WO2023109096A1 - 一种金属基底上涂覆层剥离方法及其应用 - Google Patents

一种金属基底上涂覆层剥离方法及其应用 Download PDF

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WO2023109096A1
WO2023109096A1 PCT/CN2022/103295 CN2022103295W WO2023109096A1 WO 2023109096 A1 WO2023109096 A1 WO 2023109096A1 CN 2022103295 W CN2022103295 W CN 2022103295W WO 2023109096 A1 WO2023109096 A1 WO 2023109096A1
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acid
coating layer
metal substrate
current collector
decommissioned
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PCT/CN2022/103295
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English (en)
French (fr)
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孙永明
陈子和
陆荣华
刘书源
赵建智
聂瑞超
冯睿康
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华中科技大学
武汉蔚能电池资产有限公司
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Publication of WO2023109096A1 publication Critical patent/WO2023109096A1/zh

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D9/00—Chemical paint or ink removers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
    • C23C22/03—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions containing phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/56—Treatment of aluminium or alloys based thereon
    • 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

Definitions

  • the invention belongs to the field of coating stripping, and in particular relates to a method for stripping a coating layer on a metal substrate and an application thereof.
  • Coating other materials on metal substrates is widely used in various fields, such as lithium battery technology, the active material and conductive agent are bonded and uniformly coated on aluminum/copper foil through a binder to achieve battery energy stability Output;
  • the purpose of metal anti-corrosion is achieved by coating polyurethane, fluororesin, and silicone;
  • the purpose of metal high-temperature resistance is achieved through epoxy resin and liquid rubber coating;
  • the field of metal insulation through water-based insulating varnish coating, insulating ceramic coating to achieve the purpose of metal insulation.
  • the coating layer on the outer surface has a limited service life.
  • the performance of the electrode material will decline with the increase in the number of times the battery is used.
  • Anti-corrosion coatings, high-temperature resistant coatings and insulating coatings located on the metal surface are inevitable. Friction and scratching will lead to a decrease in the overall service life of the firmware. Therefore, after the coating layer that has reached the end of its service life is peeled off, the two are further efficiently recycled, which has become a key step for secondary utilization under the premise of environmental protection.
  • CN107464963 discloses a method of detaching the coating layer from the pole piece through organic solvents such as styrene, acetone, and tetrachlorethylene after the pole piece is crushed.
  • the method utilizes an organic agent with high solubility to the binder to dissolve the binder , so that the active material and conductive carbon black fall off freely, but this type of method is often limited to the electrode coating process.
  • the degree of infiltration of the organic solvent on the electrode is limited. At present, this method It has been difficult to achieve the desired separation effect.
  • CN107706481A discloses a method based on hollow microsphere solid-phase recovery lithium battery positive electrode material, wherein the separation process is: soak the lithium ion battery pole piece in alkaline solution for 10-13 hours, and dissolve the copper/aluminum current collector to obtain filter residue of electrode material.
  • This method can effectively separate electrode materials, but just like using acid to directly dissolve copper/aluminum foil, the completely dissolved aluminum ions in the solution will be adsorbed by the conductive carbon black in the electrode material, so it is difficult to be removed in the electrode material recovery stage, reducing the Batch consistency of materials.
  • CN112442296A discloses a stripping composition containing ethers, esters, amines, alcohols and glycosides to remove coatings from surfaces and methods.
  • the method of relaxing or dissolving the coating by a solvent has certain limitations, and it is easy to cause peeling residue due to the difference in the bonding strength/corrosion degree of the coating to the substrate material.
  • CN113522596A discloses a closed spraying hanger coating physical removal machine, which realizes the drop/peeling of the coating layer by continuously colliding with the metal material coated with the coating layer. Obviously, the method of scraping off with physical violence can be used to a certain extent. Avoiding contamination, but avoiding damage to metal substrates and coating materials and improving stripping efficiency are all major challenges.
