method for recycling lithium ion batteries

专利摘要:
A method for recycling lithium ion batteries is provided which comprises isolating a mixture of anode and cathode materials from spent lithium ion batteries. Separate electrode materials can easily be collected with a high recovery rate, providing a fast, effective and low-cost method for recycling electrode materials from spent lithium-ion batteries.
公开号:BR112018074702B1
申请号:R112018074702-5
申请日:2017-06-12
公开日:2020-11-03
发明作者:Kam Piu Ho；Ranshi WANG；Peihua SHEN
申请人:Grst International Limited；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] This invention relates to methods of recycling lithium ion batteries. BACKGROUND OF THE INVENTION
[002] In the past few decades, lithium-ion batteries (LIBs) have been widely used in various applications such as consumer electronics because of their superior energy density, long life type and discharge capacity. LIBs generally include an anode, an electrolyte and a cathode that contains lithium in the form of a lithium transition metal oxide.
[003] In recent years, LIBs are beginning to be used in significant quantities for automotive propulsion as these batteries can provide many years of reliable service and are expected to last for around 10 years under normal drive conditions. LIBs can subsequently be used for storage of utility energy and are eventually considered to have reached the end of their useful life.
[004] Environmental issues of spent LIBs have attracted widespread public concern. If usable materials can be recovered from used batteries, it will be necessary to extract less raw materials from limited sources in the soil. In addition, significant negative environmental impacts caused by mining and ore processing (for example, SOX emissions from the melting of sulphide ores, such as those yielding copper, nickel and cobalt) are avoided if the used LIBs can be recycled.
[005] Currently, methods for recycling spent LIBs can be divided into two broad types: leaching method and method of combining calcination and leaching. The leaching method generally includes steps of grinding or cutting the battery, acid leaching, separation of materials leached by precipitation, complexation and / or extraction. However, leaching involves complex leaching composition and multiple separation steps creating large amounts of secondary waste.
[006] Method of combining calcination and leaching includes steps of grinding or cutting the battery, calcining, leaching with acid, separating the leached materials, etc. However, this method has the additional disadvantage of high energy consumption caused by the heat treatment process. In addition, the recovery rate of the electrode materials is low as some components of the electrode materials are burned in carbon dioxide and other harmful substances.
[007] Different attempts have been made to solve the problems and improve the performance of the recycling process. Patent publication No. CN 104577246 A describes a method of recycling LIB cathode and anode materials. However, the method is time-consuming and complicated as the recycling method requires removing the battery case.
[008] Patent publication No. CN 103449395 A discloses a method for recycling a cathode material from lithium iron phosphate batteries. However, the method requires a step of meticulously dismantling lithium iron phosphate batteries to obtain undamaged cathode plates and is limited to lithium iron phosphate batteries.
[009] Patent No. CN 101318712 B discloses a method for recovering cobalt from LIBs. However, the recycled content is only limited to LiCoθ2 and not applicable to other cathode materials.
[0010] Patent publication No. CN 104409792 A discloses a method for recovering cobalt from LIBs. The method comprises a step of separating materials of different densities based on a method of sinking and flotation in which a heavier fraction sinks to the bottom and a lighter fraction floats. This fluctuation system, although conceptually very simple, suffers from numerous disadvantages. When the solid material is wetted with water or an aqueous liquor, some of the light and heavy particles flocculate to form aggregates. And therefore, a portion of the suspended solid particles containing LiCoCb and carbon powder will settle and be removed when the heavier fraction is separated, thus complicating the separation process. In addition, the method is time-consuming and uneconomical since the lightest fraction, the heaviest fraction and the suspended solid particles need to be removed sequentially. In addition, the recycled content is also limited to LiCoCh and not applicable to other cathode materials.
[0011] In view of the above, there is always a need to develop a method to recycle LIBs with high recovery, high efficiency and low cost in mild conditions. In particular, a clean method for recycling LIBs is necessary to reduce air and water pollution formed in the recycling process. SUMMARY OF THE INVENTION
[0012] The aforementioned needs are met by several aspects and modalities revealed in this document. In one aspect, a method for recycling lithium-ion batteries is provided herein, which comprises the steps of: a) discharging lithium-ion batteries; b) cutting lithium ion batteries into pieces to provide a mixture of a structural part, a first part of conductive metal coated with a cathode layer and a second part of conductive metal coated with an anode layer; c) immerse the pieces of the cut lithium ion batteries in a polar solvent to form a heterogeneous mixture; d) process the heterogeneous mixture with mechanical stirring for a period of time from about 30 minutes to about 5 hours to dissolve a binder material in the cathode and anode layers; e) filtering the heterogeneous mixture processed to separate the structural part, the first conductive metal part and the second conductive metal part from thinner electrode materials comprising cathode and anode materials to provide a suspension with polar solvent and thinner electrodes; and f) isolating the finest electrode materials in the polar solvent suspension; g) that the polar solvent is water, alcohol, ketone or a combination thereof; wherein the cathode material is a lithium transition metal oxide selected from the group consisting of LiCoCE, LiNiCE, LiNixMnyθ2, LiNixCoyCh, Lii + zNixMnyCoi_x_yO2, LiNixCoyAlzθ2, LÍV2O5, LITHS2, LiHNH2 , LiFeCE, LiFePCU and combinations thereof; where each x is independently 0.3 to 0.8; each y being independently from 0.1 to 0.45; and each z is independently from 0 to 0.2; and wherein the binder material in each of the cathode and anode layers is independently a water-based binder material or a mixture of water-based and organic-based binder materials.
[0013] In some embodiments, lithium-ion batteries are cut by a waterjet cutting machine or a device with indentations or blades. In certain embodiments, the cut lithium-ion battery pieces have an average length of about 1.27 cm (0.5 inch) to about 10.16 cm (4.0 inches). In other embodiments, the cut lithium-ion battery pieces have an average length of about 0.635 cm (a quarter of an inch) or less.
[0014] In certain modalities, each of the first and second conducting metal parts is independently selected from the group consisting of a thin aluminum plate, a thin copper plate, a thin gold plate, a thin silver plate and a thin platinum plate.
[0015] In some embodiments, the polar solvent is water. In other embodiments, the polar solvent is a mixture of water and an alcohol. In additional modalities, alcohol is selected from methanol, ethanol, isopropanol, n-propanol, t-butanol or a combination thereof. In further embodiments, a water to alcohol weight ratio is from about 5:95 to about 95: 5.
[0016] In certain embodiments, the polar solvent is a mixture of water and ketone. In additional embodiments, the ketone is selected from acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone and methyl propyl ketone or a combination thereof. In further embodiments, a water to weight ratio of the ketone is from about 5:95 to about 95: 5.
[0017] In some embodiments, the polar solvent is a buffer solution that comprises a salt selected from the group consisting of lithium carbonate, lithium bicarbonate, lithium phosphate, sodium carbonate, sodium bicarbonate, sodium phosphate , potassium carbonate, potassium bicarbonate, potassium phosphate, ammonia carbonate, ammonium bicarbonate, ammonium phosphate and combinations thereof. In certain embodiments, the buffer solution has a pH of about 6 to about 8.
[0018] In certain modalities, the mechanical agitation step is performed by agitation, vibration, ultrasonication, vortexing or a combination thereof. In some embodiments, the mechanical stirring step is performed by a dispersion blade mixer, a stirring mixer, a screw mixer, a conical screw mixer, a planetary stirring mixer, an air jet mixer, a mixer high shear, an ultrasonic bath, an ultrasonic probe or a combination thereof.
[0019] In some embodiments, the heterogeneous mixture in step d) is heated at a temperature of about 35 ° C to about 100 ° C. In some embodiments, the heterogeneous mixture in step d) is heated to a temperature of about 55 ° C to about 75 ° C.
[0020] In some embodiments, the water-based binder material is selected from the group consisting of styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile-butadiene rubber, nitrile and butadiene rubber, copolymer of acrylonitrile-styrene-butadiene, acrylic rubber, butyl rubber, fluorine rubber, polytetrafluoroethylene, polyethylene, polypropylene, ethylene / propylene copolymers, polybutadiene, polyethylene oxide, chlorosulfonated polyethylene, polyvinylpyrrolidone, polyvinylpyridine, polyvinylpyridine, polyvinylpyridine, polyvinylpyridine, polyvinylpyridine, polyvinylpyridine, polyvinylpyridine, polyvinylpyridine, polyvinylpyridine, polyvinylpyridine, polyvinylpyridine, , polyphosphazene, polyacrylonitrile, polystyrene, latex, acrylic resins, phenolic resins, epoxy resins, carboxymethyl cellulose, hydroxypropyl cellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethyl cellulose, cyanoethylaccharide, polyether ethyl acetate polyimide, polycarboxylate, polycarboxylic acid, p acid oliacrylic, polyacrylate, polymethacrylic acid, polymethacrylate, polyacrylamide, polyurethane, fluorinated polymer, chlorinated polymer, an alginic acid salt and combinations thereof.
[0021] In certain embodiments, the organic-based binder material is selected from the group consisting of polytetrafluoroethylene (PTFE), perfluoroalkoxy polymer (PFA), polyvinylidene fluoride (PVDF), tetrafluoroethylene (TFE) copolymer and hexafluoropropylene ( HFP), fluorinated ethylene-propylene (FEP) copolymer, tetrafluoroethylene terpolymer, hexafluoropropylene and vinylidene fluoride and combinations thereof.
[0022] In some embodiments, the finer electrode materials additionally comprise a conductive agent.
[0023] In certain embodiments, the cathode material is LiNiCE, LiNixMnyO2, LiNixCoyCE, Lii + zNixMnyCoi_x_yO2, LiNixCoyAlzθ2 and combinations thereof; where each x is independently 0.5 to 0.8; each y being independently 0.1 to 0.4; and each z is independently from 0 to 0.2.
[0024] In some embodiments, the anode material is a carbonaceous material.
[0025] In certain embodiments, the finer electrode materials are filtered by passing through a sieve having a mesh width between 2 mm and 4 mm. In certain embodiments, the finer electrode materials are filtered by passing through a sieve having a mesh width between 0.5 mm and 1.0 mm.
[0026] In some modalities, the insulation of the finer electrode materials is carried out through filtration, decantation, sedimentation, centrifugation or a combination thereof.
[0027] In certain embodiments, the recovery of finer electrode material is at least 90% or at least 95%. In some embodiments, the percentage of impurity in the finer recovered electrode material is less than 2%, less than 1%, less than 0.5%, less than 0.1% or less than 0.05 %. BRIEF DESCRIPTION OF THE DRAWINGS
[0028] Figure 1 illustrates a modality of the method revealed in this document.
[0029] Figure 2 is a schematic view showing a modality of a high shear mixer. DETAILED DESCRIPTION OF THE INVENTION GENERAL DEFINITIONS
[0030] The term "mechanical agitation" refers to the application of kinetic energy in a solid mixture in contact with a liquid in order to facilitate the wetting of the solid mixture into the liquid. Some non-limiting examples of mechanical agitation include mixing, agitation, vibration, ultrasonication, vortexing and combinations thereof.
[0031] The term "waterjet cutting machine" or "waterjet cutter" refers to a tool capable of cutting a wide variety of materials using a water jet as very high pressure.
[0032] The term "heterogeneous mixture" refers to a mixture of two or more phases.
[0033] The term "electrode" refers to a "cathode" or an "anode".
[0034] The term "positive electrode" is used interchangeably with cathode. Likewise, the term “negative electrode” is used interchangeably with anode.
[0035] The term "binding material" refers to a chemical or substance used to retain an electrode material and / or a conductive agent in its place and adhere them to a conductive metal part to form an electrode. In some embodiments, the electrode does not comprise any conductive agent.
[0036] The term "water-based binder material" refers to a water-soluble or dispersive binding polymer! in water. Some non-limiting examples of water-based binder material include styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylic rubber, butyl rubber, fluorine rubber, polytetrafluoroethylene, polyethylene, polypropylene, ethylene / propylene copolymers, polybutadiene, polyethylene oxide, polyvinylpyrrolidone, polycyclohydrin, polyphosphazene, polyacrylonitrile, polystyrene, ethylene / propylene / diene copolymers, polyvinylpyridine, polyethylene chlorides, polyvinyl resins, polyvinyl resins, polyvinyl resins , carboxymethyl cellulose, hydroxypropyl cellulose and combinations thereof.
[0037] The term "organic-based binder material" refers to a binder soluble or dispersible in an organic solvent, in particular, N-methyl-2-pyrrolidone (NMP). Some non-limiting examples of organic-based binder material include polytetrafluoroethylene (PTFE), perfluoroalkoxy polymer (PFA), polyvinylidene fluoride (PVDF), tetrafluoroethylene (TFE) copolymer and hexafluoropropylene (HFP), fluoroethylene-propylene (fluoroethylene-propylene) , tetrafluoroethylene terpolymer, hexafluoropropylene and vinylidene fluoride and combinations thereof.
