammonia water and dimethylglyoxime are combined to form the complex ligand, the dimethylglyoxime capable of precipitating nickel can be efficiently dissolved, and the dimethylglyoxime can be regenerated and recycled in situ after being dissolved by oxalic acid, so that the dimethylglyoxime can be recycled, the material cost used in recycling is effectively reduced, and other ion pollution sources cannot be introduced, thereby greatly reducing the wastewater generated by wet treatment, being beneficial to protecting the ecological environment and having high economic benefit.
(3) According to the invention, when the metal manganese, cobalt and lithium are recovered by precipitation, carbonate is used as a precipitator step by step, and the carbonate can be combined with different metal ions in sequence to form precipitation, so that the separation of the valuable metal nickel, cobalt, manganese and lithium of the anode is realized, the recovery rate is high, and simultaneously, the raw materials introduced in the recovery process of the invention are very few, and the invention can be repeatedly applied and recycled in the process, thereby further reducing the material cost used in the recovery process and being beneficial to environmental protection. The ammonium carbonate or ammonium bicarbonate can also be used for removing ammonium ions in the feed liquid after the metal elements are extracted by low-temperature heating, and the ammonia can also be recovered, so that the operation condition is mild, and the pollution to the surrounding environment is also avoided.
(4) The method overcomes the defects of large environmental pollution of an organic extractant, large consumption of back-extraction acid liquor, large wastewater treatment capacity and high recovery cost in the wet recovery method of the failure ternary lithium ion battery anode material in the prior art, has simple process in the whole recovery treatment process, shorter process flow, less added auxiliary materials in the reaction process, simple treatment of three wastes, energy conservation and environmental protection, is beneficial to industrialized large-scale production, meets the requirements of the current industry, and has very wide application prospect.
Drawings
FIG. 1 is a flow chart of a method of an embodiment of the present invention;
FIG. 2 is an XRD pattern of lithium carbonate obtained in example 1 of the present invention;
FIG. 3 is an XRD pattern of manganese carbonate obtained in example 1 of the present invention;
FIG. 4 is an XRD pattern of nickel oxalate hydrate obtained in example 1 of the present invention;
FIG. 5 is an XRD pattern of cobalt carbonate obtained in example 1 of the present invention;
FIG. 6 is a photograph and an XRD pattern of nickel precipitated from dimethylglyoxime according to example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, the method for separating and recovering the failed ternary lithium ion battery positive electrode material provided by the embodiment of the invention comprises the following steps:
s1, performing saline discharge treatment on the failed ternary lithium ion battery under gradient concentration, and then performing mechanical crushing and sorting to obtain a battery shell, a diaphragm, a copper foil, an aluminum foil, electrolyte, and positive and negative electrode mixed powder.
The step-concentration brine discharge treatment in the step is to put the failed ternary lithium ion battery into strong brine with the mass fraction of 5-10% for discharge treatment for 1-48 h, and then put into dilute brine with the mass fraction of 0.5-5% for discharge treatment for 1-48 h, so that the battery is fully discharged to the voltage below the safe crushing voltage (lower than 2V); and mechanically crushing and sorting the fully discharged battery to obtain a battery shell, a diaphragm, a copper foil, an aluminum foil, electrolyte, and positive and negative electrode mixed powder, wherein the battery shell, the diaphragm, the copper foil, the aluminum foil and the electrolyte can be directly recycled.
According to the process, the positive pole piece and the negative pole piece are not required to be separated, the positive and negative mixed powder is directly obtained, the subsequent recovery process can be completed, the discharge of the failed ternary lithium ion battery can be more thorough by adopting the discharge treatment of the brine under the gradient concentration, the safe crushing and disassembly of the subsequent physical method can be guaranteed, the potential safety hazard is avoided, the disassembly mode process is relatively simple, the disassembly time is short, the requirement on equipment is low, the disassembly cost and the complexity of the waste battery are reduced, and the industrial production of the disassembly mode can be realized.
S2, adding the separated positive and negative electrode mixed powder into the alkali solution to be stirred, and removing the residual Al element.