  • CN111313120A discloses a method for recovering cobalt and lithium metal in waste lithium ion batteries, comprising: dismantling waste lithium ion batteries to obtain positive electrodes; The separation liquid of the positive plate is placed in an ultrasonic environment for a period of time, and then the aluminum foil is taken out to obtain a mixed liquid; the mixed liquid is obtained by rotary evaporation to obtain a solid substance, and the solid substance is dried to obtain a lithium-ion battery positive electrode material; after mixing the positive electrode material with a chelating agent The mechanical activation treatment is performed to obtain an activation mixture; the obtained activation mixture is subjected to acid leaching treatment to obtain an enrichment solution containing cobalt and lithium.
  • this technical solution uses a chelating agent for treatment, so that the ions are leached and precipitated to allow different elements to be recovered separately, it does not promote the separation of the metal substrate and the coating layer.
  • the prior art still lacks a method for efficiently separating the metal substrate and the coating layer.
  • the present invention provides a method for peeling off the coating layer on the metal substrate, which uses a chelating agent to form passivation on the surface of the current collector while destroying the interface between the metal substrate and the coating layer in an acidic environment layer, which not only realizes the efficient separation of the electrode material layer but also avoids the continuous dissolution of the metal substrate.
  • the method is reasonable in design, easy to implement, environmentally friendly and low in cost, can be applied to modern industrial production, and has extremely high economic and social benefits.
  • a method for peeling off the coating layer on the metal substrate is provided, the metal substrate is soaked in an acid solution for acid treatment, and the interface bonding between the metal substrate and the coating layer is invalidated, Then peel off to obtain the metal base and coating material, wherein the acid solution includes a chelating agent.
  • the chelating agent contains more than two multidentate ligands, and the functional groups of the multidentate ligands include -H 2 PO 4 , -H 2 PO 3 , -Na 2 PO 4 , -K 2 PO 4 , -Na One or more of 2 PO 3 , -COONa, -COOH, -SH and -SK.
  • the chelating agent contains more than 4 multidentate ligands, and the functional group of the multidentate ligands is one of -H 2 PO 4 , -H 2 PO 3 , -COOH and -SH.
  • the chelating agent includes phytic acid, hydroxyethylidene-1,1-diphosphonic acid (HEDP), sodium ethylenediaminetetramethylenephosphonate (EDTMPS), ethylenediaminetetraacetic acid (EDTA), amino Trimethylenephosphonic acid (ATMP), diethylenetriaminepentamethylenephosphonic acid (BNHMTPMP), triethylenetetraminehexamethylenephosphonic acid (TETHMP), bis(1,6-hexamethylene)triaminepentamethylene At least one of methylphosphonic acid (BNHMTPMP), polyaminopolyether tetramethylenephosphonic acid (PAPEMP), dimercaptopropanol, sodium gluconate and sodium phytate.
  • HEDP hydroxyethylidene-1,1-diphosphonic acid
  • EDTMPS sodium ethylenediaminetetramethylenephosphonate
  • EDTA ethylenediaminetetraacetic acid
  • AMP amino Trimethylenephosphonic acid
  • the mass proportion of the chelating agent in the acid solution is more than 10%; preferably, the content of the chelating agent is 20-75%.
  • the pH of the acid solution is ⁇ 5.
  • the solvent in the acid solution includes water, methanol, ethanol, ethylene glycol, acetone, dimethylsulfoxide, ethylenediamine, N,N-dimethylformamide, dimethylacetamide, phosphoric acid at least one of triethyl esters.
  • the acid solution is an aqueous solution of phytic acid.
  • the application includes the stripping of the current collector and the electrode material in the pole piece of the decommissioned lithium battery, and the metal polymer coating peeling, peeling of metal insulating coating or peeling of metal corrosion-resistant layer.