[0038] The term "conductive metal part" refers to a support for coating an electrode material and / or a conductive agent. Some non-limiting examples of the conductive metal part include a thin aluminum plate, a thin copper plate, a thin gold plate, a thin silver plate and a thin platinum plate.
[0039] The term "conducting agent" refers to a material that is chemically inactive and has good electrical conductivity. Therefore, the conductive agent is often mixed with an active electrode material at the time of forming an electrode to improve the electrode's electrical conductivity. In some embodiments, the conducting agent is a carbonaceous material.
[0040] The term "carbonaceous material" refers to any material that includes at least 50 mol% of carbon. Some non-limiting examples of carbonaceous material include soft carbon, rigid carbon, coke, graphite, carbon nanotubes, carbon fibers, graphite fibers, carbon nanofibers, graphite nanofibers, carbon black, activated carbon and combinations thereof.
[0041] The term "ultrasonic cleaner" refers to equipment that can apply ultrasound energy to agitate particles in a sample. Any ultrasonic cleaner that can disperse the heterogeneous mixture that can be used in this document. Some non-limiting examples of the ultrasound include an ultrasonic bath and a probe-type ultrasound.
[0042] The term "ultrasonic bath" refers to an apparatus through which ultrasonic energy is transmitted through the wall of the ultrasonic bath container in the sample liquid.
[0043] The term "probe-type ultrasound" refers to an ultrasonic probe immersed in a medium for direct ultrasound. The term "direct ultrasound" means that the ultrasound is directly coupled to the processing liquid.
[0044] The term "dispersion blade mixer" refers to a mixer comprising a vessel and a rotational cutting member having at least one blade. The blade has at least one sharp edge. In some embodiments, the rotational cutting member has a substantially vertical axis of rotation. Rotational speed can be expressed in units of revolutions per minute (rpm) which refers to the number of revolutions that a rotating body completes in one minute.
[0045] The term "stirring mixer" refers to a mixer comprising a vessel and a rotating member having at least one arm. In some embodiments, the arm is rod-shaped, paddle-shaped or plate-shaped.
[0046] The term "screw mixer" refers to a mixer comprising a vessel and a vertical mixing screw arranged in the center of the vessel. The vessel can be cylindrical, spherical or conical.
[0047] The term “conical screw mixer” refers to a mixer that comprises a vessel that tapers towards the bottom region and at least one rotationally driven mixing screw that moves in parallel and along the internal wall of the vase.
[0048] The term “planetary mixer” refers to equipment that can be used to mix or mix different materials to produce a homogeneous mixture, which consists of a single or double blade with a high speed dispersion blade.
[0049] The term "air jet mixer" refers to a mixer comprising the container having perforated walls and a plurality of nozzles from which liquid or compressed gas is ejected towards the material in the container.
[0050] The term "impact crusher" refers to an apparatus comprising a housing, a rotor assembly and a plurality of anvils positioned around the rotor assembly and configured to break the material. The rotor assembly uses centrifugal forces to launch the material at high speeds and, upon contact with the housing or anvil wall, the material breaks. The process is repeated until the broken material is discharged from the outlet. Some non-limiting examples of impact crusher include horizontal impact crusher and vertical impact crusher.
[0051] The term "room temperature" refers to a temperature of about 18 ° C to about 30 ° C, for example, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 ° C.
[0052] In the following description, all figures disclosed in this document are approximate values, regardless of whether the word "about" or "near" is used in connection with them. These numbers can vary by 1 percent, 2 percent, 5 percent, or sometimes 10 to 20 percent. If a numerical range with a lower limit, RL and an upper limit, Ru, is revealed, any number that falls within the range is specifically revealed. In particular, the following numbers within the range are specifically revealed: R = Rl + k (R "-Rl ;, where k is a variable that ranges from 1 percent to 100 percent with an increase of 1 percent, ie is, k is 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, ..., 50 percent, 51 percent, 52 percent, ..., 95 percent, 96 percent percent, 97 percent, 98 percent, 99 percent on 100 percent In addition, any numerical range defined by two or more R numbers as defined above is also specifically revealed.
[0053] A method for recycling lithium ion batteries is provided in this document which comprises the steps of: a) discharging lithium ion batteries; b) cutting lithium ion batteries into pieces to provide a mixture of a structural part, a first part of conductive metal coated with a cathode layer and a second part of conductive metal coated with an anode layer; c) immerse the pieces of the cut lithium ion batteries in a polar solvent to form a heterogeneous mixture; d) process the heterogeneous mixture with mechanical stirring for a period of time from about 30 minutes to about 5 hours to dissolve a binder material in the cathode and anode layers; e) filtering the heterogeneous mixture processed to separate the structural part, the first conductive metal part and the second conductive metal part from thinner electrode materials comprising cathode and anode materials to provide a suspension with polar solvent and thinner electrodes; and f) isolating the finest electrode materials in the polar solvent suspension; g) that the polar solvent is water, alcohol, ketone or a combination thereof; where the cathode material is a lithium transition metal oxide selected from the group consisting of LiCoCh, LiNiCh, LiNixMuyCh, LiNixCoyCh, Lii + zNixMnyCoi.x.yO2, LiNixCoyAlzO2, LÍV2O5, LÍÍSS2, LiÍS , LiMn2O4, LiFeCh, LiFePCh and combinations thereof; where each x is independently 0.3 to 0.8; each y being independently from 0.1 to 0.45; and each z is independently from 0 to 0.2; and wherein the binder material in each of the cathode and anode layers is independently a water-based binder material or a mixture of water-based and organic-based binder materials.
[0054] The present invention is intended to overcome the disadvantages of conventional recovery methods, to provide methods for recycling lithium ion batteries having greater efficiency, low cost and ease of handling. In accordance with the present invention, a method for recycling lithium ion batteries in a simple and easy manner with high efficiency can be provided.
[0055] Figure 1 is a flow chart that illustrates a modality of a process for recycling used lithium ion batteries. The present invention simplifies the process of recycling spent lithium-ion batteries and reduces operating costs.
[0056] Before recycling, lithium-ion batteries are discharged as the charge can remain stored in the batteries. In some embodiments, the remaining charge stored in the batteries is discharged by soaking the batteries in an aqueous solution containing a conductive salt. In certain embodiments, the aqueous solution is neutral or alkaline. Unloading provides an advantage with the ability to guarantee safety.
[0057] In some embodiments, the conductive salt is or comprises an alkali metal bicarbonate, such as sodium bicarbonate (NaHCO,) and potassium bicarbonate (KHCO3), an alkali metal carbonate, such as sodium carbonate (Na ^ CCF) and potassium carbonate (K2CO3), an alkaline earth metal carbonate, such as calcium carbonate (CaCCE) and magnesium carbonate (MgCCb), an alkali metal hydroxide, such as sodium hydroxide (NaOH) and hydroxide potassium (KOH), an alkaline earth metal hydroxide, such as calcium hydroxide (Ca (OH) 2), magnesium hydroxide (Mg (0H) 2) or an alkali metal or alkaline earth metal halides, such such as sodium chloride (NaCl) and calcium chloride (CaCh) or a combination thereof.
[0058] Electrical resistance of the aqueous solution can be regulated. Too little resistance of the solution leads to the risk of discharging too quickly. On the other hand, very high resistance will make the download time very long. In certain embodiments, the resistance solution can fall within a range of about 0.1 Ω to about 10 kΩ by regulating the concentration of the aqueous solution.
[0059] In certain embodiments, a total molar concentration of the conductive salt in the aqueous solution is about 1 mol / 1 to about 5 mol / 1, from about 1 mol / 1 to about 4 mol / 1, about from 1 mol / 1 to about 3 mol / 1, from about 2 mol / 1 to about 5 mol / 1, from about 2 mol / 1 to about 4 mol / 1, from about 2 mol / 1 at about 3 mol / 1 or from about 4 mol / 1 to about 5 mol / 1. Within this range, safe and controlled discharge of batteries can be achieved. In other embodiments, the aqueous solution for unloading does not comprise any conductive salt.
[0060] In some embodiments, the batteries can be punctured before being soaked in the aqueous solution. Drilled hole can be formed by impact punching, sawn blade cutting or any other means of mechanical drilling of the housing and battery pack housing.
[0061] Discharged batteries are then cut into pieces to provide a mixture of a structural part, a first part of conductive metal coated with a cathode layer and a second part of conductive metal coated with an anode layer.
[0062] In certain embodiments, lithium-ion batteries are cut by a waterjet cutting machine or a device with indentations or blades. The operation of the cutting machine can be monitored by a computer and the speed of the cutting machine can therefore be automatically adjusted to ensure that the resulting battery pieces are the desired size. In some embodiments, lithium ion batteries are disassembled to isolate the cathode electrode and anode electrode. In certain embodiments, lithium ion batteries undergo heat treatment at a temperature in the range of about 100 ° C to about 600 ° C before cutting. In some embodiments, lithium-ion batteries do not undergo heat treatment before cutting.
[0063] A cathode for a secondary lithium battery can have a structure in which a cathode layer is formed in a first conductive metal part. An anode for a secondary lithium battery can have a structure in which an anode layer is formed in a second conductive metal part. The conductive metal part acts as a current collector. Any metal having excellent electron conductivity in order to operate since the current collector can be used in this document.
[0064] In some modalities, each of the first and second conductive metal parts is independently selected from the group consisting of a thin aluminum plate, a thin copper plate, a thin gold plate, a thin silver plate and a thin platinum plate. In certain embodiments, the first conductive metal part is a thin aluminum plate. In some embodiments, the second conducting metal part is a thin copper plate.
[0065] Each battery is cut by the cutting machine into smaller pieces. In certain embodiments, the cut lithium-ion battery pieces have an average length of about 1.27 cm (0.5 inch) to about 10.16 cm (4.0 inches). In some embodiments, the cut lithium-ion battery pieces have an average length of about 0.635 cm (a quarter of an inch) or less.
[0066] The method disclosed in this document does not involve a disassembly step. Therefore, a large amount of work can be processed without disassembly.
[0067] One of the biggest challenges of recycling is that the recycling process itself creates even more toxic chemicals due to the use of many toxic and volatile organic solvents, contributing to pollution. Consequently, it is highly desirable to develop environmentally friendly recycling processes that can be conducted in an aqueous medium or water. Furthermore, using aqueous medium or water as a solvent offers many advantages, such as simple operation.
[0068] The recycling method disclosed in this document is non-toxic and environmentally friendly. The pieces of the cut lithium-ion batteries are then immersed in a polar solvent to form a heterogeneous mixture. In some embodiments, the polar solvent means a solution that contains water and that may contain an alcohol or the like in addition to water. In certain embodiments, the amount of water is at least 1%, at least 2%, at least 3%, at least 4%, at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95% for the total amount of water and solvents other than water. In some modalities, the amount of water is at most 1%, at most 2%, at most 3%, at most 4%, at most 5%, at most 10%, at most 15%, at most 20%, maximum 25%, maximum 30%, maximum 35%, maximum 40%, maximum 45%, maximum 50%, maximum 55%, maximum 60%, maximum 65%, maximum 70%, maximum 75%, maximum 80%, maximum 85%, maximum 90% or maximum 95% for the total amount of water and solvents other than water. On the other hand, the upper limit is so that the solvent consists only of water, that is, the proportion of water is 100% by volume.
[0069] In certain embodiments, a weight ratio of water to alcohol is about 99: 1 to about 1:99, about 95: 5 to about 5:95, about 10: 1 to about 1:10, about 10: 1 to about 1: 1, about 8: 1 to about 3: 1, about 5: 1 to about 3: 1, about 4: 1 to about 2: 1 or about 3: 1 to about 1: 3. In some embodiments, the water to alcohol ratio is about 1:10, 1: 9, 1: 8, 1: 7, 1: 6, 1: 5, 1: 4, 1: 3, 1: 2, 1: 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1 or 10: 1.
[0070] Some non-limiting examples of alcohol include C2-C4 alcohols, methanol, ethanol, isopropanol, n-propanol, t-butanol and combinations thereof.
[0071] Some non-limiting examples of solvents other than water include lower aliphatic ketones, such as acetone, dimethyl ketone, methyl ethyl ketone, etc .; other solvents such as ethyl acetate, isopropyl acetate, propyl acetate; and combinations thereof. In some embodiments, the volatile solvent component is methyl ethyl ketone, ethanol, ethyl acetate or a combination thereof.
[0072] In some embodiments, the polar solvent is a mixture of water and ketone. In additional embodiments, the ketone is selected from acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone and methyl propyl ketone or a combination thereof. In further embodiments, a water to weight ratio of the ketone is from about 5:95 to about 95: 5. In certain embodiments, the water to weight ratio for the ketone is about 1:10, 1: 9, 1: 8, 1: 7, 1: 6, 1: 5, 1: 4, 1: 3, 1: 2, 1: 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1 or 10: 1.
[0073] In certain embodiments, the polar solvent used to immerse the pieces of the cut lithium ion batteries is water. Some non-limiting examples of water include tap water, bottled water, purified water, pure water, distilled water, deionized water, D2O or a combination thereof. In some embodiments, the polar solvent is deionized water. In certain embodiments, the pH of water is about 6.5 to about 7.5. In some embodiments, the water pH is about 7.