In the step, a small amount of aluminum foil still remains on the positive and negative electrode mixed powder after mechanical disassembly and separation, and if the aluminum foil is not removed, the phase and the performance of a subsequently recovered positive electrode material can be influenced, so that an alkali solution is added into the separated positive and negative electrode mixed powder to obtain NaAlO2The solution and the anode and cathode mixed powder after Al removal are used for removing the residual Al element in the anode and cathode mixed powder so as to ensure the purity of the recycled anode material.
Specifically, the alkali in the step is NaOH, the concentration range of the alkali solution added into the positive and negative electrode mixed powder is 1-5 mol/L, the molar ratio of the Al element content in the positive and negative electrode mixed powder to the alkali solution is 1-5: 1, and the ratio can ensure that Al in the positive and negative electrode mixed powder is completely removed in the reaction process of the positive and negative electrode mixed powder and the alkali solution. The step can be carried out at the temperature of 30-60 ℃, the anode and cathode mixed powder is quickly dissolved in the alkali solution through a stirrer, the stirring speed of the stirrer is 500-600 rpm, the stirring time is about 2-4 hours, the solid and the liquid in the solution are separated, and the Al element is recovered from the filtrate.
S3 adding the mixed powder of the anode and the cathode after Al removal to H with a certain concentration2SO4Adding a certain amount of hydrogen peroxide (H)2O2) Heating and stirring for reaction for a period of time to obtain a leaching solution, filtering to remove insoluble graphite solids to obtain Li-containing graphite+、Ni2+、Co2+And Mn2+Solution I of (1).
Because graphite is insoluble in acid, when the mixed powder of the anode and the cathode is placed in acid with certain concentration for dissolution, the active material Li of the anode can be separated out from the leached solution+、Ni2+、Co2+And Mn2+To obtain a solution containing Li+、Ni2+、Co2+And Mn2+So as to remove the graphite material insoluble in acid, thereby separating the graphite from the positive and negative electrode mixed powders. After being separated, the graphite can be placed in a ball mill, calcined at the high temperature of 600 ℃ under inert gas, annealed and recycled.
Method for leaching Li in positive and negative electrode mixed powder by sulfuric acid+、Ni2+、Co2+And Mn2+When the reaction is carried out, a small amount of H is added2O2As a reducing agent, the metal dissolution rate in the mixed powder of the positive electrode and the negative electrode can be accelerated. Concentration of sulfuric acid, heating temperature, stirring time, stirring rate, H2O2The amount of the sulfuric acid used directly affects the leaching rate of the metal ions, so that the concentration of the sulfuric acid in the step is 1.5-4 mol/L, and H is2O2In an amount of H2O2：H2SO41: 5-10 (volume ratio), the heating temperature is 70-100 ℃, the stirring time is 3-5 h, and the stirring speed is 500-700 rpm. The above parameter ranges ensure Li+、Ni2+、Co2+And Mn2+Has high leaching rate.
S4 test for Mn in solution I2+After the content of the component (A), firstly adding concentrated ammonia water into the solution I, then adding a carbonate solution, stirring and reacting for a period of time, and filtering to obtain MnCO3Solid and Li-containing+、Ni2+And Co2+Solution II of (1).
The carbonate solution in the step can be saturated ammonium carbonate or ammonium bicarbonate solution, and excessive concentrated ammonia water can be added quickly to ensure that Ni in the solution I2+And Co2+Fully complexing with ammonia without forming precipitate, and adding slightly excessive saturated ammonium carbonate or ammonium bicarbonate solution after 1 min-2 h to make Mn2+And CO3 2—In a molar ratio of Mn2+：CO3 2—1: 1-2, excess CO3 2—Can make Mn2+Fully form MnCO3Precipitation (but if CO is present)3 2—Excessive addition of the catalyst can produce CO with high concentration3 2—Production wastewater) to obtain MnCO3Controlling the pH value of the solution to be 9-11, and stirring for reaction for 0.5-3 h to ensure that MnCO can be obtained3The precipitation was substantially complete.