  • the stripping of the current collector and the electrode material in the decommissioned lithium battery pole piece in the application includes the following steps:
  • the decommissioned electrode pole piece includes the current collector and the electrode material layer coated on the current collector;
  • the compacted density of the electrode material layer is 1.0-4.0 g/cm 3
  • the composition includes active material, binder and conductive agent
  • the active material includes ternary nickel-cobalt-manganese material, ternary nickel-cobalt-aluminum material, lithium iron phosphate material, lithium cobalt oxide material, lithium manganate material, lithium nickel manganese oxide material, lithium titanate material, niobic acid
  • ternary nickel-cobalt-manganese material ternary nickel-cobalt-aluminum material, lithium iron phosphate material, lithium cobalt oxide material, lithium manganate material, lithium nickel manganese oxide material, lithium titanate material, niobic acid
  • titanium material silicon-based material and graphite
  • the conductive agent comprises one of conductive carbon black, conductive graphite, Super P Li, Ketjen Black and carbon nanotubes;
  • the binder includes polyvinylidene fluoride (PVDF), styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), polyacrylic acid (PAA), polyacrylonitrile (PAN), polyvinyl alcohol ( PVA), lithium polyvinyl alcohol (Li-PVA);
  • PVDF polyvinylidene fluoride
  • SBR styrene-butadiene rubber
  • CMC carboxymethyl cellulose
  • PAA polyacrylic acid
  • PAN polyacrylonitrile
  • PVA polyvinyl alcohol
  • Li-PVA lithium polyvinyl alcohol
  • the current collector is an aluminum current collector or a copper current collector.
  • Super P Li conductive carbon black is a carbon black with high porosity, which can form a carbon black network structure at a very low addition amount, and endow the product with excellent electrical conductivity.
  • the present invention destroys the surface of the metal substrate in an acidic environment, while the hydrogen ion dissolves the metal, the chelating agent will passivate the metal substrate, and will continuously drive the unexposed metal protected by the coating layer to continue to react with the hydrogen ion, Destroy the bonding between the coating layer and the metal material, and finally make the bond between the metal substrate and the coating layer invalid.
  • the chelating agent will protect the dissolved metal ions, avoid the continuous dissolution of the metal substrate, and finally achieve high Efficient separation and high quality extraction.
  • the present invention can complete the separation of the electrode material layer in a short time, and can realize the efficient separation of the metal substrate and the coating layer, especially in the stripping process of the decommissioned lithium battery pole piece, which has more obvious advantages, namely Its good peeling effect is hardly affected by the compaction density of the pole piece, and has a high tolerance.
  • the chelating agent chelates the dissolved metal ions to form a dense passivation film on the surface of the metal substrate to avoid continuous dissolution of the metal substrate.
  • the test results of the generator (ICP) show that the content of impurity metal ions in the solution after stripping is at least 0.000%, which shows that this method effectively eliminates the generation of impurity metal elements during the stripping process, greatly improves the purity of the separated product, and effectively saves the subsequent complicated steps. Purification process.
  • Fig. 1 is the separation effect diagram of the decommissioned LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode sheet with a compacted density of 3.8g/ cm in Example 1;
  • Fig. 2 is an actual view of the lithium titanate negative electrode sheet with a compacted density of 2.2 g/cm 3 in Example 2 when the electrode material layer is peeled off and the electrode material layer is not dried.
  • Fig. 3 is the physical figure of aluminum foil and coating layer after direct drying in embodiment 2.
  • a pole piece was isolated from a decommissioned single crystal LiNi 0.5 Co 0.2 Mn 0.3 O 2 battery: its coating layer consisted of 4% PVDF, 4% conductive carbon black and 92% LiNi 0.5 Co 0.2 Mn 0.3 O 2 and consisted of PVDF Bonded on aluminum foil, the characterized compaction density is 3.8g/cm 3 . Soak it in an aqueous solution with phytic acid content of 75%, 50%, 35%, and 10% at 25°C for 60 seconds, and then stir the solution at 60r/min. After the coating layer and the current collector are separated, they are washed with water for 60 The product was obtained by drying at °C for 1 hour, and the separation results are shown in Table 1.
  • Fig. 1 is a separation effect diagram of the decommissioned LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode sheet in Example 1.
  • the decommissioned single crystal LiNi 0.5 Co 0.2 Mn 0.3 O 2 positive electrode piece can be soaked in an aqueous solution with a phytic acid content of 75% for 5 minutes and 18 seconds to complete the peeling of 99.97% of the aluminum foil and 99.98% of the coating layer. Both maintained good integrity after drying.
  • the surface of the aluminum foil was smooth and clean, and the electrode material layer was successfully peeled off in large flakes, with a peeling rate of 99.98%. Tested by an inductively coupled plasma spectrometer, the Al content in the electrode material layer is only 0.012%.
