EP3381080A1 - Method and apparatus for recycling lithium-ion batteries - Google Patents
Method and apparatus for recycling lithium-ion batteriesInfo
- Publication number
- EP3381080A1 EP3381080A1 EP16869162.4A EP16869162A EP3381080A1 EP 3381080 A1 EP3381080 A1 EP 3381080A1 EP 16869162 A EP16869162 A EP 16869162A EP 3381080 A1 EP3381080 A1 EP 3381080A1
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- EP
- European Patent Office
- Prior art keywords
- materials
- solution
- cathode
- battery
- desirable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Definitions
- Modern electronic devices such as cell phones, computing devices, and automobiles, demand substantial current delivery while being lightweight and small enough to avoid hindering the portability of the host device.
- NiCad nickel-cadmium
- NiMH nickel metal hydride
- Exhausted LIBs undergo a physical separation process for removing solid battery components, such as casing and plastics, and electrodes are dissolved in a solution for extracting the useful elements Co (cobalt), Ni (nickel), Mn (manganese), and Li (lithium), from mixed cathode materials and utilizing the recycled elements to produce active materials for new batteries.
- Configurations herein are based, in part, on the observation that conventional approaches do not recycle and recover Li-ion batteries with LiNiCoAlC , which is being used in automobile application (for example TeslaTM electric vehicles).
- the solution includes compounds of desirable materials such as cobalt, nickel and manganese dissolved as compounds from the exhausted cathode material of spent cells. Depending on a desired proportion, or ratio, of the desired materials, raw materials are added to the solution to achieve the desired ratio of the commingled compounds for the recycled cathode material for new cells.
- a strong base such as sodium hydroxide, raises the pH such that the desired materials precipitate out of solution without extensive heating or separation of the desired materials into individual compounds or elements.
- the resulting active cathode material has the predetermined ratio for use in new cells, and avoids high heat typically required to separate the useful elements because the desired materials remain commingled in solution and undergo only a change in concentration (ratio) by adding small amounts of pure charge material to achieve a target composition.
- Lithium-ion batteries like their NiCd (nickel-cadmium) and NiMH (nickel- metal hydride) predecessors, have a finite number of charge cycles. It is therefore expected that LIBs will become a significant component of the solid waste stream, as numerous electric vehicles reach the end of their lifespan. Recycling of the charge material in the lithium batteries both reduces waste volume and yields active charge material for new batteries.
- the disclosed approach does not separate Ni, Mn, and Co out. Instead, uniform-phase precipitation is employed as starting materials to synthesize the cathode materials as active charge material suitable for new batteries. The analytical results showed that the recycling process is practical and has high recovery efficiency, and has commercial value as well.
- Configurations herein are based, in part, on the observation that the increasing popularity of lithium ion cells as a source of portable electric power will result in a corresponding increase in spent lithium-based cathode material as the deployed cells reach the end of their useful lifetime. While 97% of lead acid batteries are recycled, such that over 50 percent of the lead supply comes from recycled batteries, lithium ion batteries are not yet being recycled widely. While the projected increase of lithium demand is substantial, analysis of Lithium's geological resource base shows that there is insufficient lithium available in the Earth's crust to sustain electric vehicle manufacture in the volumes required, based solely on Li-ion batteries. Recycling can dramatically reduce the required lithium amount. A recycling infrastructure will ease concerns that the adoption of vehicles that use lithium-ion batteries could lead to a shortage of lithium carbonate and a dependence on countries rich in the supply of global lithium reserves.
- configurations herein substantially overcome the described shortcoming of heat intensive component separation described above by generating a low temperature solution of the desired compounds that is mixed with small amounts of additional pure forms of the desirable materials to achieve a target ratio of the desired active charge materials.
- the desirable materials are extracted by precipitation to result in recycled active cathode material without separating or breaking down the
- the solution includes recovering active materials from lithium ion batteries with
- LiNiCoA10 2 chemistry in a manner that can be used to make new active materials for new lithium ion batteries.
- conventional approaches cannot recover transition metals from LiNiCoA102 in such a form that they can be used to make new cathode materials for LNiCo02 or LiNiCoA102 batteries without using expensive organic reagents.
- the recovered precursor material NiCoAl(OH) 2 or NiCo(OH) 2 can be used for making new LiNiCoA10 2 or LiNiCo0 2 cathode materials. This may include adding Al(OH) 3 to the precipitated material and/or Ni, Co, or Al sulfates to the solution prior to precipitation.