The specific reaction formula is as follows:
Ni2++Co2++10NH3·H2O＝[Ni(NH3)4]2++[Co(NH3)6]2++10H2O
s5, dissolving a certain amount of dimethylglyoxime in 25-28% of strong ammonia water to obtain dimethylglyoxime ammonia water complex ligand solution, and testing Ni in the solution II in the step S42+Then adding the dimethylglyoxime ammonia water complex ligand solution into the solution II to ensure that the dimethylglyoxime and Ni are mixed2+In a molar ratio of 1:1, stirring for reaction, and filtering to obtain nickel dimethylglyoxime Ni (DMG)2A solid, and containing Li+And Co2+Solution III of (4).
Specifically, the solid-to-liquid ratio of the dimethylglyoxime to the ammonia water complexing agent solution is 1g of dimethylglyoxime: 20ml to 500ml of ammonia water, and ultrasonically stirring for 1min to 2 h.
In the traditional method, the dimethylglyoxime is dissolved in organic solvents such as alcohol or ether and the like to be used for precipitating the nickel element, a large amount of industrial wastewater can be generated subsequently, and the wastewater treatment cost is high. The step utilizes the high-efficiency selectivity of the dimethylglyoxime to nickel ions, the dimethylglyoxime is completely dissolved in the strong ammonia water to form a complex ligand, and the dimethylglyoxime is dissolved by the aid of ultrasonic stirring, so that the high-efficiency utilization of the dimethylglyoxime is realized, and the full precipitation of the nickel ions can be ensured. After nickel is precipitated by the dimethylglyoxime and filtered, the feed liquid is heated and ammonia is evaporated, and the evaporated ammonia is introduced into an ammonia washing tower for ammonia recycling without discharging, so that the ammonia water can be recycled, and the recycling cost can be further reduced.
The specific reaction formula is as follows:
Ni2++2DMG＝Ni(DMG)2↓
s6, stirring and dissolving the solid nickel dimethylglyoxime in oxalic acid solution with the concentration of 0.2-1 mol/L, and filtering to obtain NiC2O4Solid, the dimethylglyoxime in the filtrate is recycled.
The oxalic acid adopted in the step can directly combine oxalate in oxalic acid and nickel in the nickel dimethylglyoxime into hydrated nickel oxalate without anion impurity ions, and impurities can be introduced by adopting other acid compounds.
The specific reaction formula is as follows:
Ni(DMG)2+C2H2O4+H2O＝2DMG+C2O4Ni·2H2O↓
s7 testing Co in solution III2+And CO3 2—Adding carbonate solution into the solution III, heating and stirring at low temperature for a period of time, and filtering to obtain CoCO3Heating the filtrate, stirring while replenishing carbonate solution, and filtering to obtain Li2CO3And (3) a solid.
Specifically, a carbonate solution was added to solution III to make Co2+And CO3 2—The molar ratio is 1: 1-1.5, then heating and stirring at the low temperature of 40-70 ℃ for 10 min-4 h, and filtering to obtain CoCO3After the solid is obtained, the filtrate is continuously heated to 71-100 ℃, stirred for 2-4 h and filtered to obtain Li2CO3And (5) solid, and introducing the ammonia distilled by heating into an ammonia washing tower for ammonia recycling.
The carbonate in the step is selected from ammonium carbonate or ammonium bicarbonate, and the carbonate is selected because the carbonate in the carbonate is combined with metal ions to generate precipitate, thereby being beneficial to the recovery of metal elements in the solution. Meanwhile, as the ammonium ions in the ammonium carbonate or ammonium bicarbonate are unstable and are easy to volatilize during heating, no other impurities are produced during the reaction process, no wastewater is produced, and the method is favorable for environmental protection.