  • HEDP hydroxyethylidene-1,1-diphosphonic acid at 25°C
  • PAPEMP polyamino polyether tetramethylene phosphonic acid
  • BNHMTPMP bis (1,6-hexamethylene) triamine pentamethylene phosphonic acid
  • HEDP, PAPEMP, BNHMTPMP, and phytic acid molecules have 2, 4, 5, and 6 chelating ligands, respectively. From Table 2, it can be seen that the decommissioned lithium iron phosphate pole piece is soaked in different chelating agent acid solutions with a pH of 1.0, and the chelating ligands The more complex ligands, the poorer the chelating ability, and more metal ions will be dissolved in the solution, but the faster the stripping process will be. Of course, even the less effective HEDP still has some peeling effect.
  • Fig. 2 is an actual view of the lithium titanate negative electrode sheet with a compacted density of 2.2 g/cm 3 in Example 2 when the electrode material layer is peeled off and the electrode material layer is not dried. After stirring, the undried electrode material layer is peeled off, which has a good integrity, and its mechanical strength is not broken when it is taken with tweezers. The undried electrode material layer peeled off from the decommissioned pole piece has better integrity and mechanical strength.
  • Fig. 3 is the physical picture of the aluminum foil and the coating layer after direct drying without stirring in Example 2. Due to the failure of the bond and the volume shrinkage during the drying process, the electrode material layer can be naturally detached after drying.
  • the decommissioned single-crystal LiNi 0.5 Co 0.2 Mn 0.3 O 2 battery was disassembled, and the positive electrode sheet with a compacted density of 3.8 g/cm 3 was separated and soaked in N-methylpyrrolidone (NMP) solution at 25 °C for 1 hour. Subsequently, the solution was stirred at 60 r/min, and there was no obvious observation of the falling off of the electrode material.