- the batteries be of a single stream chemistry (LiNiCoA10 2 ) however if there are other chemistries present in the L1MO2 (where M is manganese, as well as Ni, Al and Co), the manganese can be removed from solution.
- M is manganese, as well as Ni, Al and Co
- Ni, Co and Al can be used to precipitate precursor and synthesize cathode materials.
- the claimed approach defines a method of recycling Li ion batteries including generating a solution of aggregate battery materials from spent cells, and precipitating impurities from the generated solution to result in a charge material precursor. Materials are added to adjust the solution to achieve a predetermined ratio of desirable materials based on desired chemistry of the new, recycled battery. Lithium carbonate is introduced and sintered to form cathode materials in the form of LiNi x Co y Al z 02. Adjusting the desirable materials includes the addition of at least one of Ni, Co or Al, and typically the addition of desirable materials is in the form of salts or ions.
- a method of recycling Li-ion batteries therefore includes generating a solution of aggregate battery materials from spent cells, and precipitating mixtures from the generated solution.
- a recycler apparatus adjusts the solution to achieve a predetermined ratio of desirable materials, and precipitating the desirable material in the predetermined ratio to form cathode material for a new battery having the predetermined ratio of the desirable materials.
- Fig. 1 is a context diagram of a battery recycling environment suitable for use with configurations herein;
- Fig. 2 is a flowchart of lithium battery recycling in the environment of Fig. 1;
- Fig. 3 is a diagram of charge flow (electrons) during charging and discharging of the batteries of Fig. 1;
- Fig. 4 is a diagram of battery structure of the batteries of Fig. 1;
- Fig. 5 is a diagram of recycling the cathode material in the battery of Fig. 4;
- Fig. 6 is a process flow diagram of recycling lithium- aluminum ion batteries
- Fig. 7 is a process flow for an alternate configuration of recycling lithium- aluminum batteries using aluminum hydroxide
- Fig. 8 is a process flow diagram for a combined recycling process for both Ni/Mn/Co (NMC) and Ni/Co/Al (NCA) batteries for any suitable molar ratio.
- Fig. 1 is a context diagram of a battery recycling environment 100 suitable for use with configurations herein.
- electronic devices 110 such as laptops, automobiles (hybrid and pure electric), computers, smartphones, and any other type of battery supported equipment is suitable for use with the disclosed approach.
- the electronic devices contribute spent cells 120, having exhausted cathode material 122 that nonetheless includes the raw materials responsive to the recycling approach discussed herein.
- a physical separation process 124 dismantles the battery to form a granular mass 126 of the exhausted battery material including the raw materials in particulate form, usually by simply crushing and grinding the spent battery casings and cells therein.
- a recycler 130 includes physical containment of a solution 141 including the remaining granular mass 126 from the spent charge materials, typically taking the form of a powder from the agitated (crushed) spent batteries. Additional raw materials 142 are added to achieve a predetermined ratio of the desirable materials in the solution 141. Following the recycling process, as discussed further below, active charge materials 134 result and are employed to form new cells 140 including the recycled cathode material 132. The new cells 140 may then be employed in the various types of devices 110 that contributed the exhausted, spent cells 120.
- the recycler may include an apparatus for containing the solution 141 such that a pH adjuster or modifier and raw materials may be added to the solution 141.
- Fig. 2 is a flowchart of lithium battery recycling in the environment of Fig. 1.
- the method of recycling cathode material 122 as disclosed herein includes generating a solution 141 from cathode materials derived from exhausted battery cells 120, as depicted at step 200.
- the method combines additional raw material 142 to achieve a predetermined ratio of the materials in solution 141, and is such that the solution temperature is maintained sufficiently low for avoiding high temperature process common in conventional recycling approaches.
- the solution 141 precipitates the precursor materials 134 by increasing the pH of the solution 141, such that the precipitated materials 134 have the predetermined ratio and having suitable proportion for use to synthesize the cathode material 132 for the new battery cells 140.
- the desirable materials include manganese (Mn), cobalt (Co), and nickel (Ni) extracted from cathode material of battery cells.
- Mn manganese
- Co cobalt
- Ni nickel
- Fig. 3 is a diagram of charge flow (electrons) during charging and discharging of the batteries of Fig. 1. Batteries in general produce an electron flow via an
- a lithium-ion battery (LIB) 140' generates a negative electron flow 150 to power an electrical load 152 in a reversible manner (for recharge), similar to other rechargeable batteries.