[0074] In certain embodiments, the polar solvent is not an organic solvent or a mixture of water and organic solvent. In some embodiments, the polar solvent is not an alcohol, acetone or ether. In certain embodiments, the polar solvent is not N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, formic acid, ethanoic acid, oxalic acid or citric acid. In some embodiments, the polar solvent does not contain an acid or a base.
[0075] In some embodiments, the polar solvent is a buffer solution comprising a salt selected from the group consisting of lithium carbonate, lithium bicarbonate, lithium phosphate, sodium carbonate, sodium bicarbonate, sodium phosphate , potassium carbonate, potassium bicarbonate, potassium phosphate, ammonia carbonate, ammonium bicarbonate, ammonium phosphate and combinations thereof. In certain embodiments, the buffer solution has a pH of about 6 to about 8. In some embodiments, the polar solvent is not a buffer solution.
[0076] In certain modalities, the heterogeneous mixture is processed to assist the dissolution of agglutinating material under mechanical agitation. Any suitable method can be used to stir the heterogeneous mixture. Some non-limiting examples of adequate agitation can be carried out through mechanical agitation, magnetic agitation, vibration, ultrasonication, vortexing and combinations thereof.
[0077] In some embodiments, mechanical agitation is performed by an ultrasound machine. Any ultrasound that can apply ultrasound energy to agitate particles in a sample can be used in this document. In some embodiments, the ultrasonic cleaner is a probe-type ultrasonic cleaner or an ultrasonic bath.
[0078] In certain embodiments, the ultrasound is operated at a power density of about 10 W / l to about 100 W / l, about 40 W / l to about 60 W / l, about 20 W / about 100 W / l, about 30 W / l to about 100 W / l, about 40 W / l to about 80 W / l, about 40 W / l to about 70 W / l, about 40 W / l to about 50 W / l or about 50 W / l to about 60 W / l.
[0079] An advantage of ultrasonic agitation is that it reduces processing time. However, during scale-up, the problem mainly refers to the unsatisfactory transmission of the ultrasound. The range of ultrasonication should be increased when working with large quantities of samples. That is, since the amount of sample increases, so does the resistance of the sample to the movement of the ultrasound wave. Therefore, a high amplitude (ie, high intensity) is necessary to obtain the necessary mechanical vibration.
[0080] However, the high ultrasound range can lead to rapid deterioration of the ultrasonic transducer, resulting in unsatisfactory transmission of the ultrasound through the liquid medium. This problem becomes more serious when a larger container is used. On the other hand, the investment costs for ultrasonic equipment for large-scale operations are high and the energy costs are also higher than mechanically agitated processing.
[0081] In some embodiments, the heterogeneous mixture can be mechanically stirred. In certain embodiments, the heterogeneous mixture can be ultrasonically stirred. In some embodiments, mechanical stirring is performed by a stirrer in a vessel or tank. Some non-limiting examples of the agitator include a dispersing blade mixer, a stirring mixer, a planetary stirring mixer, a screw mixer, a conical screw mixer and a high shear mixer. In certain embodiments, the heterogeneous mixture can be mechanically stirred by an air-jet mixer. In some embodiments, the stirring device is not an ultrasonic cleaner, a dispersion blade mixer, a stirring mixer, a planetary stirring mixer, a screw mixer, a conical screw mixer, a high shear mixer or a mixer by air jet.
[0082] The main advantage of using mechanical agitation is that it allows reliable scale expansion from laboratory scale to pilot or large scale. Other advantages of mechanical agitation are simple mechanical construction, simple maintenance and lower operating costs, particularly reduced energy and cooling water costs, since the use of mechanical agitation would decrease the cooling water requirements.
[0083] In some embodiments, mechanical agitation can be performed for a period of time sufficient to detach electrode materials from the conductors of the metal part. In certain embodiments, the time period is about 1 hour to about 10 hours, about 1 hour to about 8 hours, about 1 hour to about 6 hours, about 1 hour to about 4 hours, about 1 hour to about 3 hours, about 1 hour to about 2 hours, about 2 hours to about 6 hours, about 15 minutes to about 2 hours or about 30 minutes to about 2 hours. In some embodiments, the time period is at least about 30 minutes, at least about 1 hour, at least about 2 hours, at least about 3 hours, at least about 4 hours, at least about 5 hours at least about 6 hours, at least about 7 hours, at least about 8 hours, at least about 9 hours, or at least about 10 hours. In certain embodiments, the time period is less than about 10 hours, less than about 9 hours, less than about 8 hours, less than about 7 hours, less than about 6 hours, less than about 5 hours, less than about 4 hours, less than about 3 hours, less than about 2 hours or less than about 1 hour.
[0084] Generally, when mechanical stirring is performed by a differently shaped shaker such as stirring mixer and the stirring time is less than 30 minutes, the amount of dissolving binder material is relatively small and large quantities electrode materials still adhere to the metal part conductors. This eventually decreases the amount of electrode materials recovered. This is particularly true when the scale of LIB recovery is increased.
[0085] In some embodiments, the heterogeneous mixture is soaked in a polar solvent for a period of time from about 1 hour to about 5 hours before being mechanically stirred. In other embodiments, the heterogeneous mixture is not soaked before being mechanically stirred. It has been found that soaking in polar solvent such as water alone is not sufficient to remove the electrode layers from the metal part conductors and soaking before mechanical stirring does not increase recovery.
[0086] Mechanical agitation is crucial for removing the electrode layers from the metal part conductors. Shear force produced in the mixer is required to separate the electrode layers from the conductors of the metal part. The separation of the electrode layers from the metal part conductors is also aided by collision between battery fragments.
[0087] In some embodiments, the agitator is a dispersion blade mixer. In certain embodiments, the spreader blade mixer comprises at least one blade with a sharp edge disposed in the center of the mixer. In some embodiments, the spreading blade rotational speed is about 1,000 rpm to about 50,000 rpm, about 5,000 rpm to about 50,000 rpm, about 10,000 rpm to about 50,000 rpm or about 10,000 rpm at about 30,000 rpm. In certain embodiments, the rotational speed of the dispersion blade is about 1,000 rpm, about 5,000 rpm, about 10,000 rpm, about 30,000 rpm or about 50,000 rpm. In some embodiments, the rotational speed of the spreading blade is less than about 50,000 rpm, less than about 30,000 rpm, less than about 10,000 rpm or less than about 5,000 rpm.
[0088] In certain embodiments, when the heterogeneous solution is agitated by at least one blade, a strong transversal shear force is exerted on the conductive metal part coated by an anode / cathode layer by the sharp edges of the blade. The transverse shear force leads to the fragmentation of part of conductive metal coated by an anode / cathode layer into smaller pieces. As a result, thinner electrode material detached from the conductive metal part is similar in size to the conductive metal part. This makes the insulation of finer electrode material from the heterogeneous mixture sieving difficult. Significant amounts of structural part and conductive part are attached to the finer electrode material.
[0089] In some embodiments, plastic microspheres are added to the heterogeneous mixture. Collisions between microspheres and electrode plates can improve the detachment of electrode materials from the electrodes and thus the recovery rate. Therefore, lower stirring speeds can be used to reduce the amount of impurity in the material collected from the finer electrode while still maintaining the recovery rate. After mechanical stirring the heterogeneous mixture, plastic microspheres can be filtered so as not to contaminate the finer electrode material.
[0090] In some embodiments, the mass ratio of the plastic microsphere to the cut battery is about 1:10 to about 1: 100, about 1:20 to about 1: 100, about 1:40 about 1: 100, about 1:60 to about 1: 100, or about 1:80 to about 1: 100. In certain embodiments, the mass ratio of the plastic microsphere to cut battery is about 1:10, about 1:20, about 1:30, about 1:40, about 1:60, about 1: 80 or about 1: 100. In some embodiments, the diameter of the plastic microsphere is about 0.1 mm to about 3 mm, about 0.1 mm to about 2 mm, about 0.1 mm to about 1 mm or about 0.1 mm to about 0.5 mm. In certain embodiments, the diameter of the plastic microsphere is about 0.1 mm, about 0.5 mm, about 1 mm, about 2 mm or about 3 mm. In some embodiments, the diameter of the plastic microsphere is less than about 3 mm, less than about 2 mm, less than about 1 mm, less than about 0.5 mm or less than about 0 , 1 mm.
[0091] In certain embodiments, the agitator is a stirring mixer. In some embodiments, the stirring mixer comprises at least one rod-shaped blade arranged in the center of the mixer. In certain embodiments, the rotational speed of the stirring mixer is about 50 rpm to about 3,000 rpm, about 50 rpm to about 2,000 rpm, about 50 rpm to about 1,500 rpm, about 50 rpm at about 1,000 rpm, from about 50 rpm to about 500 rpm, or from about 50 rpm to about 200 rpm. In some embodiments, the rotational speed of the stirring mixer is about 50 rpm, about 100 rpm, about 200 rpm, about 500 rpm, about 1,000 rpm, about 1,500 rpm, about 2,000 rpm or about 3,000 rpm.
[0092] In some embodiments, the agitator is a planetary agitation mixer. In certain embodiments, the planetary stirring mixer comprises at least one single or double planetary blade with at least one high speed dispersion blade. In certain embodiments, the rotational speed of the high-speed dispersion blade is about 500 rpm to about 2,500 rpm, about 1,000 rpm to about 3,000 rpm, about 1,000 rpm to about 2,500 rpm, about from 1,500 rpm to about 2,500 rpm or from about 2,000 rpm to about 2,500 rpm. In some embodiments, the rotational speed of the planetary blade is from about 20 rpm to about 150 rpm, from about 30 rpm to about 100 rpm, from about 50 rpm to about 300 rpm, from about 50 rpm to about 200 rpm, about 100 rpm to about 300 rpm or about 200 rpm to about 300 rpm.
[0093] In certain embodiments, the agitator is a screw mixer. In some embodiments, the screw is either a left-side screw or a right-side screw. In certain embodiments, the screw rotates clockwise or counterclockwise around its vertical geometric axis. In some embodiments, the rotational speed of the screw is about 100 rpm to about 1,000 rpm, about 100 rpm to about 800 rpm, about 100 rpm to about 600 rpm, about 100 rpm to about 400 rpm or from about 100 rpm to about 200 rpm.
[0094] In some embodiments, the agitator is a conical screw mixer. In certain embodiments, the conical screw mixer comprises a screw. In other embodiments, the conical screw mixer comprises two screws. In certain embodiments, the tapered screw mixer comprises at least one arm extending from the center to the periphery of the mixer. The screw is extended from the end of the arm and angled downward along the periphery of the mixer. The arm can revolve around the conical screw mixer vessel and the screw can rotate around itself. In some embodiments, the arm's rotational speed is about 30 rpm to about 300 rpm, about 30 rpm to about 250 rpm, about 30 rpm to about 200 rpm or about 50 rpm to about 150 rpm. In certain embodiments, the rotational speed of the screw is from about 100 rpm to about 1,000 rpm, from about 100 rpm to about 800 rpm, from about 100 rpm to about 600 rpm, from about 100 rpm to about 400 rpm or from about 100 rpm to about 200 rpm.
[0095] In some embodiments, the stirring mixer is an air jet mixer. In certain embodiments, air jet is ejected from the holes in the mixer wall. In some embodiments, the air jet pressure is from about 0.01 MPa to about 10 MPa, from about 0.01 MPa to about 1 MPa or from about 0.1 MPa to about 1 MPa. In certain embodiments, the water jet is ejected from the holes.
[0096] Generally, when a dispersion blade mixer is used, a satisfactory recovery rate can be obtained. However, the sharp edges of the blade will cut the materials in the heterogeneous mixture into small pieces. As a result, collected electrode materials are contaminated with impurities, such as part of conductive metal.
[0097] Using a stirring mixer, a screw mixer, a conical screw mixer, a planetary stirring mixer or an air jet mixer can result in electrode material with a lower impurity content compared to a blade mixer dispersion. However, surprisingly, the stirring system using a planetary stirring mixer or stirring mixer is not effective in removing the electrode layers comprising cathode material with high nickel such as LiNio.gCoo.isAlo.osCE (NCA) and LiNio, ohm, 2Coo, 202 (NMC622) of the metal part conductors. Prolonged agitation does not have a significant effect on improving effectiveness. The combined effect of agitation and ultrasonic agitation also showed no improvement. The corrosion of the aluminum current collector that arises from the high alkalinity of the aqueous cathode slurry is suspected to give rise to a stronger connection between the cathode electrode layer and the aluminum current collector. The shear force acting on the materials in the heterogeneous mixture is insufficient in the mechanical agitator mentioned above.