  • NMP N-methylpyrrolidone
  • the decommissioned single-crystal LiNi 0.5 Co 0.2 Mn 0.3 O 2 battery was disassembled, and the positive electrode sheet with a compacted density of 3.8 g/cm 3 was separated and soaked in water at 25 °C for 1 hour, and then the solution was stirred at 60 r/min. The exfoliation of the electrode material was clearly observed.

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Abstract

本发明属于涂层剥离领域，具体涉及一种金属基底上涂覆层剥离方法及其应用。本发明将金属基底浸泡在酸溶液中进行酸处理，使金属基底和涂覆层的界面粘结失效，然后进行剥离，即可获得金属基底和涂覆层材料，其中，所述酸溶液包括螯合剂。本发明在酸性环境下破坏金属基底的表面，使金属和涂覆层的粘结失效；同时，在金属基底和涂覆层界面被破坏的瞬间，螯合剂可以螯合溶出的金属离子，在金属表面形成致密的钝化层可以避免金属基底的持续溶解，因而可以实现金属基底和涂覆层的高效分离。

Description

一种金属基底上涂覆层剥离方法及其应用 【技术领域】
本发明属于涂层剥离领域，具体涉及一种金属基底上涂覆层剥离方法及其应用。
【背景技术】
金属基底上涂覆其他材料广泛应用于各个领域，如锂电池工艺中，通过粘结剂将活性物质和导电剂粘结并均匀的涂覆在铝/铜箔材上，以达到电池能量的稳定输出；在金属防腐邻域，通过将聚氨酯、氟树脂、有机硅涂层达到金属防腐的目的；在金属耐高温领域，通过环氧树脂、液态橡胶涂层达到金属耐高温的目的；金属绝缘领域，通过水性绝缘漆涂层、绝缘陶瓷涂层达到金属绝缘的目的。
然而在使用过程中，位于外表面涂覆层具有有限的使用寿命，如电极材料会随着电池使用次数的增加性能衰退、位于金属外表的防腐涂层、耐高温涂层和绝缘涂层不可避免的遭受摩擦和刮蹭会导致固件整体的使用寿命下降，因此将达到使用寿命的涂覆层剥离后进一步将两者高效回收，成为了在环保前提下二次利用的关键步骤。
CN107464963公开了一种将极片粉碎后通过苯乙烯、丙酮、四氯乙烯等有机溶剂使涂覆层从极片脱落的方法，该方法利用对粘结剂溶解度大的有机试剂使得粘结剂溶解，从而使得活性物质和导电炭黑自由脱落，但该类方法常受限于极片涂覆工艺，随着正极材料的压实度不断提高，有机溶剂对极片的浸润度有限，目前该方法已经很难达到预期的分离效果。
CN107706481A公开了一种基于中空微球固相回收锂电池正极材料的方法，其中分离过程为：将锂离子电池极片在碱液中浸泡10-13小时，溶解的铜/铝集流体以得到含电极材料的滤渣。此方法可以有效分离电极材料，但是和利用酸直接溶解铜/铝箔一样，完全溶解的铝离子在溶液中将会被电 极材料中的导电炭黑吸附，从而在电极材料回收阶段难以被去除，降低材料的批次一致性。
CN112442296A公开了一种含有醚、酯、胺、醇和糖苷的剥离组合物从表面去除涂层的组合物和方法。然而通过溶剂使涂层松弛或溶解的方法具有一定的局限性，且由于涂层对基底材料的粘结强度/腐蚀程度不同极易造成剥离残留，正如该专利所述，即使在优选条件下也会有10％以内的材料难以剥离。CN113522596A公开了一种封闭式喷涂挂具涂层物理清除机，通过对涂有涂覆层的金属材料不断碰撞实现涂覆层的掉落/剥离，显而易见，以物理暴力刮离的方法可以一定程度避免污染，但是避免对金属基底和涂覆层材料的损伤以及提高剥离效率都存在较大的挑战。