- a charger 170 provides a voltage source that causes the electron flow 15 to reverse. Lithium ions 154 move from the negative electrode 160 to the positive electrode 162 during discharge, and back when charging.
- An anode tab 161 electrically connects the negative electrodes 160 for connection to the load 152/charger 170, and a cathode tab 163 connects the positive electrodes 162.
- An electrolyte 168 surrounds the electrodes for facilitating ion 154 transfer.
- a separator prevents contact between the anode 160 and cathode 162 to allow ionic transfer via the electrolyte 168 so that the anode and cathode plates do not "short out” from contact.
- the positive electrode 162 half-reaction (cathode reaction), take LiCo02 as an example:
- the negative electrode 160 half -reaction is: xLi + +xe " +6C ⁇ Li x C 6
- the transition metal cobalt is oxidized from Co 3+ to Co 4+ , and reduced from Co 4+ to Co 3+ during discharge.
- Fig. 4 is a diagram of battery structure of Fig. 1.
- the physical structure of the cell 140 is a cylinder encapsulation of rolled sheets defining the negative electrode 160 and the positive electrode 162.
- the anode 160 negative electrode material contains graphite, carbon and PVDF (polyvinylidene fluoride) binder, coated on copper foil.
- the cathode 162 (positive) electrode contains cathode material, carbon, and PVDF binder, coated on aluminum foil.
- the cathode 162 material is generally one of three kinds of materials: a layered oxide (such as lithium cobalt or nickel oxide), a polyanion (such as lithium iron phosphate), or a spinel (such as lithium manganese oxide), and defines the cathode material 122 and recycled cathode material 132 as disclosed herein.
- a layered oxide such as lithium cobalt or nickel oxide
- a polyanion such as lithium iron phosphate
- a spinel such as lithium manganese oxide
- the electrolyte 168 is typically a mixture of organic carbonates, generally use non-coordinating anion salts such as lithium hexafluorophosphate (LiPF 6 ).
- the electrolyte 168 acts as an ionic path between electrodes.
- the outside metal casing defines the negative terminal 161 ', coupled to the anode tab 161, and the top cap 163' connects to the cathode tab 163.
- a gasket 174 and bottom insulator 176 maintains electrical separation between the polarized components.
- the cathode materials widely used in commercial lithium ion batteries include L1C0O2, LiMn 2 04, LiNi , LiNi x Co y Al z O2, LiNi x Mn y Co z 02 and LiFeP0 4 .
- LiMn 2 04 LiNi , LiNi x Co y Al z O2, LiNi x Mn y Co z 02 and LiFeP0 4 .
- Configurations disclosed herein present an example to extract compounds including the desirable elements of Co, Ni, Mn, and Li from mixed cathode materials and utilize the recycled materials to produce active materials for batteries. Alternate chemistries may be recycled using the methods disclosed.
- Fig. 5 is a diagram of recycling the cathode material in the battery of Fig. 4. Referring to Figs. 1, 4 and 5, at step 1 discharged Li ion batteries 120 are
- the metallic elements of interest are transfer to the aqueous solution as the crushed raw cathode materials form a granular mass 126 used to generate the solution of aggregate battery materials from the spent cells, as depicted at step 3.
- the pH is adjusted to extract iron, copper and aluminum as Fe(OH) 3 , Cu(OH) 2 and Al(OH) 3 . This involves adjusting the pH to a range between 3.0-7.0.
- NaOH solution is added to adjust pH number to deposit Fe(OH) 3 , Cu(OH)2 and Al(OH)3 which have a lower solubility constant, and keep Mn 2+ , Co 2+ , Ni 2+ in the solution, then Fe(OH) 3 , Cu(OH)2 and Al(OH)3 are separated by filtration.
- the above processes include maintaining the solution 141 at a temperature between 40 deg. C. and 80 deg. C, thus avoiding high heat required in conventional approaches.
- adjusting the solution includes identifying a desired ratio of the desirable materials for use in recycled cathode material resulting from the generated solution 141, and adding raw materials 142 to achieve the desired ratio, such that the raw materials include additional quantities of the desirable materials and subsequently adding the new raw materials to attain the predetermined ratio.
