CN114665182B - Method for separating and recycling current collector and negative electrode material in negative electrode of waste lithium ion battery - Google Patents
Method for separating and recycling current collector and negative electrode material in negative electrode of waste lithium ion battery Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 32
- 238000004064 recycling Methods 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 90
- 238000000926 separation method Methods 0.000 claims abstract description 63
- 238000011282 treatment Methods 0.000 claims abstract description 47
- 238000011084 recovery Methods 0.000 claims abstract description 45
- 239000004094 surface-active agent Substances 0.000 claims abstract description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 7
- 238000010494 dissociation reaction Methods 0.000 claims abstract description 6
- 230000005593 dissociations Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003093 cationic surfactant Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- -1 alcohol ether carboxylate Chemical class 0.000 claims description 5
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 4
- 239000002280 amphoteric surfactant Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 3
- 125000005227 alkyl sulfonate group Chemical group 0.000 claims description 2
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 claims description 2
- 229940073507 cocamidopropyl betaine Drugs 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- 229910019142 PO4 Chemical group 0.000 claims 1
- 239000010452 phosphate Chemical group 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 33
- 239000011889 copper foil Substances 0.000 description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000010439 graphite Substances 0.000 description 14
- 229910002804 graphite Inorganic materials 0.000 description 14
- 238000012216 screening Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
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- 239000000853 adhesive Substances 0.000 description 3
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- 238000007599 discharging Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010850 salt effect Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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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
-
- 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
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for separating and recycling a current collector and a negative electrode material in a negative electrode of a waste lithium ion battery. The separation and recovery method comprises the following steps: the method comprises the steps of enabling a negative electrode of a waste lithium ion battery to be in contact with stripping liquid, and applying mechanical stirring and/or ultrasound to carry out dissociation treatment so as to enable a negative electrode material in the negative electrode of the waste lithium ion battery to be dissociated from a current collector, wherein the negative electrode material is dispersed in the stripping liquid to form mixed liquid, and the stripping liquid contains a surfactant; separating the current collector from the mixed liquid and separating the current collector from the mixed liquid to obtain a negative electrode material and a separation liquid; and (3) carrying out precipitation treatment on the separation liquid by adopting a lithium ion precipitant to obtain a treatment liquid and lithium salt, and recycling the treatment liquid as the stripping liquid. The separation and recovery method provided by the invention is environment-friendly, efficient and low in cost, and meanwhile, the recycling times of the stripping liquid are greatly improved, the discharge of waste liquid is reduced, and the cost and the environmental pollution are further reduced.
Description
Technical Field
The invention relates to the technical field of resource classification recovery and reuse, in particular to a method for separating and recovering a current collector and a negative electrode material in a negative electrode of a waste lithium ion battery.
Background
As a new type of secondary battery, lithium ion batteries are widely used in various energy storage fields due to their advantages. With the rapid development of new energy industry, the sales volume of lithium ion power batteries is increased, but the service life of lithium ion batteries is limited due to the technical limitation, a large number of waste lithium ion batteries are required to be generated in the future, and the recovery volume of the waste lithium ion batteries in 2022 China is expected to reach 42.2 ten thousand tons. The waste lithium ion battery has the dual properties of resource value and environmental hazard, so that the valuable components in the waste lithium ion battery are reasonably and efficiently recycled and utilized. Many current researches focus on the separation of the anode electrode material and the current collector of the waste lithium ion battery and the recovery of organic metal, and less attention is paid to the recovery of the stripping agent of the anode. The current collector, such as copper foil, in the negative electrode of the waste lithium ion battery has a content of about 5-9%, and has a high recovery value. However, since the negative electrode of the lithium ion battery is manufactured by adding a binder (styrene-butadiene rubber and carboxymethyl cellulose) to bond the negative electrode material, such as graphite, to the copper foil, separation of the current collector copper foil and the negative electrode material must be achieved before the copper foil is recovered.
The existing separation technology mainly adopts the methods of water washing, solvent soaking, acid washing, crushing, winnowing and the like to realize the separation and recovery of the copper foil and the graphite.