CN111313120A公开了一种废旧锂离子电池中钴和锂金属的回收方法，包括：把废旧锂离子电池拆解，得到正极片；将所述正极片剪成小块浸泡到分离液中，将泡有正极片的分离液在超声环境中置一段时间后取出铝箔得到混合液；将混合液通过旋转蒸发得到固体物质，固体物质经烘干后得到锂离子电池正极材料；将正极材料与螯合剂混合后进行机械活化处理，得到活化混合物；得到的活化混合物经过酸浸处理，即可得到含钴和锂的富集液。该技术方案虽然使用了螯合剂进行处理，使得浸出离子后沉淀让不同元素分别回收，但并没有促进金属基底和涂覆层的分离。
综上所述，现有技术仍缺乏一种高效分离的金属基底和涂覆层的方法。
【发明内容】
针对现有技术的以上缺陷或改进需求，本发明提供了一种金属基底上涂覆层剥离方法，在酸性环境破坏金属基底和涂覆层界面的同时，利用螯合剂在集流体表面形成钝化层，既实现了电极材料层的高效分离又避免了金属基底的持续溶解。该方法设计合理、易于实施、环境友好且成本低廉，可以应用于现代工业化生产，具有极高的经济效益和社会效益。
为实现上述目的，按照本发明的一个方面，提供了一种金属基底上涂 覆层剥离方法，将金属基底浸泡在酸溶液中进行酸处理，使金属基底和涂覆层的界面粘结失效，然后进行剥离，即可获得金属基底和涂覆层材料，其中，所述酸溶液包括螯合剂。
作为优选，所述螯合剂中含有2个以上多齿配体，多齿配体的官能团包括-H 2PO 4、-H 2PO 3、-Na 2PO 4、-K 2PO 4、-Na 2PO 3、-COONa、-COOH、-SH和-SK中的一种或多种。
作为优选，所述螯合剂中含有4个以上多齿配体，多齿配体的官能团为-H 2PO 4、-H 2PO 3、-COOH和-SH中的一种。
作为优选，所述螯合剂包括植酸、羟基亚乙基-1,1-二膦酸(HEDP)、乙二胺四甲叉膦酸钠(EDTMPS)、乙二胺四乙酸(EDTA)、氨基三亚甲基膦酸(ATMP)、二乙烯三胺五亚甲基膦酸(BNHMTPMP)、三乙烯四胺六亚甲基膦酸(TETHMP)、双(1,6-亚己基)三胺五亚甲基膦酸(BNHMTPMP)、多氨基多醚基四亚甲基膦酸(PAPEMP)、二巯基丙醇、葡萄糖酸钠和植酸钠中的至少一种。
作为优选，所述酸溶液中螯合剂的质量占比为10％以上；优选地，螯合剂含量为20-75％。
作为优选，所述酸溶液的pH≤5。
作为优选，所述酸溶液中的溶剂包括水、甲醇、乙醇、乙二醇、丙酮、二甲基亚砜、乙二胺、N,N-二甲基甲酰胺、二甲基乙酰胺、磷酸三乙酯中的至少一种。
作为优选，所述酸溶液为植酸的水溶液。
按照本发明的另一个方面，提供了一种所述的在金属基底上涂覆层剥离方法的应用，所述应用包括退役锂电池极片中集流体和电极材料的剥离、金属聚合物涂层的剥离、金属绝缘涂层的剥离或金属耐腐蚀层的剥离。
作为优选，所述应用中退役锂电池极片中集流体和电极材料的剥离，包括以下步骤：
(1)将退役锂电池拆解出退役电极极片，退役电极极片包括集流体和涂覆在集流体上的电极材料层；
(2)将退役电极极片浸泡在酸溶液中进行酸处理，使电极材料层和集流体的粘结失效；
(3)将酸处理后的退役电极极片进行分离，获得活性物质和集流体；
优选地，所述电极材料层的压实密度为1.0-4.0g/cm 3，组成包括活性物质、粘结剂和导电剂；
优选地，所述活性物质包括三元镍钴锰材料、三元镍钴铝材料、磷酸铁锂材料、钴酸锂材料、锰酸锂材料、镍锰酸锂材料、钛酸锂材料、铌酸钛材料、硅基材料和石墨中的一种；
优选地，所述导电剂包括导电炭黑、导电石墨、Super P Li、科琴黑和碳纳米管中的一种；
优选地，所述粘结剂包括聚偏氟乙烯(PVDF)、丁苯橡胶(SBR)、羧甲基纤维素(CMC)、聚丙烯酸(PAA)、聚丙烯腈(PAN)、聚乙烯醇(PVA)、锂化聚乙烯醇(Li-PVA)；
优选地，所述集流体为铝集流体或铜集流体。
其中，Super P Li导电碳黑是具有高孔隙的碳黑，在很低添加量下可以形成碳黑的网状结构，并赋予产品优良的导电性能。
本发明的有益效果有：
(1)本发明在酸性环境下破坏金属基底的表面，氢离子溶解金属的同时，螯合剂会使得金属基底钝化，而且会不断驱动被涂覆层保护的未裸露金属继续与氢离子反应，进行破坏涂覆层与金属材料粘结作用，最终使金属基底和涂覆层的粘结失效，与此同时，螯合剂会保护已经被溶解的金属离子，避免金属基底的持续溶解，最终实现高效率的分离和高质量提取。