This step Co2+And CO3 2—The molar ratio is 1:1 to 1.5, can ensure CO3 2—Excess of Co2+Can fully form CoCO3Precipitate, but if CO is present3 2—Excessive addition of the catalyst can produce CO with high concentration3 2—The production wastewater. The solution III is heated and stirred at the low temperature of 40-70 ℃ so as to evaporate ammonia in the feed liquid and break the complexation of ammonia and cobalt, and the dissociated Co2+With CO3 2—Combine to form CoCO3And (4) precipitating. Because the solubility of the lithium carbonate is in negative correlation with the temperature relationship, the cobalt is precipitated by ammonia distillation at the low temperature of 40-70 ℃, so that the influence of precipitation of the lithium carbonate on CoCO can be effectively avoided3The purity of (2). In Co2+After the precipitation is completely filtered, the temperature of the feed liquid is raised to 71-100 ℃, and the solubility of lithium carbonate is reduced, thereby being beneficial to a large amount of Li1+With CO3 2—Fast association to form Li2CO3And (4) precipitating.
The specific reaction formula is as follows:
Co2++CO3 2—＝CoCO3↓
in the step, because the ammonia water is unstable and volatile in heating, the evaporated ammonia can be introduced into the ammonia washing tower for ammonia recycling in two heating processes of low-temperature heating and stirring and heating and stirring at a high temperature without being discharged, so that the ammonia can be recycled, and the recovery cost is further reduced.
The specific reaction formula is as follows:
the present invention will be described in further detail with reference to examples.
Example 1:
s1, firstly, discharging the failed ternary lithium ion battery for 15 hours in strong brine with the mass fraction of 8%, then, discharging the failed ternary lithium ion battery for 36 hours in dilute brine with the mass fraction of 2%, so that the full discharge voltage of the battery is below the safe crushing voltage, then, mechanically crushing and sorting the fully discharged battery to obtain a battery shell, a diaphragm, copper foil, aluminum foil, electrolyte, positive and negative electrode mixed powder, and directly recycling the battery shell, the diaphragm, the copper foil, the aluminum foil and the electrolyte.
S2 adding 4g of the separated electrode powder into 2mol/L NaOH solution, heating to 45 ℃, stirring and reacting for 3 hours by a stirrer at 500rpm, and filtering. Adding seed crystal into the filtrate and recovering Al element.
S3 adding the positive and negative electrode mixed powder obtained by filtering after removing Al into 100mL of H with the concentration of 3mol/L2SO4Adding 10mL hydrogen peroxide slowly, heating to 90 deg.C, stirring in a stirrer at 600rpm for 4 hr to obtain leachate, filtering to remove insoluble graphite solid to obtain Li-containing solution+，Ni2+，Co2+And Mn2+Solution I of (1).
S4 test for Mn in solution I2+Adding excessive concentrated ammonia water, adding slightly excessive saturated ammonium carbonate solution after 60 min to obtain Mn2+：CO3 2—The solution was stirred for 1 hour at pH 10 (molar ratio) 1:1.3, filtered to obtain MnCO3Solid, and after Mn removalContaining Li+，Ni2+And Co2+Solution II of (1).
S5, dissolving 1.5g of dimethylglyoxime in 150mL of 28% concentrated ammonia water, adding ultrasonic treatment for 1 hour to completely dissolve dimethylglyoxime to obtain a dimethylglyoxime ammonia water complex solution, and testing Ni in a solution II2+Adding a proper amount of dimethylglyoxime ammonia water complex ligand solution into the solution II to ensure that dimethylglyoxime and Ni are mixed2+Is 1:1, stirring for reaction for 1 hour, filtering to obtain the nickel dimethylglyoxime solid and the Li-containing material+And Co2+Solution III of (4).
S6, dissolving the nickel dimethylglyoxime solid by using the oxalic acid solution stirring solution with the concentration of 0.5mol/L, filtering to obtain hydrated nickel dimethylglyoxime solid, and recycling the dimethylglyoxime in the filtrate.
S7 testing Co in solution III2+And CO3 2—Adding a proper amount of ammonium carbonate solution into the solution III, heating and stirring at the low temperature of 50 ℃ for 2 hours, and filtering to obtain CoCO3Solid, then will contain Li+Heating the filtrate to 95 deg.C, stirring, adding saturated ammonium carbonate solution, and hot filtering to obtain Li2CO3And (3) a solid. And introducing ammonia distilled out in the two processes of low-temperature heating and stirring and heating and stirring into an ammonia washing tower for ammonia recycling.
