ABSTRACT
Abstract
Cathode material from exhausted lithium ion batteries are dissolved in a solution for extracting the useful elements Co (cobalt), Ni (nickel), Al (Aluminum) and Mn (manganese) to produce active cathode materials for new batteries. The solution includes compounds of valuable charge materials such as cobalt, nickel, aluminum and manganese dissolved as compounds from the exhausted cathode material of spent cells. However, LiFePO4 is a waste stream charge material often discarded due to infeasibility of recycling. LiFePO4 is precipitated as FePO4 and remains as a by-product, along with graphite and carbon, which are not dissolved into the solution. FePO4 can be separated from graphite and carbon, FePO4 can be used to synthesize LiFePO4 as cathode materials and graphite can be regenerated as anode materials.
Description
RELATED APPLICATIONS
This patent application claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional Patent App. No. 62/504,699, filed May 11, 2017, entitled âMETHOD OF RECOVERING LiFePO4 AND GRAPHITE FROM LITHIUM ION BATTERIES,â and is a Continuation-in-Part (CIP) of U.S. patent application Ser. No. 15/358,862, filed Nov. 22, 2016, which claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional Patent App. No. 62/259,161, filed Nov. 24, 2015, entitled âMETHOD AND APPARATUS FOR RECYCLING LITHIUM-ION BATTERIES,â and is a Continuation-in-Part (CIP) of U.S. patent application Ser. No. 13/855,994, filed Apr. 3, 2013, entitled âMETHOD AND APPARATUS FOR RECYCLING LITHIUM-ION BATTERIES,â now U.S. Pat. No. 9,834,827, which claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional Patent App. No. 61/620,051, filed Apr. 4, 2012, entitled âFULL CLOSED LOOP FOR RECYCLING LITHIUM ION BATTERIES,â all incorporated herein by reference in entirety.
BACKGROUND
For decades, portable electrical power supplies have taken the form of batteries that release electrical energy from an electrochemical reaction. Various battery chemistries, such as traditional âdry cellâ carbon flashlight batteries, and lead acid âwetâ cells common in automobiles have provided adequate portable electrical power. Modern electronics, however, place significantly greater demands on the longevity and mass of batteries. Battery power has traditionally come at a premium of the mass required for the charge material for generating sufficient current. Conventional flashlight batteries deliver only low current. Automobile batteries for delivering an intense but brief high amperage flow to a starter motor are very dense and large. 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.
Rechargeable nickel-cadmium (NiCad) and nickel metal hydride (NiMH) had gained popularity for rechargeable batteries for portable devices. Recently, however, advances in lithium-ion batteries (LIBs) have been significant such that they have become the most popular power source for portable electronics equipment, and are also growing in popularity for military, electric vehicle, and aerospace applications. Continuing development of personnel electronics, hybrid and electric vehicles, ensures that Li-ion batteries will continue to be increasingly in demand.
SUMMARY
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 LiNiCoAlO 2 , which is being used in automobile application (for example Tesla⢠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.
Recycling can dramatically reduce the required lithium amount. Various chemicals in lithium ion batteries include valuable metals such as cobalt, manganese, and nickel. Additionally, battery disposal would require that fresh metals be mined for cathode material, and mining has a much bigger environmental impact and cost than simple recycling would. In short, recycling of lithium ion batteries not only protects the environment and saves energy, but also presents a lucrative outlet for battery manufacturers by providing an inexpensive supply of active cathode material for new batteries.
Current recycling procedures for Li-ion cells are generally focused on LiCoO 2 cathode materials. Although some posted their methods to recycle more kinds of cathode materials, all are complex and not necessarily economical or practical. A simple methodology with high efficiency is proposed in order to recycle Li-ion batteries economically and with industrial viability. The disclosed approach results in synthesis of cathode materials (particularly valuable in Li-ion batteries) from recycled components. In contrast to conventional approaches, 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.
Unfortunately, conventional approaches to the above approaches suffer from the shortcoming that recycling approaches include high temperature processes to separate the compounds of the desirable materials of cobalt, manganese, nickel and lithium. This high-temperature process results in breaking down the compounds for separation, but only to recombine them again for new active material. The high temperature approach therefore requires substantial energy, expense, and processing for separating and recombining the desirable materials.
Accordingly, 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 compounds, allowing a lower temperature and less expensive process to generate the active cathode materials.