- Adding the raw materials includes adding additional quantities of the desirable materials for achieving the desired ratio without separating the individual desirable materials already in solution form, therefore the mixed desirable materials (Co, Mn, Ni) do not need to be separately drawn or extracted as in conventional approaches, which usually involve high heat to break the molecular bonds of the compounds. Furthermore, in an alternate
- the pH may be adjusted to extract one or more metal ions or other elements prior to adjusting the solution for the predetermined ratio of desirable materials, and subsequent extract the remaining desirable materials in the predetermined ratio.
- the concentration of Mn 2+ , Co 2+ , Ni 2+ in the solution is tested, and adjusted the ratio of them to 1: 1: 1 or other suitable ratio with additional C0SO4, N1SO4, MnSC .
- NaOH solution is added to increase the pH to around 11, usually within a range of 10.0-13, thus adjusting a pH of the solution such that the desirable materials for the new (recycled) charge materials precipitate.
- Nii/3Mm/3Coi/30(OH) or a mixture thereof can be coprecipitated such that the respective mole ratio is 1: 1: 1, as depicted at step 4.
- NixMn y CozO(OH) or a mixture with different ratios of x, y, and z can also be precipitated.
- Na 2 C03 is added in the solution to deposit L12CO3, as depicted at step 5..
- the recovered Nii/3Mm/3Coi/3(OH) 2 and L12CO3 are sintered to produce the cathode material.
- the desirable materials include manganese (Mn), cobalt (Co), and nickel (Ni) extracted from charge material 122 of the spent battery cells 120, in which the desirable materials remain commingled in the solution 141 during precipitation.
- Adjusting the pH includes adding a substance, such as NaOH (sodium hydroxide, also referred to as lye or caustic soda) for raising the pH such that the desirable materials precipitate, however any suitable substance for raising the pH may be employed.
- adjusting the pH includes adding sodium hydroxide for raising the pH to permit precipitation of the desirable materials for use as cathode precursor material without separately precipitating the individual compounds defining the desirable materials.
- the precipitation of the desirable materials occurs at temperatures below 80 deg.
- Li 2 C0 3 is added in the solution to deposit Li 2 C0 3 at about 40°C. After filtrating, Li 2 C0 3 can be recycled as the starting material to synthesis the active cathode material LiNii/ 3 Mm/ 3 Coi/ 3 0 2 , as shown at steps 5 and 5a. Therefore, the method adds back the lithium to the precipitated desirable materials to form active cathode material suitable for the new battery, and precipitates the desirable material in the predetermined ratio to form charge material for a new battery 140 having the predetermined ratio of the desirable materials.
- the coprecipitated materials Nii/ 3 Mm/ 3 Coi/ 3 (OH) 2 or Nii/ 3 Mm/ 3 Coi/ 3 0(OH) or their mixture and recovered Li 2 C0 3 , with additional Li 2 C0 3 in molar ratio 1.1 of Li versus M are mixed and grinded in mortar, as depicted at step 6.
- the mixture may be reformulated by any suitable processing to form the active cathode material 134 for new batteries 140.
- the mixture was sintered at 900 for 15 hours.
- the reaction product may be ground into powder for subsequent distribution and reformation into new cells 140.
- the LiNii/ 3 Mm/ 3 Coi/ 3 0 2 is sintered by a high temperature solid-state method at 900°Cfor 15 hours.
- Battery chemistries including aluminum (Al) are becoming popular for applications such as electric vehicles, using chemistry such as LiNiCoA10 2 .
- NiCoAl(OH)2 or NiCo(OH) 2 can be used for making new LiNiCoA10 2 or LiNiCo0 2 cathode materials. This may include adding Al(OH) 3 to the precipitated material and/or Ni,Co, or Al sulfates to the solution prior to precipitation.
- solution of nickel and cobalt sulfates was from recycled material.
- A1 2 (S04)3- 18H 2 0 as Al starting material was dissolved in distilled water.
- chelating agent 5- sulfosalicylic acid was dissolved in the solution of aluminum sulfates.
- Solutions of transition metal sulfates, aluminum sulfate, ammonia, and NaOH were pumped into a continuous stirred tank reactor. Total concentration of solutions of the metal sulfates was 1.5 M or other concentrations. Concentration of the chelating agent is 0.05M- 0.5M. pH was controlled 10-pH. Stirring speed was 500- 1000 rpm and the
- NiCoAl(OH) 2 co-precipitate was filtered, washed and dried.
- the metal hydroxide co-precipitate precursor was mixed with 5% excess lithium carbonate thoroughly. The mixture was at first calcined at 450°C for 4-6h in air, and then sintered at 750-850°C for 15-20h in an oxygen atmosphere or air to obtain LiNi x Co y Al z 02 powder to form charge material suitable for use in new batteries.