[0098] In some embodiments, the agitator is a high shear mixer. Figure 2 is a diagram illustrating an embodiment of a high shear mixer used to stir the heterogeneous mixture. The high shear mixer comprises a mixing vessel 9 which has an upper part 9a and a lower part which taper conically 9b. In certain embodiments, the upper part 9a is cylindrical or conical. The mixing vessel 9 comprises an inlet 8 in an upper part 9a for introducing small pieces of cut lithium ion batteries and an outlet 10 in the lower part 9b for discharging the heterogeneous mixture produced in the vessel.
[0099] The high shear mixer shown in Figure 2 comprises a screw 1 arranged vertically in the center of the mixing vessel 9. The screw 1 comprises a pivoting rod la and a spiral blade 1b wound in a spiral around the pivoting rod la 1. The rotating rod la of screw 1 is connected to a drive medium. In certain embodiments, the drive means is an electric motor 11. In some embodiments, the spiral blade 1b rotates around the rotating rod la of screw 1 counterclockwise from an axial end of screw 1. Therefore, through of the rotation of screw 1 in a clockwise direction (in the direction indicated by the arrow R2 in Figure 2), the mixing material M around screw 1 is propelled upwards. When material M is propelled upwards, it is propelled simultaneously in a centrifugal manner. As a result, screw 1 creates an upward, centrifugal flow of M material in its vicinity.
[00100] In some embodiments, the rotational speed of screw 1 is from about 500 rpm to about 2,500 rpm, from about 500 rpm to about 2,000 rpm, from about 500 rpm to about 1,500 rpm, about 1,000 rpm at about 2,500 rpm or from about 1,000 rpm at about 2,000 rpm. In certain embodiments, the rotational speed of screw 1 is about 500 rpm, about 1,000 rpm, about 1,500 rpm, about 2,000 rpm or about 2,500 rpm.
[00101] The high shear mixer comprises a rotating unit 2 for impelling the mixing material M in the centripetal and downward directions. In some embodiments, the high shear mixer comprises two or more rotating units 2. The rotating unit 2 comprises a cylindrical rotating rod 7 of the rotating unit 2 coaxially arranged around the rotating rod la of screw 1, a pair of rotating arms 6 which extend horizontally radially from the swivel rod 7 of the swivel unit 2, support bars 4 vertically extending from the swivel arms 6, stirrer vanes 3 held by the support bars 4 and rectifier plates 5 attached to the swivel unit 2. The reed of agitator 3 comprises an upper portion 3a flexed in direction relative to the direction of rotation of the rotating unit 2 in order to urge the material downward, a median portion 3b attached to the support bars 4 and an inclined lower portion 3c relative to the radial direction of in order to propel the material in a centripetal way. Stirrer vanes 3 extend along the inner wall of the mixing vessel 9.
[00102] The rectifier plate 5 is arranged between the screw 1 and the stirrer paddle 3 in order to impart a centripetal movement to the mixing material M. In certain embodiments, the rectifier plate 5 can be replaced with the structure having a bar of support 4 and a stirrer paddle 3 to increase the shear friction brought about by the collision of the mixing material M. In some embodiments, the rectifier plate 5 can be omitted. The rotating unit 2 is driven by an electric motor 12.
[00103] In some embodiments, the rotational speed of the rotating unit 2 is about 50 rpm to about 1,000 rpm, about 50 rpm to about 800 rpm, about 50 rpm to about 600 rpm, about from 50 rpm to about 500 rpm or from about 50 rpm to about 300 rpm. In some embodiments, the rotational speed of the rotating unit 2 is about 50 rpm, about 100 rpm, about 250 rpm, about 300 rpm, about 500 rpm or about 1,000 rpm.
[00104] In certain embodiments, the heterogeneous mixture is stirred in the high shear mixer for about 5 minutes to about 5 hours, about 5 minutes to about 3 hours, about 5 minutes to about 2 hours, about 5 minutes to about 1 hour, about 5 minutes to about 30 minutes, about 15 minutes to about 1 hour, about 30 minutes to about 5 hours, about 30 minutes to about 2 hours, about 30 minutes to about 1 hour, about 1 hour to about 5 hours, or about 2 hours to about 5 hours. In some embodiments, the heterogeneous mixture is stirred in the high shear mixer for less than about 2 hours, less than about 1 hour, less than about 30 minutes, less than about 20 minutes or less than about 10 minutes. In certain embodiments, the heterogeneous mixture is stirred in the high shear mixer for at least about 10 minutes, at least about 20 minutes, at least about 30 minutes, at least about 1 hour, at least about 2 hours, at least about 3 hours, at least about 4 hours or at least about 5 hours.
[00105] By rotating the screw 1 and the rotating unit 2 in opposite directions, the material in the vessel around the screw 1 is pushed up and out and the material around the stirrer paddle 3 is pushed down and inside. Therefore, the materials thus driven in a centrifugal and centripetal manner collide with each other in the region between the screw 1 and the stirrer blade 3 to form a region of high pressure between them. In this region, the materials are subjected to intense shearing friction. Since the heterogeneous mixture in the mixing vessel 9 can be effectively circulated by convection although it causes collisions between the fragments, the cathode electrode layer can be removed from the aluminum current collector in a short time with high efficiency. Additionally, since the detachment of the cathode layer from the conductive metal part originates from shear friction, the conductive metal part and structural part remains as recognizable pieces without being in pieces or fine particles. As a result, thinner electrode materials are obtained with low impurity. Another advantage of the high shear mixer is that the high recovery rate can be achieved in a short processing time, even during scaling. Any temperature that can process the heterogeneous mixture with mechanical stirring can be used in this document. In some embodiments, the binder material is water-based and soluble in cold water. In certain embodiments, the processing temperature is about 14 ° C, about 16 ° C, about 18 ° C, about 20 ° C, about 22 ° C, about 24 ° C or about 26 ° Ç. In certain embodiments, mechanical stirring can be carried out at room temperature. In some embodiments, mechanical stirring can be performed at a temperature below 30 ° C, below 25 ° C, below 22 ° C, below 20 ° C, below 15 ° C or below 10 ° C. After processing, the heterogeneous mixture, the cathode and anode layers are separated from the metal part conductors and the particles of the electrode materials fall from the electrode layers.
[00106] The separation efficiency can be increased by high temperatures. In certain embodiments, mechanical stirring can be carried out with heating at a temperature of about 35 ° C to about 100 ° C, from about 35 ° C to about 80 ° C, from about 35 ° C to about 60 ° C, about 35 ° C to about 50 ° C, about 55 ° C to about 100 ° C, about 55 ° C to about 75 ° C or about 55 ° C to about 65 ° C. After the heat treatment, due to the difference in thermal expansion between the cathode and anode layers and the metal part conductors, the cathode and anode layers can be easily separated from the metal part conductors. In certain embodiments, mechanical stirring is carried out at room temperature. In other embodiments, mechanical stirring is performed at a temperature less than 20 ° C, less than 25 ° C, less than 30 ° C, less than 35 ° C, less than 40 ° C, less than 50 ° C, less than 60 ° C, less than 70 ° C, less than 80 ° C, less than 90 ° C or less than 100 ° C.
[00107] In some embodiments, the bonding material is a mixture of water-based and organic-based bonding materials. Patent application no. U.S. 20130034651 A1 discloses that the organic based binder material such as PVDF can be used in a water based slurry for the manufacture of battery electrodes when the slurry comprises a combination of PVDF and other water based binder materials. It has been found that the method disclosed in this document is also applicable to that binder system and the cathode and anode layers can be separated from the metal part conductors.
[00108] However, it is difficult to dissolve binders with a purely organic base due to their low solubility in water. In this case, the adhesive resistance between the cathode and anode layers and the metal part conductors remains strong, and therefore the cathode and anode layers are less likely to be separated from the metal part conductors.
[00109] A positive electrode includes a layer of cathode supported on a first part of conductive metal. Typically, the first conductive metal part is an aluminum or other conductive / metallic foil substrate. The cathode layer contains at least one cathode material and a binder material. The cathode layer can further comprise a conducting agent to enhance the electron conductivity of the cathode layer. The positive electrode can include a significant amount of a binder material such as a polymeric binder and the binder material is used to attach the cathode material to the first conductive metal part.
[00110] A negative electrode includes an anode layer supported on a second part of conductive metal. Typically, the second conductive metal part is a copper or other conductive / metallic foil substrate. The anode layer contains at least one anode material and one binder material. The anode layer can further comprise a conductive agent to enhance electron conductivity of the anode layer. The negative electrode can include a significant amount of a binder material for connecting the anode material to the second conductive metal part.
[00111] In certain embodiments, the binding materials in the cathode and anode layers are the same or different. In some embodiments, the binder material is or comprises a water-based binder material or a mixture of water-based and organic-based binder materials. In certain embodiments, the binder material is not an organic-based binder material or a mixture of water-based binder material and organic-based binder material.
[00112] In certain embodiments, the water-based binder material is selected from the group consisting of unsaturated polymer, conjugated diene polymer, styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile-butadiene rubber , nitrile and butadiene rubber, acrylonitrile-styrene-butadiene copolymer, rubber, acrylic rubber, butyl rubber, fluorine rubber, polytetrafluoroethylene, polyolefin, polyethylene, polypropylene, ethylene / propylene copolymers, polybutylene, polyethylene oxide, polyethylene chloride , polyvinylpyrrolidone, polyvinylpyridine, polyvinyl compound, polyvinyl alcohol, polyvinyl acetate, polycyclohydrin, polyphosphazene, polyacrylonitrile, polystyrene, latex, acrylic resins, phenolic resins, epoxy resins, cellulose, acetyl cellulose, cellulose, acetyl cellulose, hydroxypropyl cellulose cellulose, cellulose acetate propionate, cyanoethylcellulose, c ianoethylsuccharose, polyester, polyamide, polyether, polyimide, polycarboxylate, polycarboxylic acid, polyacrylic acid, polyacrylate, polymethacrylic acid, polymethacrylate, polyacrylamide, polyurethane, halogenated polymer, fluorinated polymer, chlorinated polymer, a mixture of the same alginic acid.
[00113] Some non-limiting examples of the polyvinyl compound include those that consist of N-vinylamide monomers such as N-vinyl formamide or N-vinyl acetamide or that contain those monomers. The poly-N-vinyl compound is distinguished by good wettability. Homopolymers, copolymers and block copolymers can also be used in this document. In some embodiments, the polyvinyl compound is a random, block or alternating interpolymer. In additional embodiments, the polyvinyl compound is an interpolymer with two blocks, three blocks or with multiple blocks.
[00114] Some non-limiting examples of rubber include natural rubber, isoprene rubber, butadiene rubber, chloroprene rubber, styrene and butadiene rubber and nitrile and butadiene rubber. These rubbers contain unsaturated double bonds. In some embodiments, rubber is a random, block or alternating interpolymer. In additional modalities, the rubber is the interpolymer with two blocks, three blocks or with multiple blocks. Unsaturated polymers are generally distinguished by good adhesive properties.
[00115] In certain embodiments, the alginic acid salt comprises a cation selected from Na, Li, K, Ca, NH4, Mg, Al or a combination thereof.
[00116] In some embodiments, the water-based binder material is a monomer containing a carboxylic acid group, a sulfonic acid group or a combination thereof.
[00117] Some non-limiting examples of the monomer having a carboxylic acid group include monocarboxylic acid, dicarboxylic acid, dicarboxylic acid anhydride and derivatives thereof. Some non-limiting examples of monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-ethylacrylic acid and isocrotonic acid. Some non-limiting examples of dicarboxylic acid include maleic acid, fumaric acid, itaconic acid and methyl maleic acid. Some non-limiting examples of dicarboxylic acid anhydride include maleic anhydride, acrylic anhydride, maleic methyl anhydride and maleic dimethyl anhydride.
[00118] Some non-limiting examples of the monomer having a sulfonic acid group include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, (meth) acrylic acid-2-ethyl sulfonate, 2-acrylamide-2 acid -methylpropanesulfonic acid, 3-allyloxy-2-hydroxypropanesulfonic acid and 2- (N-acryloyl) amino-2-methyl-1,3-propane-disulfonic acid.
[00119] In some embodiments, the organic-based binder material is selected from the group consisting of polytetrafluoroethylene (PTFE), perfluoroalkoxy polymer (PFA), polyvinylidene fluoride (PVDF), tetrafluoroethylene (TFE) copolymer and hexafluoropropylene (TFE) HFP), fluorinated ethylene-propylene (FEP) copolymer, tetrafluoroethylene terpolymer, hexafluoropropylene and vinylidene fluoride and combinations thereof. In other embodiments, the organic-based binder material is not polytetrafluoroethylene (PTFE), perfluoroalkoxy polymer (PFA), polyvinylidene fluoride (PVDF), tetrafluoroethylene (TFE) copolymer and hexafluoropropylene (HFP), fluorinated ethylene-propylene (fluoroethylene-propylene) copolymer or terpolymer of tetrafluoroethylene, hexafluoropropylene fluoride and vinylidene.