Through determination, the recovery rate of manganese and cobalt elements in the embodiment is more than 98%, the recovery rate of nickel elements is more than 99.5%, and the recovery rate of lithium elements is more than 97%.
As shown in fig. 2 to 5, in this example, characteristic peaks of lithium carbonate, manganese carbonate, nickel oxalate hydrate, cobalt carbonate, and nickel dimethylglyoxime are significant, and there is no impurity peak. The photograph of the solid nickel dimethylglyoxime shown in FIG. 6 showed a uniform pink color without other impure color impurities.
Example 2:
s1, firstly, discharging the failed ternary lithium ion battery for 5 hours in strong brine with the mass fraction of 10%, then, discharging the failed ternary lithium ion battery for 40 hours in dilute brine with the mass fraction of 1%, so that the full discharge voltage of the battery is below the safe crushing voltage, then, mechanically crushing and sorting the fully discharged battery to obtain a battery shell, a diaphragm, copper foil, aluminum foil, electrolyte, positive and negative electrode mixed powder, and directly recycling the battery shell, the diaphragm, the copper foil, the aluminum foil and the electrolyte.
S2 adding 4g of the separated electrode powder into 4mol/L NaOH solution, heating to 30 ℃, stirring and reacting for 4 hours at 550rpm of a stirrer, and filtering. Adding seed crystal into the filtrate and recovering Al element.
S3 adding the positive and negative electrode mixed powder obtained by filtering after removing Al into 100mL of H with the concentration of 3mol/L2SO4Adding 10mL hydrogen peroxide slowly, heating to 80 deg.C, stirring in a stirrer at 650rpm for 4.5 hr to obtain leachate, filtering to remove insoluble graphite solid to obtain Li-containing solution+，Ni2+，Co2+And Mn2+Solution I of (1).
S4 test for Mn in solution I2+Adding excessive concentrated ammonia water quickly, and adding slightly excessive saturated ammonium carbonate solution after 10 minutes to make Mn2+：CO3 2—The solution was stirred for 1.5 hours at pH 9.5 (molar ratio) and filtered to obtain MnCO3Solid, and Li-containing after Mn removal+，Ni2+And Co2+Solution II of (1).
S5, dissolving 1.5g of dimethylglyoxime in 160mL of 28% concentrated ammonia water, adding ultrasonic treatment for 1.5 hours to completely dissolve dimethylglyoxime to obtain a dimethylglyoxime ammonia water complex ligand solution, and testing Ni in a solution II2+Adding a proper amount of dimethylglyoxime ammonia water complex ligand solution into the solution II to ensure that dimethylglyoxime and Ni are mixed2+Is 1:1, stirring and reacting for 1.5 hours, filtering to obtain the nickel dimethylglyoxime solid and the Li-containing+And Co2+Solution III of (4).
S6, dissolving the nickel dimethylglyoxime solid by using the oxalic acid solution stirring solution with the concentration of 0.6mol/L, filtering to obtain hydrated nickel dimethylglyoxime solid, and recycling the dimethylglyoxime in the filtrate.
S7 testing Co in solution III2+And CO3 2—Adding a proper amount of ammonium carbonate solution into the solution III, heating and stirring at the low temperature of 60 ℃ for 2 hours, and filtering to obtain CoCO3Solid, then will contain Li+Heating the filtrate to 100 deg.C, stirring, adding saturated ammonium carbonate solution, and hot filtering to obtain Li2CO3And (3) a solid. And introducing ammonia distilled out in the two processes of low-temperature heating and stirring and heating and stirring into an ammonia washing tower for ammonia recycling.
Through determination, the recovery rate of manganese and cobalt elements in the embodiment is more than 98%, the recovery rate of nickel elements is more than 99%, and the recovery rate of lithium elements is more than 97%.