- the batteries be of a single stream chemistry (LiNiCoA10 2 ) however if there are other chemistries present in the L1MO2 (where M is manganese, as well as Ni, Al and Co), the manganese can be removed from solution.
- M is manganese, as well as Ni, Al and Co
- Ni, Co and Al can be used to precipitate precursor and synthesize cathode materials.
- Fig. 6 is a process flow diagram of recycling lithium ion batteries.
- Fig. 7 is a process flow for an alternate configuration of recycling lithium ion batteries using aluminum hydroxide.
- the cathode powders in order to undergo the recovery process, the cathode powders must be separated from the batteries/current collectors. Physical agitation of spent cell materials are used to extract cathode material by leaching crushed spent battery materials in a sealed system or containment to separate current collectors in a solution, as depicted at step 601. An example method of how this could be done is by shredding and sizing. Then the powders can be leached into solution using a
- leaching may include forming a solution from addition of at least one of hydrogen peroxide and sulfuric acid.
- Impurities can be removed by adjusting a pH of the solution for removing impurities by precipitating hydroxides and filtering. This may be performed by increasing the pH to 5-7, precipitating the respective hydroxides and filtering, as disclosed at step 602.
- Aluminum hydroxide may also be removed in this step.
- Mn ions in the solution can also be removed by adding suitable chemicals. The concentration of ions in solution will be measured and adjusted to the desired ratio based on the industrial needs.
- Precursor materials may then be recovered by precipitating using at least one of sodium hydroxide or potassium hydroxide, as shown at step 605. Sintering the recovered precursor materials with lithium carbonate forms active cathode material, as depicted at steps 606 and 607.
- the precipitate from step 605 can be sold to material or battery manufacturers or can then be mixed and sintered with the lithium carbonate to form active LiNiCoA10 2 .
- steps 701-703 proceed as their counterparts in Fig. 6. If it is desirable to recover LiNiCo0 2 material the procedure follows Fig. 6 but no aluminum is added back into the solution or precipitate. Accordingly, the process includes adding only Ni or Co prior to precipitating the recovered charge materials at step 704. The process defers addition of aluminum hydroxide (step 706) until after precipitation (step 705) and before sintering at step 708. In general, using the processes depicted in Figs.
- active charge material formed includes LiNixCoxAlz02 where x, y and z are integers defining the composition of the resulting active charge material.
- Other materials including Cu, Al, steel, carbon, lithium carbonate, and other materials including transition metals can also be recovered
- the above approaches converge to a single stream recycling process including both Ni/Mn/Co (NMC) and Ni/Co/Al (NCA) chemistries, by recognizing the common aspects of pH changes and recombining pure (virgin) cathode materials to form a combined precursor having a molar ratio based on the chemistry requirements for the new, recycled cathode materials.
- NMC Ni/Mn/Co
- NCA Ni/Co/Al
- Fig. 8 is a process flow diagram for a combined recycling process for both Ni/Mn/Co and Ni/Co/Al batteries for any suitable molar ratio. In the approach of Fig. 8, the following benefits are achieved:
- Both LiNixMnyCozC and LiNi x Co y Al z 02 are cathode materials for Li- ion batteries. These cathode materials can be synthesized in the recycling process. These recovered cathode materials have similar performance with the virgin materials and can be used to make new batteries.
- LiNixMn y Co z 02 and LiNixCoyAlz02 can be synthesized by sintering their carbonates or hydroxides with L12CO3.
- LiNi x Mn y Co z 02 is synthesized by sintering Ni x Mn y Co z (OH)2 and L12CO3. It should be noted that both the elemental composition (e.g.
- NMC or NCA NMC or NCA
- molar ratio of those elements are determined both by the molar ratios following leaching, and the addition of pure raw materials to the leached solution, designated by the subscripts x,y,z specifying the respective molar ratios.
- Other suitable battery chemistries may be formed using the disclosed approach.
- LiNi x Mn y Co z 02 or LiNi x Co y Al z 02 can be synthesized. If the recycling stream includes Mn based batteries or Mn compound is added, LiNixMnyCoz02 is synthesized. If the recycling stream does not include Mn based batteries or Mn is removed, LiNixCoyAlz02 is synthesized.
- impurities can be removed by increasing the pH to 5-7, precipitating their hydroxides and filtering. 5.