(2)本发明能够在短时间内完成电极材料层的分离，可以实现金属基底和涂覆层的高效分离，尤其是在退役锂电池极片的剥离过程中，具有更 为明显的优势，即其良好的剥离效果几乎不受极片压实密度的影响，具有较高的宽容度。
(3)本发明通过酸性溶液破坏金属基底和涂覆层界面的同时，螯合剂螯合溶出的金属离子在金属基底表面形成致密的钝化膜，避免金属基底的持续溶解，经电感耦合等离子体发生仪(ICP)测试结果表明剥离后溶液中杂质金属离子含量最低为0.000％，表明该方法有效杜绝了剥离过程中产生杂质金属元素，大大提高了分离产物的纯度，有效省去了后续复杂的提纯过程。
【附图说明】
图1为实施例1中压实密度为3.8g/cm 3的退役LiNi 0.5Co 0.2Mn 0.3O 2正极极片的分离效果图；
图2为实施例2中压实密度为2.2g/cm 3的钛酸锂负极片剥离出电极材料层未干燥时的实物图。
图3为实施例2中直接干燥后铝箔和涂覆层的实物图。
【具体实施方式】
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1
从退役单晶LiNi 0.5Co 0.2Mn 0.3O 2电池中分离出极片：其涂覆层由4％PVDF、4％导电炭黑和92％LiNi 0.5Co 0.2Mn 0.3O 2组成并由其中的PVDF粘结在铝箔上，经表征压实密度为3.8g/cm 3。将其浸泡在25℃植酸含量为75％、50％、35％、10％的水溶液中60秒，随后对溶液进行60r/min搅拌，涂覆层和集流体分离后分别经水洗涤，60℃干燥1小时获得产物，分离结果如 表1所示。
表1实施例1分离结果表
植酸质量比 10％ 35％ 50％ 75％
剥离时长 30分17秒 15分22秒 7分20秒 5分18秒
溶液中铝含量 0.000％ 0.000％ 0.006％ 0.012％
涂覆层剥离率 98.65％ 99.73％ 99.98％ 99.98％
集流体剥离率 100％ 100％ 99.99％ 99.97％
由表1可知，退役单晶LiNi 0.5Co 0.2Mn 0.3O 2极片涂覆层和铝金属剥离时长随溶液酸度(植酸含量)提高而缩短，当植酸含量为75wt％，实现99.98％涂覆层的剥离仅需5分钟18秒，但是酸度低的同时会导致铝金属微量的溶出，但满足工业级应用要求。综合而言，35％的植酸分离效果较为理想。
图1为实施例1中退役LiNi 0.5Co 0.2Mn 0.3O 2正极极片的分离效果图。
由图1可知，退役单晶LiNi 0.5Co 0.2Mn 0.3O 2正极极片浸泡在植酸含量为75％的水溶液中5分18秒即可完成99.97％铝箔和99.98％涂覆层的剥离，在干燥后两者均保持较好的完整度。
铝箔表面平整且干净，电极材料层也以大的片状成功剥离，剥离率为99.98％。经电感耦合等离子光谱发生仪测试，电极材料层中Al含量仅为0.012％。
实施例2
将退役磷酸铁锂电池拆解，分离出压实密度为2.2g/cm 3的钛酸锂负极片，将其浸泡在25℃含量为50％的羟基亚乙基-1,1-二膦酸(HEDP)、多氨基多醚基四亚甲基膦酸(PAPEMP)、双(1,6-亚己基)三胺五亚甲基膦酸(BNHMTPMP)的水/乙醇混合溶液(v/v＝1)中，利用硫酸酸将Ph调节至1.0，随后在室温下对溶液100r/min搅拌2分钟，将剥离后的集流体和电极材料层分别用水洗涤，80℃干燥1小时获得产物，结果如下表2所示。
表2实施例2分离结果表
Figure PCTCN2022103295-appb-000001
HEDP、PAPEMP、BNHMTPMP和植酸分子分别具有2、4、5和6个螯合配体，由表2可知，将退役磷酸铁锂极片浸泡在pH为1.0的不同螯合剂酸溶液中，螯合配体较少，螯合能力较差，溶液中会溶解有较多的金属离子，但该剥离过程速率越快。当然，即使是效果较差的HEDP仍具有一定的剥离效果。
图2为实施例2中压实密度为2.2g/cm 3的钛酸锂负极片剥离出电极材料层未干燥时的实物图。搅拌后剥离未干燥的电极材料层，其具备较好的完整度，且其机械强度满足在镊取的时候不破碎。退役极片剥离出未干燥的电极材料层具有较好的完整度与机械强度。
图3为实施例2中未搅拌直接干燥后铝箔和涂覆层的实物图。由于粘结失效，以及干燥过程中的体积收缩，使得干燥后电极材料层可以自然脱离。
实施例3