For example, chinese patent (CN 103985919B) discloses that the negative electrode sheet obtained after the discharge and disassembly of the waste lithium ion battery is subjected to a heating, stirring and cleaning process in a mixed solution of ethanol and water, and the screened material is copper foil after screening and drying, and the screened material is subjected to suction filtration and drying at 70-90 ℃ to obtain graphite. The method has small treatment capacity, the ethanol can volatilize in the treatment process, the loss is large, and the tail liquid treatment is required to be additionally carried out. Chinese patent (CN 108365287A) discloses that the negative electrode of the waste lithium ion battery is separated from the copper foil of the current collector by adopting a supercritical fluid solvent in a reaction kettle at a certain temperature and under a certain pressure, and the separation efficiency of the final copper foil reaches 94.68 percent. The final separation efficiency of the method is low, the pressure of the reaction kettle in the separation process reaches 10-12MPa, the requirement on equipment is high, and the treatment cost is high. Chinese patent (CN 103474721B) puts the waste lithium battery negative plate into water solution, manually washes the negative plate or stirs for a certain time, then takes out the copper foil, filters to obtain graphite and conductive agent, adds Na 2CO3 solution with a certain concentration into the filtrate under a certain condition to precipitate and recycle Li 2CO3 product. However, the method has the disadvantages of rough separation process of the copper foil and the electrode material, low separation efficiency, high manual treatment cost and incapability of large-scale application. Chinese patent (CN 105304967B) pulverizes the waste lithium battery negative electrode plate to below 20 μm by using a superfine pulverizer, then obtains coarse copper powder and coarse graphite powder with different densities by using a cyclone separator, then obtains copper powder with the purity of 99.9% by separating the coarse copper powder by cyclone for multiple times, and obtains graphite powder by acid dissolution, centrifugation and drying of the coarse graphite powder. Although copper powder with higher purity is obtained by the method, the loss rate of the copper foil in the crushing and multiple cyclone separation processes is too high, and part of copper powder is dissolved and lost along with the graphite powder acid treatment process, so that the recovery rate of the copper foil is lower, and the whole process is complex.
Summarizing, the existing separation and recovery method of the lithium battery cathode has the following problems: (1) The stripping agent has higher price and higher loss, and the acid-base solvent can corrode equipment to generate toxic and harmful gas, so that a wastewater treatment system or a tail gas treatment device is required to be installed, and the process cost is higher; (2) The separation process has higher requirements on equipment, causes larger loss in order to achieve higher copper foil purity, has low separation efficiency and low treatment capacity; (3) The negative plate is crushed at the initial stage of the process to mix the graphite and the copper foil, so that the subsequent separation difficulty is increased, and the recovery process is complicated; (4) The prior art cannot realize the separation and recovery of the low-cost and environment-friendly separation and recovery by recycling the stripping liquid while separating and recovering the collected fluid and the anode material with high efficiency and high yield.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for separating and recycling a current collector and a negative electrode material in a negative electrode of a waste lithium ion battery.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the invention provides a method for separating and recycling current collector and negative electrode material in a negative electrode of a waste lithium ion battery, which comprises the following steps:
1) Contacting a negative electrode of a waste lithium ion battery with stripping liquid, and applying mechanical stirring and/or ultrasonic to carry out dissociation treatment so as to dissociate a negative electrode material in the negative electrode of the waste lithium ion battery from a current collector, wherein the negative electrode material is dispersed in the stripping liquid to form a mixed liquid, and the stripping liquid contains a surfactant;
2) Separating the current collector from the mixed liquid and separating the current collector from the mixed liquid to obtain a negative electrode material and a separation liquid;
3) And (3) carrying out precipitation treatment on the separation liquid by adopting a lithium ion precipitant to obtain a treatment liquid and lithium salt, and recycling the treatment liquid as the stripping liquid.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that:
the method for separating and recycling the current collector and the negative electrode material in the waste lithium ion battery negative electrode provided by the invention has the advantages that a large amount of organic solvents, high-temperature heating and other treatment means with high pollution or high energy consumption are not applied, the current collector and the negative electrode material can be separated and recycled with high efficiency and high recycling rate by only using the environment-friendly, easy-to-use and environment-friendly surfactant, the recycling frequency of stripping liquid is greatly increased, the cost of separation and recycling is reduced, and the discharge of waste liquid is reduced.
The above description is only an overview of the technical solutions of the present application, and in order to enable those skilled in the art to more clearly understand the technical means of the present application, the present application may be implemented according to the content of the specification, and the following description is given of the preferred embodiments of the present application with reference to the detailed drawings.
Drawings
Fig. 1 is a schematic flow chart of a method for separating and recovering a current collector from a negative electrode material in a negative electrode of a waste lithium ion battery according to an exemplary embodiment of the invention.