Example 3:
s1, firstly, discharging the failed ternary lithium ion battery for 24 hours in strong brine with the mass fraction of 8%, then, discharging the failed ternary lithium ion battery for 30 hours in dilute brine with the mass fraction of 4%, so that the full discharge voltage of the battery is below the safe crushing voltage, then, mechanically crushing and sorting the fully discharged battery to obtain a battery shell, a diaphragm, copper foil, aluminum foil, electrolyte, positive and negative electrode mixed powder, and directly recycling the battery shell, the diaphragm, the copper foil, the aluminum foil and the electrolyte.
S2 adding 4g of the separated electrode powder into 5mol/L NaOH solution, heating to 30 ℃, stirring and reacting for 3 hours by a stirrer at 500rpm, and filtering. Adding seed crystal into the filtrate and recovering Al element.
S3 adding the positive and negative electrode mixed powder obtained by filtering after removing Al into 100mL of H with the concentration of 3.5mol/L2SO4Adding 10mL hydrogen peroxide slowly, heating to 95 deg.C, stirring in a stirrer at 700rpm for 3 hr to obtain leachate, filtering to remove insoluble graphite solid to obtain Li-containing solution+，Ni2+，Co2+And Mn2+Solution I of (1).
S4 test for Mn in solution I2+Adding excessive concentrated ammonia water quickly, adding slightly excessive saturated ammonium bicarbonate solution after 30 minutes to ensure that Mn is added2+：CO3 2—The solution was stirred for 1 hour with the pH of 11 controlled at 1:1.3 (molar ratio), and filtered to obtain MnCO3Solid, and Li-containing after Mn removal+，Ni2+And Co2+Solution II of (1).
S5, dissolving 1.5g of dimethylglyoxime in 180mL of 28% concentrated ammonia water, adding ultrasonic treatment for 40min to completely dissolve dimethylglyoxime to obtain a dimethylglyoxime ammonia water complex solution, and testing Ni in a solution II2+Adding a proper amount of dimethylglyoxime ammonia water complex ligand solution into the solution II to ensure that dimethylglyoxime and Ni are mixed2+Is 1:1, stirring for reaction for 1 hour, filtering to obtain the nickel dimethylglyoxime solid and the Li-containing material+And Co2+Solution III of (4).
S6, dissolving the nickel dimethylglyoxime solid by using the oxalic acid solution stirring solution with the concentration of 0.7mol/L, filtering to obtain hydrated nickel dimethylglyoxime solid, and recycling the dimethylglyoxime in the filtrate.
S7 testing Co in solution III2+And CO3 2—Adding a proper amount of ammonium bicarbonate solution into the solution III, heating and stirring at the low temperature of 55 ℃ for 2 hours, and filtering to obtain CoCO3Solid, then will contain Li+The filtrate is continuously heated to 100 ℃, stirred and supplemented with a proper amount of saturated ammonium bicarbonate solution, and is filtered when the filtrate is hot to obtain Li2CO3And (3) a solid. And introducing ammonia distilled out in the two processes of low-temperature heating and stirring and heating and stirring into an ammonia washing tower for ammonia recycling.
Through determination, the recovery rate of manganese and cobalt elements in the embodiment is more than 98%, the recovery rate of nickel elements is more than 99%, and the recovery rate of lithium elements is more than 96.8%.
The above-described embodiments of the present invention are merely exemplary and not intended to limit the present invention, and those skilled in the art may make various modifications, substitutions and improvements without departing from the spirit of the present invention.
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Address after: C709-1, 7 / F, Institute of Tsinghua University, 019 Gaoxin South 7th Road, high tech Zone community, Yuehai street, Nanshan District, Shenzhen, Guangdong 518000 Patentee after: Shenzhen Qingyan Lithium Industry Technology Co.,Ltd. Address before: C709-1, 7 / F, Institute of Tsinghua University, 019 Gaoxin South 7th Road, high tech Zone community, Yuehai street, Nanshan District, Shenzhen, Guangdong 518000 Patentee before: Shenzhen Qingyan Equipment Technology Co.,Ltd. |