[00120] In certain embodiments, the mass ratio of the water-based binder material to the organic-based binder material in the layer electrode is from about 10: 1 to about 1:10, from about 10: 1 to about from 1: 1, from about 10: 1 to about 2: 1, from about 10: 1 to about 4: 1, from about 10: 1 to about 6: 1 or from about 10: 1 about 8: 1. In some embodiments, the mass ratio of the water-based binder material to the organic-based material on the electrode layer is about 10: 1, about 8: 1, about 6: 1, about 4: 1, about 2: 1 or about 1: 1.
[00121] After dissolving the binder material, the processed heterogeneous mixture is filtered to separate the structural part, the first conductive metal part and the second conductive metal part from thinner electrode materials comprising cathode and anode materials to provide a suspension equipped with polar solvent and the finest electrode materials.
[00122] In certain embodiments, the finer electrode materials are filtered by passing through a sieve having a mesh width between 2 mm and 4 mm. In some embodiments, the finer electrode materials are filtered by passing through a sieve having a mesh width between 0.5 mm and 1.0 mm.
[00123] In some embodiments, the finer electrode materials additionally comprise a conductive agent. In that case, the suspension comprises the polar solvent and the finer electrode materials containing the anode and cathode materials and conductive agent.
[00124] In certain embodiments, the cathode material is lithium metal oxide. In additional modalities, the lithium metal oxide is selected from the group consisting of LiNiCE, Lii + zNixMnyO2, Lii + zNixMuyCoi x-yCh, Lii + zNixCoyAlzO2, LÍV2O5, LÍTÍS2, LÍM0S2, LiMnCE, LiCoθ2 (LM) , LiM ^ CU (LMO), LiFePCU (LFP) and combinations thereof, where each x is independently 0.3 to 0.8; each y being independently from 0.1 to 0.45; and each z is independently from 0 to 0.2.
[00125] In some embodiments, lithium metal oxide may include NMC (Lii + zNixMnyCoi_x_yO2) with various Ni: Mn: Co ratios, for example, 1: 1: 1; 5: 3: 2; 4: 4: 2; 8: 1: 1. In certain embodiments, the lithium metal oxide is LiNio, 33Mno, 33Cθo, 33θ2 (NMC333), LiNio, sMno, 3Cθo.2θ2 (NMC532), LiNi0.6Mno.2Cθo, 2θ2 (NMC622), LiNio, 8Mn0, iCo0, iθ2 (NMC811), LiNio, 8Cθo.i5Alo, o5θ2 (NCA) and combinations thereof. In other embodiments, lithium metal oxide is not LiNiCh, Lii + zNixMny02, Lii + zNixMnyCoi_x_yO2, Lii + zNixCoyAlzO2, LÍV2O5, LiTiS2, LÍM0S2, LiMnO2, LiCoh2, LiChn2 , 3 to 0.8; each y being independently from 0.1 to 0.45; and each z is independently from 0 to 0.2. In certain embodiments, the lithium metal oxide is not LiNio, 33Mno, 33Cθo, 33θ2 (NMC333), LiNio, sMno, 3Cθo, 2θ2 (NMC532), LiNio, omno, 2Coo, 202 (NMC622), LiNio, 8Mno, iCθo , iθ2 (NMC811) or LiNio, 8Cθo, i5Alo, o5θ2 (NCA).
[00126] In certain modalities, the anode material is selected from the group consisting of natural graphite particulate, synthetic graphite particulate, Sn particulate, Li4Ti50i2 particulate, Si particulate, Si-C composite particulate and combinations thereof.
[00127] In some embodiments, the conductive agent is a carbonaceous material. In certain embodiments, the carbonaceous material is soft carbon, rigid carbon, coke, graphite, carbon nanotubes, carbon fibers, graphite fibers, carbon nanofibers, graphite nanofibers, carbon black, activated carbon or a combination thereof.
[00128] After the filtering step, the finer electrode materials in the suspension are isolated from the polar solvent. The cathode material and anode material can be recycled simultaneously, therefore, simplifying the recycling method. Isolated electrode materials can be easily collected and the recycling rate of electrode materials is high.
[00129] The isolation of the finest electrode materials can be accomplished by a variety of methods known in the art including, but not limited to, filtration, settling, sedimentation and centrifugation.
[00130] In some embodiments, the finer electrode materials in the suspension can be collected from the polar solvent through filtration. Suitable filtration methods include gravity filtration, pressure filtration or vacuum filtration.
[00131] When the amount of battery fragments in the heterogeneous mixture is large and the mechanical stirring time is very long (for example about 5 hours), it is observed that the water-based binder material can form a colloid that tends to form flakes when the amount of battery fragments in the heterogeneous mixture is large. In this way, the sieve holes tend to quickly become clogged with the colloid. As a result, the screen becomes partially or totally inoperative. Surprisingly, the use of a buffer solution suppresses the formation of the colloid. Therefore, the time required for the relevant process can be shortened and the filtering efficiency has improved.
[00132] In some embodiments, the recovery of finer electrode material is at least 80%, at least 85%, at least 90% or at least 95%. In certain embodiments, the recovery of thinner electrode material is about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98% or about 99%.
[00133] In some embodiments, the percentage of impurity in the finer recovered electrode material is less than 10%, less than 8%, less than 6%, less than 4%, less than 2%, less than 1%, less than 0.5%, less than 0.1% or less than 0.05%.
[00134] Generally, the electrode coating is dried and cured and then compressed on a table to increase the density of the electrode coating. In comparison to the anode electrode layer, the cathode electrode layer has a higher compressed density and thus energy density. Therefore, it is more difficult to separate the cathode electrode layer from the cathode current collector.
[00135] The recycling method disclosed in this document involves an aqueous based recycling technology. A high temperature or strongly acidic environment is not necessary and the aqueous processes are particularly environmentally friendly. Furthermore, the method disclosed in this document is simple and can be easily extended and operated at low cost.
[00136] The following examples are presented to exemplify modalities of the invention, but are not intended to limit the invention to the specific modalities established. Unless otherwise stated, all parts and percentages are by weight. All numerical values are approximate. When numerical ranges are given, it should be understood that modalities outside the ranges mentioned may still be within the scope of the invention. Specific details described in each example should not be constructed as necessary resources of the invention. EXAMPLES
[00137] The impurity of the isolated electrode materials was measured by an inductively coupled plasma mass spectrometer (obtained from PerkinElmer, Inc.). EXAMPLE 1 ASSEMBLY OF TOTAL LITHIUM ION BATTERIES IN POCKET SHAPE PREPARATION OF POSITIVE ELECTRODES
[00138] For the preparation of positive electrode, 94% by weight of NMC333 cathode material (LNMC TLM 310, obtained from Xinxiang Tianli Energia Co. Ltd., China), 3% by weight of carbon black (SuperP; obtained together with Timcal Ltd, Bodio, Switzerland) as a conductive agent and 3% by weight polyacrylonitrile (LA 132, Chengdu indigo Power Sources Co., Ltd., China) as a binder were dispersed in deionized water to form a slurry with a solids content of 50% by weight. The slurry was then uniformly spread on the aluminum foil as a chain catcher using a scraper blade coater (obtained from Shenzhen KejingStar Technology Ltd., China; model No. MSK-AFA-III) and dried at 50 ° C. ° C for 12 hours to obtain a cathode aluminum foil. PREPARATION OF NEGATIVE ELECTRODES
[00139] For the preparation of negative electrode, 90% by weight of rigid carbon (HC; 99.5% purity, obtained from Ruifute Technology Ltd., Shenzhen, Guangdong, China) with 5% by weight polyacrylonitrile as a binder and 5% by weight of carbon black as a conductive agent was dispersed in deionized water to form another slurry with a solids content of 50% by weight. The slurry was then uniformly spread on the copper foil as a current collector using a scraper blade coater and dried at 50 ° C for 12 hours to obtain an anode copper film. BATTERY ASSEMBLY IN POCKET FORMAT
[00140] After drying, the resulting cathode foil and anode foil were used to prepare the cathode foil and the anode foil respectively by cutting into rectangular pieces in the size of 8 cm x 12 cm. Pouch-shaped batteries were prepared by stacking the anode and cathode sheets in an alternating manner and separated by porous polyethylene separators (Celgard, LLC, US) having a thickness of 25 pm. The electrolyte was a solution of LiPF6 (1 M) in a mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) in a 1: 1: 1 volume ratio. The cells were assembled in an argon atmosphere with high purity with oxygen and moisture content <1 ppm. After filling the electrolyte, the cell-shaped cells were vacuum sealed and then mechanically pressed using a standard shaped punch tool.
[00141] The assembled bag-shaped batteries were then subjected to repeated charge and discharge cycles at a constant current rate of 1C between 3.0 V and 4.2 V to mimic real-life usage patterns. The actual cell capacity was about 5 Ah. Nominal capacity has dropped below 80% of its initial rated capacity after 800 cycles. BATTERY RECYCLING
[00142] Used lithium ion batteries (0.5 kg) were fully discharged by soaking in 6% NaCl solution for 12 hours. After discharging, the lithium ion batteries were cut into pieces by a waterjet cutting machine (YCWJ-3038-L2015-1D, obtained from YC Industry Co., Ltd., Jiangsu, China). The pieces of the cut lithium ion batteries, having an average length of about 1.27 cm (0.5 inch) to about 2.54 cm (1.0 inch) were immersed in deionized water (5 1) at 20 ° C to form a heterogeneous mixture. The mixture was mechanically stirred by a dispersion blade mixer (10 1, obtained from Chienemei Industry Co. Ltd., China) for 1 hour at 20 ° C. The rotational speed of the mixing blade is 15,000 rpm. The cathode material was detached from the aluminum foil, although the anode material fell from the copper foil. After stirring, the structural part, copper foil and aluminum foil were removed by passing through a sieve having a mesh width of 4 mm to yield a suspension with water and electrode materials. After removing the structural part, copper foil and aluminum foil, the suspension was filtered to obtain the electrode materials. The recovered electrode materials were dried in an oven for 5 hours at 80 ° C under atmospheric pressure and obtained in a 90% yield. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 2 ASSEMBLY OF TOTAL POCKET-SHAPED LITHIUM-ION BATTERIES
[00143] Lithium ion batteries in the form of a bag were prepared according to Example 1. The assembled bag-shaped batteries were then subjected to repeated charge and discharge cycles at a constant current rate of 1C between 3, 0 V and 4.2 V to mimic real life usage patterns. The actual cell capacity was about 5 Ah. Nominal capacity has dropped below 80% of its initial rated capacity after 800 cycles. BATTERY RECYCLING
[00144] Used lithium ion batteries (~ 20 kg) were fully discharged by soaking in 6% NaCI solution for 12 hours. After discharging, the lithium ion batteries were cut into pieces by a waterjet cutting machine (YCWJ-3038-L2015-1D, obtained from YC Industry Co., Ltd., Jiangsu, China). The pieces of the cut lithium ion batteries, having an average length of about 1.27 cm (0.5 inch) to about 2.54 cm (1.0 inch) were immersed in deionized water (25 1) at 20 ° C to form a heterogeneous mixture. The mixture was stirred by an ultrasonic probe (NP2500; obtained from Guangzhou Newpower Ultrasonic Electronic Equipment Co., Ltd., China) with an input power of 200 W for 2 hours at 20 ° C. The cathode material was detached from the aluminum foil, although the anode material fell from the copper foil. After ultrasonic processing, the structural part, copper foil and aluminum foil were removed by passing through a sieve having a mesh width of 4 mm to yield a suspension with water and electrode materials. After removing the structural part, copper foil and aluminum foil, the suspension was filtered to obtain the electrode materials. The recovered electrode materials were dried in an oven for 5 hours at 80 ° C under atmospheric pressure and obtained in a 63% yield. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 3 ASSEMBLY OF TOTAL POCKET-SHAPED LITHIUM-ION BATTERIES
[00145] Bag-shaped lithium ion batteries were prepared according to Example 1. The assembled bag-shaped batteries were then subjected to repeated charge and discharge cycles at a constant current rate of 1C between 3, 0 V and 4.2 V to mimic real life usage patterns. The actual cell capacity was about 5 Ah. Nominal capacity has dropped below 80% of its initial rated capacity after 800 cycles. BATTERY RECYCLING
[00146] Used lithium ion batteries (~ 20 kg) were fully discharged by soaking in a solution with 6% NaCl for 12 hours. After discharging, the lithium ion batteries were cut into pieces by a waterjet cutting machine (YCWJ-3038-L2015-1D, obtained from YC Industry Co., Ltd., Jiangsu, China). The pieces of the cut lithium-ion batteries, having an average length of about 1.27 cm (0.5 inch) to about 2.54 cm (1.0 inch) were immersed in deionized water (25 1) at 20 ° C to form a heterogeneous mixture. The mixture was mechanically stirred by a dispersion blade mixer (30L, obtained from Chienemei Industry Co. Ltd., China) for 2 hours at 20 ° C. The cathode material was detached from the aluminum foil, although the anode material fell from the copper foil. After stirring, the structural part, copper foil and aluminum foil were removed by passing through a sieve having a mesh width of 4 mm to yield a suspension with water and electrode materials. After removing the structural part, copper foil and aluminum foil, the suspension was filtered to obtain the electrode materials. The recovered electrode materials were dried in an oven for 5 hours at 80 ° C under atmospheric pressure and obtained in a 93% yield. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 4 ASSEMBLY OF TOTAL HANDBAG LITHIUM ION BATTERIES PREPARATION OF POSITIVE ELECTRODES
[00147] For the preparation of positive electrode, 92% by weight of LMO cathode material (LiMu2θ4 obtained from HuaGuan HengYuan LiTech Co. Ltd., Qingdao, China), 3% by weight of carbon black (SuperP; obtained from to Timcal Ltd, Bodio, Switzerland) as a conductive agent and 1% by weight carboxymethyl cellulose (CMC, BSH-12, DKS Co. Ltd., Japan), 3% by weight styrene and butadiene rubber (SBR) (AL- 2001, NIPPON A & l INC., Japan) and 2% by weight of polyvinylidene fluoride (PVDF; Solef® 5130, obtained from Solvay SA, Belgium) as a binder were dispersed in N-methyl-2-pyrrolidone (NMP; purity > 99%, Sigma-Aldrich, USA) to form a slurry with a solids content of 50% by weight. The slurry was then uniformly spread on the aluminum foil as a current collector using a scraper blade coater and dried at 50 ° C for 12 hours to obtain a cathode aluminum film. PREPARATION OF NEGATIVE ELECTRODES
[00148] For the preparation of negative electrode, 90% by weight of rigid carbon (HC; 99.5% purity, obtained from Ruifute Technology Ltd., Shenzhen, Guangdong, China) with 1.5% by weight CMC ( BSH-12, DKS Co. Ltd., Japan) and 3.5 wt% SBR (AL-2001, NIPPON A & l INC., Japan) as a binder and 5 wt% carbon black as a conductive agent were dispersed in deionized water to form another slurry with a solids content of 50% by weight. The slurry was then uniformly spread on the copper foil as a current collector using a scraper blade coater and dried at 50 ° C for 12 hours to obtain an anode copper film. BATTERY ASSEMBLY IN POCKET FORMAT
[00149] After drying, the resulting cathode foil and anode foil were used to prepare the cathode foil and anode foil respectively by cutting into rectangular pieces in the size of 8 cm x 12 cm. Pouch-shaped batteries were prepared by stacking the anode and cathode sheets in an alternating manner and separated by porous polyethylene separators (Celgard, LLC, US) having a thickness of 25 pm. The electrolyte was a solution of LiPF6 (1 M) in a mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) in a 1: 1: 1 volume ratio. The cells were assembled in an argon atmosphere with high purity with oxygen and moisture content <1 ppm. After filling the electrolyte, the cell-shaped cells were vacuum sealed and then mechanically pressed using a standard shaped punch tool.