Detailed Description
In view of the shortcomings in the prior art, the inventor of the present invention has long studied and practiced in a large number of ways to propose the technical scheme of the present invention. The technical scheme, the implementation process, the principle and the like are further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
Referring to fig. 1, an embodiment of the invention provides a method for separating and recovering a current collector and a negative electrode material in a negative electrode of a waste lithium ion battery, which comprises the following steps:
1) And enabling the negative electrode of the waste lithium ion battery to be in contact with stripping liquid, and applying mechanical stirring and/or ultrasonic to carry out dissociation treatment so as to dissociate the negative electrode material in the negative electrode of the waste lithium ion battery from the current collector, wherein the negative electrode material is dispersed in the stripping liquid to form mixed liquid, and the stripping liquid contains a surfactant.
2) And separating the current collector from the mixed liquid to obtain a negative electrode material and a separation liquid.
3) And (3) carrying out precipitation treatment on the separation liquid by adopting a lithium ion precipitant to obtain a treatment liquid and lithium salt, and recycling the treatment liquid as the stripping liquid.
The waste lithium ion battery negative electrode can be obtained by disassembling an aged lithium ion battery, can also be negative electrode piece scraps and the like during the production of the lithium ion battery, and is mainly derived from the fields of waste electronic products, waste power automobiles, scraps and the like generated in the production process of battery negative electrodes. The lithium ion battery may be, for example, a lithium cobalt oxide, lithium manganate, lithium iron phosphate, nickel cobalt manganese (ternary) type lithium ion battery; it can be understood that when the lithium ion battery is disassembled, the lithium ion battery needs to be fully discharged, and the discharging mode can be soaking by using conductive liquid, discharging by using special discharging equipment, and the like, and the disassembly can be manual disassembly or automatic disassembly such as mechanical breaking.
The above step numbers are only for labeling, and do not mean a specific implementation sequence, for example, according to different processing amounts and process selections, the steps 1), 2), and 3) may be selected to be continuously circulated according to the technical concept of the present invention, or the steps 1) and 2) may be selected to be circulated for a certain number of times (i.e., the separation solution in the step 2 is used as the stripping solution to continue to use for several small cycles, and then the step 3 is performed to perform the large cycle, thereby forming a plurality of groups of cycles.
The inventor of the invention finds in long-term practice that lithium ions carried by a negative electrode material inevitably enter stripping liquid in the separation process, after the circulation times are increased or after the primary treatment capacity is large, the dissolution of the binder on the surface of the negative electrode sheet is affected when the concentration of the lithium ions reaches a certain concentration, because the premise of separation is that the binder is dissolved into liquid, from the perspective of a solution dissolution system, the two substances cannot react with each other, but as the ion concentration of one substance in the solution system is increased, the molecular gap is reduced, the dissolution capacity is negatively affected, and the circulation capacity of the stripping liquid is further affected. Therefore, the inventor provides the technical scheme of the invention, and the lithium ion precipitant is required to be dripped after a period of circulation to precipitate lithium ions in the lithium ion precipitant, so that impurity ions in the lithium ion precipitant are reduced, and high separation efficiency is ensured, thereby realizing large recycling times.
In some prior art, although the recycling of the liquid is also involved, the purpose of adding the lithium ion precipitant is to recover lithium in the liquid, not to increase the recycling times of the liquid, the mechanical force is utilized to separate the anode material, the stripping action of the surfactant is not utilized, the used liquid only plays a role of an intermediate carrier for recovering lithium ions, and the problem of activity reduction of the stripping agent such as the surfactant in the liquid is not involved; in other words, even if the lithium ions are not precipitated, the stripping effect of the liquid during the recycling is not affected, and only the continuous dissolution and recovery of the lithium ions in the negative electrode after the treatment are affected; this is significantly different from the inventive concept of the present invention.
As a typical application example, referring to fig. 1, the waste lithium ion battery is disassembled to obtain a negative plate or negative electrode leftover materials generated in the process of producing and coating the negative electrode of the battery are taken as raw materials, surfactants with different concentrations are mixed with diluted ethanol solution to be taken as stripping solution, and the mixture of the oversize material current collector and the undersize graphite is obtained by heating and stirring or ultrasonic treatment in the stripping solution with a certain concentration and then screening. And washing the oversize material, and drying at a certain temperature to obtain the current collector copper foil. The undersize is centrifugally separated and dried to obtain negative black powder, and centrifugal liquid (namely, one situation of the separating liquid is the same as the situation) is circularly treated for multiple times, so that the efficiency of the separating agent is reduced due to the fact that the molecular gaps in the solution are reduced, lithium ions in the separating agent are precipitated by using a lithium ion precipitating agent, and the separating agent is recovered in a lithium ion precipitation mode.