将以聚氨酯涂料为防腐蚀涂层的钢材浸泡至10℃，20％乙二胺四乙酸(EDTA)、20％植酸钠、5％植酸的pH分别为1.0、1.5和2.0的盐酸和乙 酸混合的水溶液中，待涂覆层表面具有明显皱褶后用水冲洗并干燥，干燥后剥离结果如下表3所示。
表3实施例3分离结果表
Figure PCTCN2022103295-appb-000002
由表2、3可知，由于防腐涂层较为致密，防腐涂层的剥离相对极片中涂覆层的剥离需要更长的时间，同时较高的pH有助于缩短分离时长。
对比实施例1
退役单晶LiNi 0.5Co 0.2Mn 0.3O 2电池拆解，分离出压实密度为3.8g/cm 3的正极片，将其浸泡在25℃，N-甲基吡咯烷酮(NMP)溶液中1小时，随后对溶液进行60r/min搅拌，没有明显观察到电极材料的脱落。
对比实施例2
退役单晶LiNi 0.5Co 0.2Mn 0.3O 2电池拆解，分离出压实密度为3.8g/cm 3的正极片，将其浸泡在25℃水中1小时，随后对溶液进行60r/min搅拌，没有明显观察到电极材料的脱落。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种金属基底上涂覆层剥离方法，其特征在于，将金属基底浸泡在酸溶液中进行酸处理，使金属基底和涂覆层的界面粘结失效，然后进行剥离，即可获得金属基底和涂覆层材料，其中，所述酸溶液包括螯合剂。
  2. 根据权利要求1所述的方法，其特征在于，所述螯合剂中含有2个以上多齿配体，多齿配体的官能团包括-H 2PO 4、-H 2PO 3、-Na 2PO 4、-K 2PO 4、-Na 2PO 3、-COONa、-COOH、-SH和-SK中的一种或多种。
  3. 根据权利要求1所述的方法，其特征在于，所述螯合剂中含有4个以上多齿配体，多齿配体的官能团为-H 2PO 4、-H 2PO 3、-COOH和-SH中的一种。
  4. 根据权利要求2或3所述的方法，其特征在于，所述螯合剂包括植酸、羟基亚乙基-1,1-二膦酸、乙二胺四甲叉膦酸钠、乙二胺四乙酸、氨基三亚甲基膦酸、二乙烯三胺五亚甲基膦酸、三乙烯四胺六亚甲基膦酸、双(1,6-亚己基)三胺五亚甲基膦酸、多氨基多醚基四亚甲基膦酸、二巯基丙醇、葡萄糖酸钠和植酸钠中的至少一种。
  5. 根据权利要求2或3所述的方法，其特征在于，所述酸溶液中螯合剂的质量占比为10％以上；优选地，螯合剂含量为20-75％。
  6. 根据权利要求1所述的方法，其特征在于，所述酸溶液的pH≤5。
  7. 根据权利要求2所述的方法，其特征在于，所述酸溶液中的溶剂包括水、甲醇、乙醇、乙二醇、丙酮、二甲基亚砜、乙二胺、N,N-二甲基甲酰胺、二甲基乙酰胺、磷酸三乙酯中的至少一种。
  8. 根据权利要求1所述的方法，其特征在于，所述酸溶液为植酸的水溶液。
  9. 根据权利要求1-8任一项所述的在金属基底上涂覆层剥离方法的应用，其特征在于，所述应用包括退役锂电池极片中集流体和电极材料的剥离、 金属聚合物涂层的剥离、金属绝缘涂层的剥离或金属耐腐蚀层的剥离。
  10. 根据权利要求9所述的应用，其特征在于，所述应用中退役锂电池极片中集流体和电极材料的剥离，包括以下步骤：
    (1)将退役锂电池拆解出退役电极极片，退役电极极片包括集流体和涂覆在集流体上的电极材料层；
    (2)将退役电极极片浸泡在酸溶液中进行酸处理，使电极材料层和集流体的粘结失效；
    (3)将酸处理后的退役电极极片进行分离，获得活性物质和集流体；
    优选地，所述电极材料层的压实密度为1.0-4.0g/cm 3，包括活性物质、粘结剂和导电剂；
    优选地，所述活性物质包括三元镍钴锰材料、三元镍钴铝材料、磷酸铁锂材料、钴酸锂材料、锰酸锂材料、镍锰酸锂材料、钛酸锂材料、铌酸钛材料、硅基材料和石墨中的一种；
    优选地，所述导电剂包括导电炭黑、导电石墨、Super P Li、科琴黑和碳纳米管中的一种；
    优选地，所述粘结剂包括聚偏氟乙烯、丁苯橡胶、羧甲基纤维素、聚丙烯酸、聚丙烯腈、聚乙烯醇、锂化聚乙烯醇；
    优选地，所述集流体为铝集流体或铜集流体。
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