The solution includes recovering active materials from lithium ion batteries with LiNiCoAlO 2 chemistry in a manner that can be used to make new active materials for new lithium ion batteries. To date, conventional approaches cannot recover transition metals from LiNiCoAlO2 in such a form that they can be used to make new cathode materials for LNiCoO2 or LiNiCoAlO2 batteries without using expensive organic reagents. The recovered precursor material NiCoAl(OH) 2 or NiCo(OH) 2 can be used for making new LiNiCoAlO 2 or LiNiCoO 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.
In the proposed approach, it is desirable that the batteries be of a single stream chemistry (LiNiCoAlO 2 ) however if there are other chemistries present in the LiMO 2 (where M is manganese, as well as Ni, Al and Co), the manganese can be removed from solution. Ni, Co and Al can be used to precipitate precursor and synthesize cathode materials.
It is likely that cells of various chemistries will appear in the recycling stream. In particular, LiFePO 4 is received and recycled by alternate configurations disclosed below. However, LiFePO 4 is a waste stream charge material often discarded due to infeasibility of recycling. In configurations disclosed herein, LiFePO 4 is precipitated as FePO4 and remains as a by-product, along with graphite and carbon, which are not dissolved into the solution. FePO 4 can be separated from graphite and carbon, FePO 4 can be used to synthesize LiFePO 4 and graphite can be regenerated.
The claimed approach, outlined in more detail below, 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 batteries. Lithium carbonate is introduced and sintered to form cathode materials in the form of LiNi x Co y Al z O 2 . 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.
In the approach disclosed below, 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. It should be noted that although the methods and apparatus disclosed herein employ Li-ion batteries as an example, the principles are intended as illustrative and could be applied to other types of cathode materials suited to other battery chemistries.
In the battery recycling process for acidic leaching of charge materials from a waste stream of crushed and shredded battery contents, a method for recycling lithium iron phosphate from residual iron phosphate after acidic leaching Ni, Mn and Co may include removing solid battery components including casing and electrode materials from exhausted lithium ion batteries (LIBs) by physical separation from the acidic leach solution resulting in a granular mass of exhausted charge materials including carbon, graphite and iron phosphate. An inorganic acid is added to the granular mass to separate graphite and carbon from the iron phosphate to yield a solution of iron chloride and phosphoric acid with undissolved carbon and graphite. Adjusting the pH of the iron chloride and phosphoric acid solution precipitates an iron phosphate precursor. Lithium carbonate may be combined with the precipitated iron phosphate by agitation, and the combined mixture of lithium carbonate and iron phosphate sintered to yield cathode powders adapted for use as charge materials.
In the discussion below, this defines a secondary recycling/leach stream after removing solid battery components including casing and electrode materials from exhausted lithium ion batteries (LIBs) by physical separation resulting in a granular mass of exhausted charge materials including carbon, graphite and residual cathode materials. A first inorganic acid is added to the granular mass for leaching charge materials other than iron phosphate from the exhausted charge materials. A leach solution resulting from the leached charge materials is directed to a recycling stream. A second inorganic acid is added to the remaining granular mass to generate a leach solution including iron chloride and phosphoric acid and leaving carbon and graphite undisturbed. The secondary stream adjusts the pH of the generated leach solution to precipitate an iron phosphate precursor, such that the iron phosphate precursor is responsive to lithium carbonate and sintering for forming lithium iron phosphate.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other features will be apparent from the following description of particular embodiments disclosed herein, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.
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. 9 shows an alternative configuration for processing residual charge material as in FIG. 8 ; and
FIGS. 10 a - b are a flowchart for recycling lithium iron phosphate (LiFePO 4 ) from the residual charge material of FIG. 9 .