The advantages of the exemplary scheme described above are: (1) environmental protection. The used surfactant stripping agent has biodegradability, has small influence on environment, and does not produce wastewater discharge in the whole process. (2) advanced technology. The whole process consists of simple physical procedures such as ultrasonic or mechanical stirring washing, screening, centrifuging, drying and the like, and is simple, but the recovery efficiency and the product purity of the separated copper foil reach higher indexes. (3) is suitable for continuous industrial production. Compared with the prior art, the process can obtain larger treatment capacity only by larger equipment volume, the influence of the increased treatment capacity on the separation efficiency and purity of the copper foil in the liquid-solid ratio range of the process is smaller, and the process is suitable for large-scale industrial application.
As a further refinement of the above technical solutions, in some embodiments, the stripping solution may further comprise an auxiliary stripping agent, which may include a water-soluble organic solvent.
In some embodiments, the water-soluble organic solvent may include any one or a combination of two of ethanol and acetone, but is not limited thereto.
The auxiliary stripping agent used in the invention can carry the adhesive molecules to the surface of the liquid to form directional arrangement due to the surface adsorption effect after the adhesive is dissolved in the water, thereby increasing the solubility of the adhesive in a solution system and improving the stripping efficiency. The binder itself is preferably dissolved in an aqueous 60% ethanol solution, and therefore ethanol is preferably added as an auxiliary stripping agent. The above effects also improve the tolerance of the reduction of the dissolution capacity of the stripping solution, reduce the negative influence of the reduction of the dissolution capacity of the stripping solution caused by the increase of the impurity ion content on the recycling of the stripping solution, and further improve the recycling times of the stripping solution.
With respect to step 1) above, in some embodiments, the volume fraction of surfactant in the stripping solution may preferably be from 0.5 to 10%.
In some embodiments, the auxiliary stripper may be diluted 6-8 times and mixed with a surfactant to obtain the stripping liquid.
In some embodiments, the volume ratio of surfactant to the diluent of the auxiliary stripper may preferably be in the range of 10:1 to 1:1.
In some embodiments, the surfactant may include any one or a combination of two or more of an anionic surfactant, a cationic surfactant, and an amphoteric surfactant.
In some embodiments, the anionic surfactant may include any one or a combination of two or more of alcohol ether carboxylate, alkylbenzenesulfonate, sodium alpha-alkenyl sulfonate, secondary alkyl sulfonate, fatty alcohol sulfate, and phosphate salt, but is not limited thereto.
In some embodiments, the cationic surfactant may include any one or a combination of two of octadecyl trimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, but is not limited thereto.
In some embodiments, the amphoteric surfactant may include any one or a combination of both of cocamidopropyl betaine and ammonium oxide, but is not limited thereto.
In some embodiments, in step 1), the temperature of the dissociation treatment may preferably be 20-95 ℃ and the time may preferably be 10-720min.
In some embodiments, the mass to volume ratio of the stripping solution to the negative electrode of the spent lithium ion battery may preferably be 100:1 to 5:1 mL/g.
In some embodiments, the spent lithium ion battery negative electrode is sheared into a sheet-like body that may preferably have an area of 0.5-25cm 2.
In some embodiments, the stirring rate of the mechanical stirring may preferably be 10-1200rpm, and the power density of the ultrasound may preferably be 5-10W/cm 2.
With respect to step 2) above, in some embodiments, the mixed liquor in step 2) may be subjected to centrifugation to obtain the negative electrode material and a separation liquor.
In some embodiments, the rotational speed of the centrifugation process may preferably be 1500-12000r/min.
As some typical examples of application, in the above step 2), the separation of the current collector from the mixed liquor may be performed in various existing manners, for example, screening, including standard screening, vibration screening, ultrasonic screening, etc., and the mesh size may be selected to be 4-2000 mesh, for example, 4.75mm-0.0065mm. The current collector obtained by screening, such as copper foil, is used as a copper foil product after cleaning and drying, wherein the drying temperature of the copper foil can be 30-120 ℃ and the time can be 0.5-24h. The cleaning liquid used for cleaning can also be recycled.