- the carbonate and hydroxide precursor precipitates can be obtained by controlling their solubility in the solution.
- the method for recycling lithium-ion batteries comprising includes, at step 801, receiving a recycling stream of expended, discarded and/or spent lithium ion batteries, and agitating the batteries to expose the internal components and charge material by physical crushing, shredding and/or disengagement to provide surface area open to liquid exposure, as depicted at step 802.
- a leached solution is formed by combining crushed battery material from the lithium battery recycling stream with an acidic leach agent and hydrogen peroxide (H2O2) to separate cathode materials from undissolved material,, as depicted at step 804.
- a low pH solvent bath, leach liquor or other suitable combination immerses the agitated materials of the recycling stream for dissolving the cathode materials such as Ni, Mn, Co and Al.
- the acidic leach agent may be concentration of sulfuric acid in the range of 2-5 M (molar), and in a particular arrangement, the acidic leach agent is 4M sulfuric acid.
- a particular feature of the disclosed approach is adaptability to various target chemistries for the recycled batteries, and sourced from various unknown chemistries in the recycling stream.
- Design or demand specifications determine material parameters for a recycled battery by identifying a molar ratio and elements of cathode materials corresponding to a charge material chemistry of a recycled battery.
- Battery usage as directed by a customer may be an overriding factor, such as automotive electric or hybrid vehicle usage, portable electronic devices, etc.
- the identified battery chemistry, specifying particular elements and molar ratios, results in the specific electrical characteristics of the recycled batteries produced by the disclosed approach.
- a test or sample is employed to determine a composition of the leach solution by identifying a molar ratio of the ions dissolved therein, thus clarifying the previously unknown collective composition of the input recycling stream. Recall that all charge material has remained comingled in the leach solution- extraction or precipitation of individual elements has not been required.
- Ni, Co, Mn or Al salts in a sulfate (xS0 4 ) or hydroxide (xOH) form are added to the leach solution to adjust the molar ratio of the dissolved cathode material salts in the leach solution to correspond to the identified molar ratio for the recycled battery.
- a NMC chemistry with 1: 1: 1 ratio may be sought, or alternatively, a NCA chemistry with 1:2: 1.
- Any suitable ratio and combination of charge materials may be selected.
- One particular selection may be the determination of whether manganese (Mn) is included or whether NCA manganese-free formulation will be employed.
- impurities Prior to adjusting the molar ratio, impurities may be precipitated from the leach solution by adding sodium hydroxide until the pH is in a range between 5.0-7.0 for precipitating hydroxide forms of the impurities outside the determined material parameters, as depicted at step 805.
- the determined battery chemistry and source recycling stream results in a decision point from step 805. If the chemistry for the recycled battery include manganese (Mn), then the cathode material salts include Ni, Mn and Co in a hydroxide form, as depicted at step 806. Otherwise, if the recycled battery is devoid of Mn, then the cathode material salts include Ni, Co and Al in a hydroxide form, as shown at step 809. In the non-Mn formulation, prior to adding raw material for adjusting the molar ratio, manganese ions may be removed from the leach solution.
- Mn manganese
- sodium hydroxide is added for raising the pH of the leach solution to at least lOfor precipitating and filtering metal ions of the cathode materials to form a charge material precursor by coprecipitating the Ni, Co, Mn and Al salts remaining in the leach solution as a combined hydroxide (OH), (OH) 2 or carbonate (C0 3 ) having a molar ratio corresponding to the identified molar ratio for the recycled battery, the charge precursor material responsive to sintering for forming active cathode materials in an oxide form following sintering with lithium carbonate (Li2C0 3 ).
- charge precursor material is generated by raising the pH to a range of 10-13.0 for precipitating hydroxide charge material, and more specifically, may include raising pH by adding sodium hydroxide to increase the pH to 11.0, as depicted at steps 807 and 810.
- the resulting charge material precursor has the form
- the aluminum sulfate is mixed with a chelating agent, and the aluminum sulfate solution and nickel cobalt sulfate solutions are added with ammonium water and sodium hydroxide to a reactor.
- a pH monitor constantly monitors and releases additional sodium hydroxide to maintain the pH at 10.0 or other suitable pH to result in coprecipitation of the NCA precursor.
- Fig. 8 The generalized process of Fig. 8 is intended to accommodate Al based battery chemistries without Mn, but may also be used for any suitable formulation by modifying the molar ratios at steps 806 or 809, as applicable.
Abstract
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Claims
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