[00150] The assembled bag-shaped batteries were then subjected to repeated charge and discharge cycles at a constant current rate of 1C between 3.0 V and 4.3 V to mimic real-life usage patterns. The actual cell capacity was about 4.2 Ah. Nominal capacity has dropped below 80% of its initial rated capacity after 1,000 cycles. BATTERY RECYCLING
[00151] Used lithium ion batteries (0.5 kg) were fully discharged by soaking in 4% NaCl solution for 12 hours. After discharging, the lithium-ion batteries were cut into pieces by a battery cutting machine (Kaidi Machinery, Zhengzhou, China). The pieces of the cut lithium ion batteries, having an average length of about 1 inch to about 1.5 inches (from 2.4 cm to 3.81 cm) were immersed in deionized water (10 1) at room temperature to form a heterogeneous mixture. The mixture was stirred ultrasonically in an ultrasonic bath (G-100ST, obtained from Shenzhen Geneng Cleaning Equipment Co. Limited.) At room temperature for 0.5 hour. The cathode material was detached from the aluminum foil, although the anode material fell from the copper foil. After stirring, the structural part, copper foil and aluminum foil were removed by passing through a sieve having a mesh width of 2 mm to yield a suspension with water and electrode materials. After removing the structural part, copper foil and aluminum foil, the suspension was filtered to obtain the electrode materials. The recovered electrode materials were dried in an oven for 5 hours at 80 ° C under atmospheric pressure and obtained in a 93% yield. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 5 ASSEMBLY OF TOTAL LITHIUM ION BATTERIES IN POCKET FORM PREPARATION OF POSITIVE ELECTRODES
[00152] For the preparation of positive electrode, 94% by weight of LiCoθ2 cathode material (LCO) (obtained from Xiamen Tungsten Co. Ltd., China), 3% by weight of carbon black (SuperP; obtained from Timcal Ltd, Bodio, Switzerland) as a conductive agent and 3 wt% polyacrylic acid (PAA, # 181285, obtained from Sigma-Aldrich, US) as a binder were dispersed in deionized water to form a slurry with a 50% by weight solids. The slurry was then uniformly spread on the aluminum foil as a current collector using a scraper blade coater and dried at 50 ° C for 12 hours to obtain a cathode aluminum film. PREPARATION OF NEGATIVE ELECTRODES
[00153] For the preparation of negative electrode, 90% by weight of rigid carbon (HC; 99.5% purity, obtained from Ruifute Technology Ltd., Shenzhen, Guangdong, China) with 1.5% by weight CMC ( BSH-12, DKS Co. Ltd., Japan) and 3.5 wt% SBR (AL-2001, NIPPON A & l INC., Japan) as a binder and 5 wt% carbon black as a conductive agent were dispersed in deionized water to form another slurry with a solids content of 50% by weight. The slurry was then uniformly spread on the copper foil as a current collector using a scraper blade coater and dried at 50 ° C for 12 hours to obtain an anode copper film. BATTERY ASSEMBLY IN POCKET FORMAT
[00154] After drying, the resulting cathode foil and anode foil were used to prepare the cathode foil and anode foil respectively by cutting into rectangular pieces in the size of 8 cm x 12 cm. Pouch-shaped batteries were prepared by stacking the anode and cathode sheets in an alternating manner and separated by porous polyethylene separators (Celgard, LLC, US) having a thickness of 25 pm. The electrolyte was a solution of LiPF6 (1 M) in a mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) in a 1: 1: 1 volume ratio. The cells were assembled in an argon atmosphere with high purity with oxygen and moisture content <1 ppm. After filling the electrolyte, the cell-shaped cells were vacuum sealed and then mechanically pressed using a standard shaped punch tool.
[00155] The assembled bag-shaped batteries were then subjected to repeated charge and discharge cycles at a constant current rate of 1C between 3.0 V and 4.3 V to mimic real-life usage patterns. The actual cell capacity was about 5.2 Ah. Nominal capacity has dropped below 80% of its initial rated capacity after 650 cycles. BATTERY RECYCLING
[00156] Used lithium ion batteries (0.5 kg) were fully discharged by soaking in a solution with 6% NaCI for 12 hours. After discharging, the lithium ion batteries were cut into pieces by a waterjet cutting machine (YCWJ-3038-L2015-1D, obtained from YC Industry Co., Ltd., Jiangsu, China). The pieces of the cut lithium ion batteries, having an average length of about 1.27 cm (0.5 inch) to about 2.54 cm (1.0 inch) were immersed in deionized water (5 1) at 20 ° C to form a heterogeneous mixture. The mixture was mechanically stirred by a dispersion blade mixer (10 1, obtained from Chienemei Industry Co. Ltd., China) for 2 hours at 20 ° C. The cathode material was detached from the aluminum foil, although the anode material fell from the copper foil. After stirring, the structural part, copper foil and aluminum foil were removed by passing through a sieve having a mesh width of 4 mm to yield a suspension with water and electrode materials. After removing the structural part, copper foil and aluminum foil, the suspension was filtered to obtain the electrode materials. The recovered electrode materials were dried in an oven for 5 hours at 70 ° C under atmospheric pressure and obtained in a 90% yield. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 6 ASSEMBLY OF TOTAL POCKET-SHAPED LITHIUM-ION BATTERIES
[00157] Bag-shaped lithium ion batteries were prepared according to Example 5. The assembled bag-shaped batteries were then subjected to repeated charge and discharge cycles at a constant current rate of 1C between 3, 0 V and 4.2 V to mimic real life usage patterns. The actual cell capacity was about 5 Ah. Nominal capacity has dropped below 80% of its initial rated capacity after 700 cycles. BATTERY RECYCLING
[00158] Used lithium ion batteries (0.5 kg) were fully discharged by soaking in 6% NaCl solution for 12 hours. After discharging, the lithium ion batteries were cut into pieces by a waterjet cutting machine (YCWJ-3038-L2015-1D, obtained from YC Industry Co., Ltd., Jiangsu, China). The pieces of the cut lithium ion batteries, having an average length of about 1.27 cm (0.5 inch) to about 2.54 cm (1.0 inch) were immersed in a 0.05 M solution of phosphate buffer (5 1) having a pH value of about pH 6.8 at 20 ° C to form a heterogeneous mixture. The phosphate buffer solution was prepared by dissolving 39 g of sodium phosphate monobasic dihydrate (NaH2PO4 • 2H2O, obtained from Sigma-Aldrich, US) in deionized water (5 1). The mixture was mechanically stirred by a dispersion blade mixer (10 1, obtained from Chienemei Industry Co. Ltd., China) for 2 hours at 20 ° C. The cathode material was detached from the aluminum foil, although the anode material fell from the copper foil. After stirring, the structural part, copper foil and aluminum foil were removed by passing through a sieve having a mesh width of 4 mm to yield a suspension provided with the buffer solution and electrode materials. After removing the structural part, copper foil and aluminum foil, the suspension was filtered to obtain the electrode materials. The recovered electrode materials were dried in an oven for 5 hours at 80 ° C under atmospheric pressure and obtained in a 95% yield. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 7 ASSEMBLY OF TOTAL HANDBAG LITHIUM ION BATTERIES PREPARATION OF POSITIVE ELECTRODES
[00159] For the preparation of positive electrode, 91% by weight of LiFePO4 cathode material (LFP) (obtained from Xiamen Tungsten Co. Ltd., China), 5% by weight of carbon black (SuperP; obtained from Timcal Ltd, Bodio, Switzerland) as a conductive agent and 4% by weight of sodium alginate (SA, # 180947, obtained from Sigma-Aldrich, US) as a binder were dispersed in deionized water to form a slurry with a solids content of 50% by weight. The slurry was then uniformly spread on the aluminum foil as a current collector using a scraper blade coater and dried at 50 ° C for 12 hours to obtain a cathode aluminum film. PREPARATION OF NEGATIVE ELECTRODES
[00160] For the preparation of negative electrode, 90% by weight of rigid carbon (HC; 99.5% purity, obtained from Ruifute Technology Ltd., Shenzhen, Guangdong, China) with 1.5% by weight CMC ( BSH-12, DKS Co. Ltd., Japan) and 3.5 wt% SBR (AL-2001, NIPPON A & l INC., Japan) as a binder and 5 wt% carbon black as a conductive agent were dispersed in deionized water to form another slurry with a solids content of 50% by weight. The slurry was then uniformly spread on the copper foil as a current collector using a scraper blade coater and dried at 50 ° C for 12 hours to obtain an anode copper film. BATTERY ASSEMBLY IN POCKET FORMAT
[00161] After drying, the resulting cathode foil and anode foil were used to prepare the cathode foil and anode foil respectively by cutting into pieces of rectangular shape in the size of 8 cm x 12 cm. Pouch-shaped batteries were prepared by stacking the anode and cathode sheets in an alternating manner and separated by porous polyethylene separators (Celgard, LLC, US) having a thickness of 25 pm. The electrolyte was a solution of LiPF6 (1 M) in a mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) in a 1: 1: 1 volume ratio. The cells were assembled in an argon atmosphere with high purity with oxygen and moisture content <1 ppm. After filling the electrolyte, the cell-shaped cells were vacuum sealed and then mechanically pressed using a standard shaped punch tool.