The negative electrode material and the separating liquid can be obtained by separating from the mixed liquid by various existing methods, for example, a high-speed centrifugal method can be adopted, the rotating speed of the high-speed centrifugal machine is 1500-12000r/min, the negative electrode material obtained by centrifugation, such as graphite, is dried to obtain a finished product, and the drying temperature is 30-120 ℃ for 0.5-24h.
With respect to step 3) above, in some embodiments, the lithium ion precipitant is an alkaline precipitant.
In some embodiments, the alkaline precipitant may include any one or a combination of two of sodium carbonate, sodium bicarbonate, and sodium phosphate.
In some embodiments, the lithium ion precipitant is formulated for addition as a solution to the separation liquid, and in some further preferred embodiments, is formulated for addition as a saturated solution.
In some embodiments, the rate of addition of the lithium ion precipitant per liter of the separation liquid may preferably be 0.5 to 1mL/min.
In some embodiments, the lithium ion precipitant may be added for a time of preferably 1 to 10 minutes.
In some embodiments, a lithium ion precipitant is selected for addition to a pH greater than 9 as an endpoint for the addition of the lithium ion precipitant.
In the above technical solution, determination of the addition end point of the lithium ion precipitant is very important, because when the precipitation of lithium ions is insufficient, the residual lithium ions may continue to affect the solubility of the stripping solution; when the lithium ion precipitant is excessively added, the formed precipitate is dissolved due to the effects of salt effect and coordination effect, so that the proper and easily-distinguished addition end point of the lithium ion precipitant has important significance for the application of the technical scheme of the invention.
In some embodiments, after the addition is completed, the lithium ion precipitant and the separation liquid are allowed to stand still and react for 30-60min at the temperature of 80-100 ℃ to obtain the lithium salt and the treatment liquid through solid-liquid separation; so as to realize sufficient precipitation and aging of lithium ions, and ensure the cycle times of the stripping liquid and simultaneously ensure that the precipitated lithium salt is easy to separate and recycle.
In some embodiments, the solid-liquid separation may employ centrifugation or filtration.
In some embodiments, the number of cycles of the recycling can be up to 5 or more.
The purity of the current collector obtained by the separation and recovery method provided by the embodiment of the invention is more than 99.9%, and the recovery rate is close to 100%; the cathode material can be used for manufacturing related products after being recycled. Incidentally, the purity of the recovered lithium salt product is more than 95%. The stripping liquid used in the whole process, particularly the stripping agent in the stripping liquid, the generated separating liquid and flushing water can be recycled, no waste water is generated, and the selected stripping agent has excellent biodegradability and low price, is a green short-flow separation process with high separation efficiency, large treatment capacity and good environmental protection, and is suitable for industrial continuous production.
The foregoing is an exemplary description of the present invention and is further defined below to be described in detail with reference to the accompanying drawings. However, the examples chosen are the preferred ones of the many possible embodiments only to illustrate the invention and to make it easy for those skilled in the art to understand the invention without limiting its scope.
Example 1
The method comprises the steps of taking a waste lithium cobalt oxide battery negative electrode plate as a raw material, and mixing a cationic surfactant octadecyl trimethyl ammonium chloride solution and an ethanol solution diluted by 6 times according to a volume ratio of 2:1 to obtain stripping solution;
The separation and recovery conditions are as follows: surfactant concentration 7% (volume concentration), liquid-solid ratio 5:1 mL/g, treatment temperature 50 ℃, stirring rotation speed 50rpm, treatment time 40min;
And (3) screening and separating the mixture by a standard sieve with the particle size of 100 meshes, and drying the oversize product at the temperature of 50 ℃ for 8 hours to obtain the current collector copper foil. Centrifuging the undersize solution at a centrifuge rotating speed of 5000r/min to obtain negative black powder and centrifugate, and drying at 80 ℃ for 20h;
the centrifugate is dropwise added with saturated sodium carbonate solution at a dropwise adding rate of 0.5mL/min for 5min for each liter of centrifugate until the PH is more than 9, and the centrifugate is stood and aged for 30min at 80 ℃ to obtain lithium salt precipitate and a new stripping solution capable of being recycled, wherein the recovery rate of lithium ions is more than 98%.
Under the condition, the separation yield and purity of the copper foil are both more than 99 percent. The negative black powder can be used for manufacturing related graphite products after subsequent treatment. The centrifugate is recycled as new stripping liquid and can be recycled to 5-6 cycles without significant reduction of recovery rate of each material and time efficiency of recovery.
Example 2
The negative electrode plate of the waste ternary battery is used as a raw material, and an anionic surfactant sodium dodecyl benzene sulfonate solution is used as stripping liquid.
The separation and recovery conditions are as follows: surfactant concentration 7% (volume concentration), liquid-solid ratio 5:1 mL/g, treatment temperature 50 ℃, stirring rotation speed 50rpm, treatment time 40min;
and (3) screening and separating the mixture by a standard sieve with the particle size of 100 meshes, and drying the oversize product at the temperature of 50 ℃ for 8 hours to obtain the current collector copper foil. Centrifuging the undersize solution at a centrifuge rotating speed of 5000r/min to obtain negative black powder and centrifugate, and drying graphite at 80 ℃ for 20 hours;
The centrifugate is dropwise added with saturated sodium carbonate solution at a dropwise adding rate of 0.6mL/min for 5min, the PH is more than 9, the centrifugate is stood and aged for 30min at 80 ℃, and lithium salt precipitation and a new stripping solution capable of being recycled are obtained, wherein the recovery rate of lithium ions is more than 98%.
Under the condition, the separation yield of the copper foil reaches 97.5%, and the purity is more than 99%. The negative black powder can be used for manufacturing related graphite products after subsequent treatment. The centrifugate can be recycled as stripping agent for 5-6 cycles without significant reduction in recovery rate of each material and time efficiency of recovery.
Example 3
The negative electrode plate of the waste lithium iron phosphate battery is used as a raw material, and a cationic surfactant octadecyl trimethyl ammonium chloride and an ethanol solution diluted by 6 times are mixed according to the volume ratio of 10:1 to be used as stripping liquid.
The separation and recovery conditions are as follows: surfactant concentration 1% (volume concentration), liquid-solid ratio 5:1 mL/g, treatment temperature 50 ℃, stirring rotation speed 50rpm, treatment time 20min;
and (3) screening and separating the mixture by a standard sieve with the particle size of 100 meshes, and drying the oversize product at the temperature of 50 ℃ for 8 hours to obtain the current collector copper foil. Centrifuging the undersize solution at a centrifuge rotating speed of 5000r/min to obtain negative black powder and centrifugate, and drying graphite at 70 ℃ for 10 hours;
the centrifugate is dripped for 8min at the dripping rate of 0.8mL/min corresponding to each liter of centrifugate by using saturated solution of sodium carbonate until the PH is more than 9, and is stood and aged for 30min at 80 ℃ to obtain lithium salt precipitate and a new stripping solution capable of being recycled, wherein the recovery rate of lithium ions is more than 98%.
Under the condition, the separation efficiency and purity of the copper foil are both more than 99 percent. The negative black powder can be used for manufacturing related graphite products after subsequent treatment. The centrifugate was recycled for 5-6 cycles without significant reduction in recovery rate of each material and time efficiency of recovery.
Example 4
Mixing a negative plate of a waste lithium iron phosphate battery with a cationic surfactant and an anionic surfactant in a molar mass ratio of 1:1, and diluting the mixture with an acetone solution with a volume ratio of 10:3 to obtain a stripping solution;
The separation and recovery conditions are as follows: surfactant concentration 5% (volume concentration), liquid-solid ratio 5:1 mL/g, treatment temperature 60 ℃, stirring rotation speed 50rpm, treatment time 60min;
And (3) screening and separating the mixture by a standard sieve with the particle size of 100 meshes, and drying the oversize product at the temperature of 50 ℃ for 8 hours to obtain the current collector copper foil. Centrifuging the undersize solution at a centrifuge rotating speed of 6000r/min to obtain negative black powder and centrifugate, and drying graphite at 80 ℃ for 20 hours;
The centrifugate is dripped with saturated sodium carbonate solution at the dripping rate of 0.6mL/min for 5min until the PH is more than 9, and is kept stand and aged for 40min at 80 ℃ to obtain lithium salt precipitate and new stripping liquid capable of being recycled, wherein the recovery rate of lithium ions is more than 98%.
Under the condition, the separation efficiency and purity of the copper foil are both more than 99 percent. The negative black powder can be used for manufacturing related graphite products after subsequent treatment. The centrifugate was recycled for 5-6 cycles without significant reduction in recovery rate of each material and time efficiency of recovery.