[00162] The assembled bag-shaped batteries were then subjected to repeated charge and discharge cycles at a constant current rate of 1C between 2.5 V and 3.6 V to mimic real-life usage patterns. The actual cell capacity was about 4 Ah. Nominal capacity has dropped below 80% of its initial rated capacity after 500 cycles. BATTERY RECYCLING
[00163] Used lithium ion batteries (0.5 kg) were fully discharged by soaking in a solution with 6% NaCl for 12 hours. After discharging, the lithium ion batteries were cut into pieces by a waterjet cutting machine (YCWJ-3038-L2015-1D, obtained from YC Industry Co., Ltd., Jiangsu, China). The pieces of the cut lithium-ion batteries, having an average length of about 1.27 cm (0.5 inch) to about 2.54 cm (1.0 inch) were immersed in a mixture of deionized water (6 , 5 1) and ethanol (1.5 1) at 20 ° C to form a heterogeneous mixture. The mixture was mechanically stirred by a dispersion blade mixer (10 1, obtained from Chienemei Industry Co. Ltd., China) for 1 hour at 20 ° C. The cathode material was detached from the aluminum foil, although the anode material fell from the copper foil. After stirring, the structural part, copper foil and aluminum foil were removed by passing through a sieve having a mesh width of 4 mm to yield a suspension with water and ethanol and electrode materials. After removing the structural part, copper foil and aluminum foil, the suspension was filtered to obtain the electrode materials. The recovered electrode materials were dried in an oven for 5 hours at 80 ° C under atmospheric pressure and obtained in a 91% yield. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 8 ASSEMBLY OF TOTAL LITHIUM-ION BATTERIES IN POCKET FORM PREPARATION OF POSITIVE ELECTRODES
[00164] For the preparation of positive electrode, 94% by weight of LiNio cathode material, 33Mno, 33Cθo, 33θ2 (NMC333) (obtained from Shenzhen Tianjiao Technology Co. Ltd., China), 3% by weight of black carbon (SuperP; obtained from Timcal Ltd, Bodio, Switzerland) as a conductive agent and 1.5% by weight of polyacrylic acid (PAA, # 181285, obtained from Sigma-Aldrich, US) and 1.5% by weight polyacrylonitrile (LA 132, Chengdu indigo Power Sources Co., Ltd., China) as a binder were dispersed in deionized water to form a slurry with a solids content of 50% by weight. The slurry was then uniformly spread on the aluminum foil as a current collector using a scraper blade coater and dried at 50 ° C for 12 hours to obtain a cathode aluminum film. PREPARATION OF NEGATIVE ELECTRODES
[00165] For the preparation of negative electrode, 90% by weight of rigid carbon (HC; 99.5% purity, obtained from Ruifute Technology Ltd., China) with 1.5% by weight CMC (BSH-12, DKS Co. Ltd., Japan) and 3.5 wt% SBR (AL-2001, NIPPON A & l INC., Japan) as a binder and 5 wt% carbon black as a conductive agent were dispersed in deionized water to form another slurry with a solids content of 50% by weight. The slurry was then uniformly spread on the copper foil as a current collector using a scraper blade coater and dried at 50 ° C for 12 hours to obtain an anode copper film. BATTERY ASSEMBLY IN POCKET FORMAT
[00166] After drying, the resulting cathode foil and anode foil were used to prepare the cathode foil and anode foil respectively by cutting into pieces of rectangular shape in the size of 8 cm x 12 cm. Pouch-shaped batteries were prepared by stacking the anode and cathode sheets in an alternating manner and separated by porous polyethylene separators (Celgard, LLC, US) having a thickness of 25 pm. The electrolyte was a solution of LiPF6 (1 M) in a mixture of ethylene carbonate (EC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DMC) in a 1: 1: 1 volume ratio. The cells were assembled in an argon atmosphere with high purity with oxygen and moisture content <1 ppm. After filling the electrolyte, the cell-shaped cells were vacuum sealed and then mechanically pressed using a standard shaped punch tool.
[00167] The assembled bag-shaped batteries were then subjected to repeated charge and discharge cycles at a constant current rate of 1C between 3.0 V and 4.2 V to mimic real-life usage patterns. The actual cell capacity was about 5.1 Ah. Nominal capacity has dropped below 80% of its initial rated capacity after 900 cycles. BATTERY RECYCLING
[00168] Used lithium ion batteries (0.5 kg) were fully discharged by soaking in 6% NaCl solution for 12 hours. After discharging, the lithium ion batteries were cut into pieces by a waterjet cutting machine (YCWJ-3038-L2015-1D, obtained from YC Industry Co., Ltd., Jiangsu, China). The pieces of the cut lithium-ion batteries, having an average length of about 1.27 cm (0.5 inch) to about 2.54 cm (1.0 inch) were immersed in a mixture of deionized water (5 1) and acetone (11) at 20 ° C to form a heterogeneous mixture. The mixture was mechanically stirred by a dispersion blade mixer (10 1, obtained from Chienemei Industry Co. Ltd., China) for 1 hour at 20 ° C. The cathode material was detached from the aluminum foil, although the anode material fell from the copper foil. After stirring, the structural part, copper foil and aluminum foil were removed by passing through a sieve having a mesh width of 4 mm to yield a suspension with water and acetone and electrode materials. After removing the structural part, copper foil and aluminum foil, the suspension was filtered to obtain the electrode materials. The recovered electrode materials were dried in an oven for 5 hours at 75 ° C under atmospheric pressure and obtained in a 92% yield. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. Example 9
[00169] Pouch-shaped batteries were prepared in the same manner as in Example 1 except cathode material LiNio.6Mno.2Cθo, 2θ2 (NMC622) (obtained from Hunan Rui Xiang New Material Co., Ltd., Changsha, China ) was used instead of NMC333. The assembled bag-shaped batteries were then subjected to repeated charge and discharge cycles at a constant current rate of 1C between 3.0 V and 4.2 V to mimic real-life usage patterns. The actual cell capacity was about 5.5 Ah. Nominal capacity has dropped below 80% of its initial rated capacity after 1,879 cycles.
[00170] Used lithium ion batteries were recycled in the same way as in Example 1. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 10
[00171] Pouch-shaped batteries were prepared in the same manner as in Example 1 except that LiNio cathode material, 8Mno, iCoo, i02 (NMC811) (obtained from Henan Kelong NewEnergy Co., Ltd., Xinxiang, China) used instead of NMC333. The assembled bag-shaped batteries were then subjected to repeated charge and discharge cycles at a constant current rate of 1C between 3.0 V and 4.2 V to mimic real-life usage patterns. The actual cell capacity was about 4.7 Ah. Nominal capacity has dropped below 80% of its initial rated capacity after 1,270 cycles.
[00172] Used lithium ion batteries were recycled in the same way as in Example 1. The recycling and formulation conditions of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 11
[00173] Pouch-shaped batteries were prepared in the same manner as in Example 1 except that LiNio cathode material, 8Cθo, i5Alo, o5θ2 (NCA) (obtained from Hunan Rui Xiang New Material Co., Ltd., Changsha, China ) was used instead of NMC333. The assembled bag-shaped batteries were then subjected to repeated charge and discharge cycles at a constant current rate of 1C between 3.0 V and 4.2 V to mimic real-life usage patterns. The actual cell capacity was about 4.2 Ah. Nominal capacity has dropped below 80% of its initial rated capacity after 996 cycles.
[00174] Used lithium ion batteries were recycled in the same way as in Example 1. The formulation of the cathode, anode and recycling conditions are shown in table 1. The recycling results are shown in table 3. Example 12
[00175] Pouch-shaped batteries were prepared in the same manner as in Example 1. Used lithium-ion batteries were recycled in the same manner as in Example 1 except that the rotational speed of the mixing blade was 4,000 rpm instead of 15,000 rpm. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 13
[00176] Pouch-shaped batteries were prepared in the same manner as in Example 1. Used lithium-ion batteries were recycled in the same manner as in Example 12 except that the stirring time is 0.16 hours instead of 1 hour . The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 14
[00177] Pouch-shaped batteries were prepared in the same manner as in Example 1 except that LCO was used as a cathode material instead of NMC333. The assembled bag-shaped batteries were then subjected to repeated charge and discharge cycles at a constant current rate of 1C between 3.0 V and 4.2 V to mimic real-life usage patterns. The actual cell capacity was about 3 Ah. Nominal capacity has dropped below 80% of its initial rated capacity after 1,300 cycles.
[00178] Used lithium ion batteries were recycled in the same way as in Example 3 except that a high shear mixer was used instead of a dispersion blade mixer and the stirring time was 0.5 hour instead of 2 hours. The rotational speed of the screw and the rotating unit were 2,000 rpm and 250 rpm respectively. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 15
[00179] Pouch-shaped batteries were prepared in the same manner as in Example 1 except that LFP was used as a cathode material instead of NMC333. The assembled bag-shaped batteries were then subjected to repeated charge and discharge cycles at a constant current rate of 1C between 3.0 V and 4.2 V to mimic real-life usage patterns. The actual cell capacity was about 15 Ah. Nominal capacity has dropped below 80% of its initial rated capacity after 2,100 cycles.
[00180] Used lithium ion batteries were recycled in the same way as in Example 14. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 16
[00181] Pouch-shaped batteries were prepared in the same manner as in Example 1. Used lithium-ion batteries were recycled in the same manner as in Example 14. The recycling and formulation conditions of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLES 17-20
[00182] Pouch-shaped batteries were prepared in the same manner as in Example 1 except that NMC532, NMC622, NMC811 and NCA were used in Examples 17, 18, 19 and 20 respectively instead of NMC333. Used lithium ion batteries were recycled in the same way as in Example 14. The recycling conditions and formulation of the cathode and anode are shown in table 1. The results of the recycling are shown in table 3. EXAMPLE 21
[00183] Pouch-shaped batteries were prepared in the same manner as in Example 14. Used lithium-ion batteries were recycled in the same manner as in Example 5 except that a tapered screw mixer (obtained from Shuanglong Group Co., Ltd ) was used instead of a dispersion blade mixer. The rotational speed of the arm was 150 rpm and the rotational speed of the screw was 300 rpm. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 22
[00184] Pouch-shaped batteries were prepared in the same manner as in Example 15. Used lithium-ion batteries were recycled in the same manner as in Example 21. The recycling and formulation conditions of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 23
[00185] Pouch-shaped batteries were prepared in the same manner as in Example 14. Used lithium-ion batteries were recycled in the same manner as in Example 5 except that a planetary stirrer was used instead of a blade blender. dispersal. The rotational speeds of the planetary blade and high speed dispersion blade were 150 rpm and 1,000 rpm respectively. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 24
[00186] Pouch-shaped batteries were prepared in the same manner as in Example 15. Used lithium-ion batteries were recycled in the same manner as in Example 23. The conditions for recycling and formulating the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 25
[00187] Pouch-shaped batteries were prepared in the same manner as in Example 14. Used lithium-ion batteries were recycled in the same manner as in Example 5 except that an air jet mixer (obtained from ALPA Powder Technology & Equipment Co ., Ltd) was used instead of a dispersion blade mixer. The air jet pressure was 0.3 MPa. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 26
[00188] Pouch-shaped batteries were prepared in the same manner as in Example 15. Used lithium ion batteries were recycled in the same manner as in Example 25. The conditions for recycling and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 27
[00189] Pouch-shaped batteries were prepared in the same manner as in Example 14. Used lithium-ion batteries were recycled in the same manner as in Example 1 except that an additional 30 g of plastic microsphere having a microsphere size of 0.5 mm were added to the heterogeneous mixture; the rotational speed of the dispersion blade mixer was 4,000 rpm instead of 15,000 rpm; and the stirring time was 0.5 hour instead of 1 hour. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 28
[00190] Pouch-shaped batteries were prepared in the same manner as in Example 1. Used lithium-ion batteries were recycled in the same manner as in Example 27. The conditions for recycling and formulating the cathode and anode are shown in table 1. The recycling results are shown in table 3. EXAMPLE 29
[00191] Bag-shaped batteries were prepared in the same manner as in Example 10. Used lithium-ion batteries were recycled in the same manner as in Example 27. The conditions for recycling and formulation of the cathode and anode are shown in Table 1. The recycling results are shown in table 3. COMPARATIVE EXAMPLE 1
[00192] Pouch-shaped batteries were prepared in the same manner as in Example 15. Used lithium-ion batteries were recycled in the same manner as in Example 1 except that the cut batteries were soaked for 1 hour without shaking. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. COMPARATIVE EXAMPLE 2
[00193] Pouch-shaped batteries were prepared in the same manner as in Example 4. Used lithium-ion batteries were recycled in the same manner as in Example 4 except for the use of 20 kg of used batteries instead of 0.5 kg and changing the water volume to 25 1. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. COMPARATIVE EXAMPLE 3
[00194] Pouch-shaped batteries were prepared in the same way as in Example 1. Used lithium-ion batteries were recycled in the same way as in Example 4 except that the amount of water used was 5 1 instead of 10 1 and the heterogeneous mixture was stirred for 2 hours instead of 0.5 hour. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. COMPARATIVE EXAMPLE 4
[00195] Pouch-shaped batteries were prepared in the same way as in Example 10. Used lithium-ion batteries were recycled in the same way as in Comparative Example 3. The recycling and formulation conditions of the cathode and anode are shown in table 1 The recycling results are shown in table 3. COMPARATIVE EXAMPLE 5