Comparative example 1
This comparative example is substantially identical to example 1, except that:
The step of precipitating and treating lithium ions by using sodium carbonate solution is omitted, and the centrifugate obtained by centrifugation is directly used as new stripping liquid for continuous use.
This comparative example showed a significant decrease in recovery rate and recovery time efficiency in the 3 rd cycle, and could not be used.
Based on the above examples and comparative examples, it is clear that the method for separating and recovering the current collector from the negative electrode material in the negative electrode of the waste lithium ion battery provided by the invention does not use a large amount of organic solvents and high-temperature heating and other treatment means with high pollution or high energy consumption, and can realize the separation and recovery of the current collector from the negative electrode material with high efficiency and high recovery rate by using only the environment-friendly surfactant.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (9)
1. The method for separating and recycling the current collector and the negative electrode material in the negative electrode of the waste lithium ion battery is characterized by comprising the following steps of:
1) Contacting a negative electrode of a waste lithium ion battery with stripping liquid, and applying mechanical stirring and/or ultrasonic to carry out dissociation treatment so as to dissociate a negative electrode material in the negative electrode of the waste lithium ion battery from a current collector, wherein the negative electrode material is dispersed in the stripping liquid to form a mixed liquid, and the stripping liquid contains a surfactant;
2) Separating the current collector from the mixed liquid and separating a negative electrode material from the mixed liquid and a separation liquid;
3) Carrying out precipitation treatment on the separation liquid by adopting a lithium ion precipitant to obtain a treatment liquid and lithium salt, and recycling the treatment liquid as the stripping liquid;
The lithium ion precipitant is an alkaline precipitant, wherein the alkaline precipitant comprises any one or combination of sodium carbonate, sodium bicarbonate and sodium phosphate, the adding rate of the lithium ion precipitant corresponding to each liter of the separating liquid is 0.5-1mL/min, the adding time of the lithium ion precipitant is 1-10min, and the pH value is more than 9 as the adding end point of the lithium ion precipitant.
2. The separation and recovery method according to claim 1, wherein the stripping liquid further comprises an auxiliary stripping agent, and the auxiliary stripping agent comprises a water-soluble organic solvent.
3. The separation and recovery method according to claim 2, wherein the water-soluble organic solvent comprises any one or a combination of two of ethanol and acetone.
4. The separation and recovery method according to claim 3, wherein the volume fraction of the surfactant in the stripping liquid is 0.5 to 10%;
The auxiliary stripping agent is diluted by 6-8 times and then mixed with a surfactant to obtain the stripping liquid; the volume ratio of the surfactant to the diluent of the auxiliary stripping agent is 10:1-1:1.
5. The separation and recovery method according to claim 1, wherein the surfactant comprises any one or a combination of two or more of an anionic surfactant, a cationic surfactant, and an amphoteric surfactant;
The anionic surfactant comprises any one or more than two of alcohol ether carboxylate, alkylbenzenesulfonate, alpha-sodium alkenyl sulfonate, secondary alkyl sulfonate, fatty alcohol sulfate and phosphate;
The cationic surfactant comprises any one or the combination of two of octadecyl trimethyl ammonium chloride and dialkyl dimethyl ammonium chloride;
the amphoteric surfactant comprises any one or combination of two of cocamidopropyl betaine and ammonium oxide.
6. The separation and recovery method according to claim 1, wherein in step 1), the temperature of the dissociation treatment is 20 to 95 ℃ for 10 to 720 minutes;
The volume-mass ratio of the stripping liquid to the negative electrode of the waste lithium ion battery is 100:1-5:1mL/g;
The stirring speed of the mechanical stirring is 10-1200rpm, and the power density of the ultrasonic is 5-10W/cm.
7. The separation and recovery method according to claim 1, wherein the mixed solution in step 2) is subjected to centrifugal treatment to obtain the negative electrode material and the separation solution, and the rotational speed of the centrifugal treatment is 1500-12000r/min.
8. The separation and recovery method according to claim 1, wherein after the addition of the alkaline precipitant is completed, the lithium ion precipitant and the separation liquid are allowed to stand still at 80-100 ℃ for 30-60min, and then solid-liquid separation is performed to obtain the lithium salt and the treatment liquid, wherein the solid-liquid separation is performed by a centrifugation method or a filtration method.
9. The separation and recovery method according to claim 1, wherein the number of cycles of the recycling can be up to 5 or more.
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