[00196] Pouch-shaped batteries were prepared in the same manner as in Example 5. Used lithium-ion batteries were recycled in the same manner as in Example 5 except for the use of 20 kg of used batteries instead of 0.5 kg; changing the water volume to 25 1; and stirring the heterogeneous mixture with a stirring mixer and ultrasonic bath instead of a dispersion blade mixer. The agitation speed of the stirring mixer was 500 rpm and the input power of the ultrasonic bath was 200 W. The heterogeneous mixture was simultaneously stirred and subjected to ultrasonication for 20 minutes. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. COMPARATIVE EXAMPLE 6
[00197] Pouch-shaped batteries were prepared in the same manner as in Example 5 except that NMC811 a cathode material was used instead of LCO. Used lithium ion batteries were recycled in the same way as in Comparative Example 5 except that the amount of water used was 5 1 instead of 25 1 and 0.5 kg of used lithium ion batteries was used instead of 20 kg . The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. COMPARATIVE EXAMPLE 7
[00198] Pouch-shaped batteries were prepared in the same manner as in Example 15. Used lithium-ion batteries were recycled in the same manner as in Comparative Example 6 except that the stirring time was 1 hour instead of 20 minutes. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. COMPARATIVE EXAMPLE 8
[00199] Pouch-shaped batteries were prepared in the same manner as in Example 14. Used lithium-ion batteries (0.1 kg) were recycled using an impact crusher (PLS-550, obtained from Luoyang Dahua Heavy Type Machinery Co., Ltd., China) at a rotational speed of 2,500 rpm for 0.011 hours. The volume of water used was 1 1. After stirring, the structural part, copper foil and aluminum foil were removed by passing through a sieve having a mesh width of 4 mm to yield a suspension with water and electrode materials. After removing the structural part, copper foil and aluminum foil, the suspension was filtered to obtain the electrode materials. The recovered electrode materials were dried in an oven for 5 hours at 80 ° C under atmospheric pressure. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. COMPARATIVE EXAMPLES 9-11
[00200] Bag-shaped batteries of Comparative Examples 9, 10 and 11 were prepared in the same manner as in Examples 15, 1 and 10 respectively. Used lithium-ion batteries from Comparative Examples 9, 10 and 11 were recycled in the same way as in Comparative Example 8. The recycling conditions and formulations of the cathodes and anodes are shown in table 1. The recycling results are shown in table 3 . COMPARATIVE EXAMPLE 12
[00201] Pouch-shaped batteries were prepared in the same manner as in Example 14. Used lithium-ion batteries were recycled in the same manner as in Example 5 except that a screw mixer (obtained from Shuanglong Group Co., Ltd) was used instead of a dispersion blade mixer. The rotational speed of the screw was 500 rpm. The recycling conditions and formulation of the cathode and anode are shown in table 1. The recycling results are shown in table 3. COMPARATIVE EXAMPLES 13, 14 AND 15
[00202] Bag-shaped batteries of Comparative Examples 13, 14 and 15 were prepared in the same manner as in Examples 15, 1 and 10 respectively. Used lithium-ion batteries from Comparative Examples 13, 14 and 15 were recycled in the same way as in Comparative Example 12. The recycling conditions and formulations of the cathodes and anodes are shown in table 1. The recycling results are shown in table 3 . COMPARATIVE EXAMPLES 16 AND 17
[00203] Bag-shaped batteries of Comparative Examples 16 and 17 were prepared in the same manner as in Examples 1 and 10 respectively. Used lithium-ion batteries from Comparative Examples 16 and 17 were recycled in the same way as in Example 21. The recycling conditions and formulations of the cathodes and anodes are shown in table 1. The recycling results are shown in table 3. COMPARATIVE EXAMPLES 18 AND 19
[00204] Bag-shaped batteries of Comparative Examples 18 and 19 were prepared in the same manner as in Examples 1 and 10 respectively. Used lithium-ion batteries from Comparative Examples 18 and 19 were recycled in the same way as in Example 23. The recycling conditions and formulations of the cathodes and anodes are shown in table 1. The recycling results are shown in table 3. COMPARATIVE EXAMPLES 20 AND 21
[00205] Bag-shaped batteries from Comparative Examples 20 and 21 were prepared in the same manner as in Examples 1 and 10 respectively. Used lithium-ion batteries from Comparative Examples 20 and 21 were recycled in the same way as in Example 25. The recycling conditions and formulations of the cathodes and anodes are shown in table 1. The recycling results are shown in table 3. REFERENCE EXAMPLE 1
[00206] Pouch-shaped batteries of Reference Example 1 were prepared in the same manner as in Example 1. Used lithium-ion batteries were disassembled and 1 kg of cathode electrodes was isolated. The isolated cathode electrodes were immersed in 5 l of deionized water at 20 ° C to form a mixture that was stirred by a high shear mixer for 0.5 hour. The rotational speed of the rotating unit was 250 rpm and the rotational speed of the screw was 2000 rpm. The cathode material was detached from the aluminum foil. After stirring, the aluminum foil was removed by passing through a sieve having a mesh width of 4 mm to provide a suspension with water and electrode materials. After removing the aluminum foil, the suspension was filtered to obtain the electrode materials. The recovered electrode materials were dried in an oven for 5 hours at 80 ° C under atmospheric pressure. The recycling conditions and the cathode formulation are shown in table 2. The recycling results are shown in table 3. REFERENCE EXAMPLE 2
[00207] Pouch-shaped batteries of Reference Example 2 were prepared in the same manner as in Example 10. Used lithium ion batteries were disassembled and 1 kg of cathode electrodes was isolated. The isolated cathode electrodes were recycled in the same way as in Reference Example 1. The recycling conditions and the cathode formulation are shown in table 2. The recycling results are shown in table 3. REFERENCE EXAMPLE 3
[00208] Pouch-shaped batteries of Reference Example 3 were prepared in the same manner as in Example 1. Used lithium-ion batteries were disassembled and 1 kg of cathode electrodes was isolated. The isolated cathode electrode was recycled in the same way as in Reference Example 1 except that a dispersion blade mixer was used instead of a high shear mixer. The rotational speed of the mixing blade was 15,000 rpm. The recycling conditions and the cathode formulation are shown in table 2. The recycling results are shown in table 3. REFERENCE EXAMPLE 4
[00209] Pouch-shaped batteries of Reference Example 4 were prepared in the same manner as in Example 1. Used lithium ion batteries were disassembled and 1 kg of anode electrodes was isolated. The isolated anode electrodes were recycled in the same way as in Reference Example 1. The recycling conditions and anode formulation are shown in table 2. The recycling results are shown in table 3. REFERENCE EXAMPLE 5
[00210] Pouch-shaped batteries of Reference Example 5 were prepared in the same manner as in Example 1. Used lithium-ion batteries were disassembled and 1 kg of anode electrodes was isolated. The isolated anode electrodes were recycled in the same way as in Reference Example 3. The recycling conditions and anode formulation are shown in table 2. The recycling results are shown in table 3. TABLE 1


Note: 1The rotational speed of the dispersion blade mixer was 4,000 rpm. 2The rotational speed of the dispersion blade mixer was 4,000 rpm and plastic microspheres (30 g) were added to the heterogeneous mixture. 3 The cut batteries were soaked in H2O for 1 hour without shaking. TABLE 2


[00211] The yields of the recovered electrode materials are shown in table 3 below. The methods disclosed in this document can improve the recovery efficiency of different types of cathode materials. High nickel cathode materials can also be recovered. TABLE 3


[00212] Although the invention has been described in relation to a limited number of modalities, the features specific to one modality should not be allocated to the other modalities of the invention. In some embodiments, the methods may include numerous steps not mentioned in this document. In other embodiments, the methods do not include or are substantially free of any steps not listed in this document. There are variations and modifications to the described modalities. The attached claims are intended to cover all such modifications and variations, as they fall within the scope of the invention.

权利要求:
Claims (18)
[0001]
1. Method for recycling lithium ion batteries, characterized by the fact that it comprises the steps of: a) discharging lithium ion batteries; b) cutting lithium ion batteries into pieces to provide a mixture of a structural part, a first part of conductive metal coated with a cathode layer, and a second part of conductive metal coated with an anode layer; c) immerse the cut lithium ion battery pieces in a polar solvent to form a heterogeneous mixture; d) processing the heterogeneous mixture with mechanical stirring for a period of time from about 15 minutes to about 2 hours to dissolve a binder material in the cathode and anode layers; e) filtering the heterogeneous mixture processed to separate the structural part, first part of conductive metal, and second part of conductive metal from thinner electrode materials comprising cathode and anode materials to provide a suspension with polar solvent and materials thinner electrode; and f) isolating the finest electrode materials in the suspension from the polar solvent; wherein the polar solvent is a buffer solution having a pH of about 6 to about 8.
[0002]
2. Method according to claim 1, characterized by the fact that step d) is performed at room temperature.
[0003]
Method according to claim 1, characterized by the fact that the heterogeneous mixture in step d) is heated at a temperature of about 35 ° C to about 100 ° C, or from about 55 ° C to about 75 ° Ç.
[0004]
4. Method according to claim 1, characterized in that the binder material comprises a water-based binder material selected from the group consisting of unsaturated polymer, conjugated diene polymer, styrene-butadiene rubber, styrene rubber -acrylated butadiene, acrylonitrile-butadiene rubber, acrylic rubber, butyl rubber, fluorine rubber, polyvinylpyrrolidone, polyolefin, polyethylene, polypropylene, ethylene / propylene copolymers, polybutadiene, polyethylene oxide, polyethylene pyridine, polyvinyl chloride, polyvinyl chloride, polyvinyl chloride polyvinyl, polyvinyl alcohol, polyvinyl acetate, polyhepichlorohydrin, polyphosphazene, polyacrylonitrile, polystyrene, latex, acrylic resins, phenolic resins, epoxy resins, cellulose, carboxymethyl cellulose, hydroxypropyl cellulose, cellulose acetate, butylate acetate cellulose acetate, cyanoethyl cellulose, cyanoethyl saccharose, p oliester, polyamide, polyether, polyimide, polycarboxylate, polycarboxylic acid, polyacrylic acid, polyacrylate, polymethacrylate, polymethacrylate, polyacrylamide, polyurethane, halogenated polymer, fluorinated polymer, chlorinated polymer, an alginic acid salt, and combinations thereof.
[0005]
Method according to claim 4, characterized by the fact that the alginic acid salt comprises a cation selected from Na, Li, K, Ca, NH4, Mg, Al, or a combination thereof.
[0006]
Method according to claim 1, characterized in that the binder material comprises a water-based binder which is a monomer containing a carboxylic acid group, a sulfonic acid group, or a combination thereof.
[0007]
7. Method according to claim 1, characterized in that the lithium ion batteries are cut by a water jet cutting machine or a cut device with indentations or blades.
[0008]
8. Method according to claim 1, characterized in that the pieces of the cut lithium ion batteries have an average length of about 0.5 inch (1.27 cm) to about 4.0 inches (10 , 16 cm).
[0009]
9. Method according to claim 1, characterized by Petipã <i ^ a®aí «t) 7Waid ^ fflft®mopjgg37 / 99 the fact that the pieces of the cut lithium ion batteries have an average length of about one quarter inch (0.635 cm) or less.
[0010]
10. Method according to claim 1, characterized in that each of the first and the second conductive metal parts is independently selected from the group consisting of a thin aluminum plate, a thin copper plate, a plate thin gold, a thin silver plate, and a thin platinum plate.
[0011]
11. Method according to claim 1, characterized in that that buffer solution comprises a salt selected from the group consisting of lithium carbonate, lithium bicarbonate, lithium phosphate, sodium carbonate, sodium bicarbonate, sodium phosphate, potassium carbonate, potassium bicarbonate, potassium phosphate, ammonium carbonate, ammonium bicarbonate, ammonium phosphate, and combinations thereof.
[0012]
12. Method according to claim 1, characterized by the fact that the mechanical agitation of the processing step is performed by agitation, vibration, ultrasonication, vortexing, or a combination thereof.
[0013]
13. Method according to claim 1, characterized in that the binder material further comprises an organic based binder material.
[0014]
14. Method according to claim 13, characterized by the fact that said organic-based binder material is selected from the group consisting of polytetrafluoroethylene, perfluoroalkoxy polymer, polyvinylidene fluoride, tetrafluoroethylene and hexafluoropropylene copolymer, ethylene-copolymer fluorinated propylene, tetrafluoroethylene terpolymer, hexafluoropropylene and vinylidene fluoride, and combinations thereof.
[0015]
15. Method according to claim 1, characterized by the fact that the finer electrode materials additionally comprise a conductive agent.
[0016]
16. Method according to claim 1, characterized by the fact that the cathode material is a lithium metal oxide selected from the group consisting of LiNiCh, LiNixMnyC> 2, Lii + zNixMnyCθi.x.yθ2, LiNixCoyAlzO2, LÍV2O5, LiTiS2 , LÍM0S2, LiMnO2, LÍCOO2, LiCrO2, LiMn2O4, LiFePO4, and their combinations; where each x is independently 0.3 to 0.8; where each y is independently 0.1 to 0.45; and wherein each z is independently from 0 to 0.2; and wherein the anode material is a carbonaceous material.
[0017]
17. Method according to claim 1, characterized by the fact that the finer electrode materials are filtered by passing through a sieve having a mesh width between 2 mm and 4 mm, or between 0.5 mm and 1.0 mm.
[0018]
18. Method according to claim 1, characterized by the fact that isolation of the finest electrode materials is carried out through filtration, decantation, sedimentation, centrifugation, or a combination thereof.

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法律状态:
2020-10-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-11-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/06/2017, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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