DETAILED DESCRIPTION
Depicted below is an example method and apparatus for recycling batteries such as lithium ion batteries. The proposed approach is an example and is applicable to other lithium and non-lithium batteries for recycling spent batteries and recovering active cathode material suitable for use in new batteries. FIG. 1 is a context diagram of a battery recycling environment 100 suitable for use with configurations herein. Referring to FIG. 1 , in the battery recy
RELATED APPLICATIONS
This patent application claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional Patent App. No. 62/504,699, filed May 11, 2017, entitled âMETHOD OF RECOVERING LiFePO4 AND GRAPHITE FROM LITHIUM ION BATTERIES,â and is a Continuation-in-Part (CIP) of U.S. patent application Ser. No. 15/358,862, filed Nov. 22, 2016, which claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional Patent App. No. 62/259,161, filed Nov. 24, 2015, entitled âMETHOD AND APPARATUS FOR RECYCLING LITHIUM-ION BATTERIES,â and is a Continuation-in-Part (CIP) of U.S. patent application Ser. No. 13/855,994, filed Apr. 3, 2013, entitled âMETHOD AND APPARATUS FOR RECYCLING LITHIUM-ION BATTERIES,â now U.S. Pat. No. 9,834,827, which claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional Patent App. No. 61/620,051, filed Apr. 4, 2012, entitled âFULL CLOSED LOOP FOR RECYCLING LITHIUM ION BATTERIES,â all incorporated herein by reference in entirety.
BACKGROUND
For decades, portable electrical power supplies have taken the form of batteries that release electrical energy from an electrochemical reaction. Various battery chemistries, such as traditional âdry cellâ carbon flashlight batteries, and lead acid âwetâ cells common in automobiles have provided adequate portable electrical power. Modern electronics, however, place significantly greater demands on the longevity and mass of batteries. Battery power has traditionally come at a premium of the mass required for the charge material for generating sufficient current. Conventional flashlight batteries deliver only low current. Automobile batteries for delivering an intense but brief high amperage flow to a starter motor are very dense and large. 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.
Rechargeable nickel-cadmium (NiCad) and nickel metal hydride (NiMH) had gained popularity for rechargeable batteries for portable devices. Recently, however, advances in lithium-ion batteries (LIBs) have been significant such that they have become the most popular power source for portable electronics equipment, and are also growing in popularity for military, electric vehicle, and aerospace applications. Continuing development of personnel electronics, hybrid and electric vehicles, ensures that Li-ion batteries will continue to be increasingly in demand.
SUMMARY
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 LiNiCoAlO 2 , which is being used in automobile application (for example Tesla⢠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.
Recycling can dramatically reduce the required lithium amount. Various chemicals in lithium ion batteries include valuable metals such as cobalt, manganese, and nickel. Additionally, battery disposal would require that fresh metals be mined for cathode material, and mining has a much bigger environmental impact and cost than simple recycling would. In short, recycling of lithium ion batteries not only protects the environment and saves energy, but also presents a lucrative outlet for battery manufacturers by providing an inexpensive supply of active cathode material for new batteries.
Current recycling procedures for Li-ion cells are generally focused on LiCoO 2 cathode materials. Although some posted their methods to recycle more kinds of cathode materials, all are complex and not necessarily economical or practical. A simple methodology with high efficiency is proposed in order to recycle Li-ion batteries economically and with industrial viability. The disclosed approach results in synthesis of cathode materials (particularly valuable in Li-ion batteries) from recycled components. In contrast to conventional approaches, 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.
Unfortunately, conventional approaches to the above approaches suffer from the shortcoming that recycling approaches include high temperature processes to separate the compounds of the desirable materials of cobalt, manganese, nickel and lithium. This high-temperature process results in breaking down the compounds for separation, but only to recombine them again for new active material. The high temperature approach therefore requires substantial energy, expense, and processing for separating and recombining the desirable materials.
Accordingly, 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 compounds, allowing a lower temperature and less expensive process to generate the active cathode materials.
The solution includes recovering active materials from lithium ion batteries with LiNiCoAlO 2 chemistry in a manner that can be used to make new active materials for new lithium ion batteries. To date, conventional approaches cannot recover transition metals from LiNiCoAlO2 in such a form that they can be used to make new cathode materials for LNiCoO2 or LiNiCoAlO2 batteries without using expensive organic reagents. The recovered precursor material NiCoAl(OH) 2 or NiCo(OH) 2 can be used for making new LiNiCoAlO 2 or LiNiCoO 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.
In the proposed approach, it is desirable that the batteries be of a single stream chemistry (LiNiCoAlO 2 ) however if there are other chemistries present in the LiMO 2 (where M is manganese, as well as Ni, Al and Co), the manganese can be removed from solution. Ni, Co and Al can be used to precipitate precursor and synthesize cathode materials.
It is likely that cells of various chemistries will appear in the recycling stream. In particular, LiFePO 4 is received and recycled by alternate configurations disclosed below. However, LiFePO 4 is a waste stream charge material often discarded due to infeasibility of recycling. In configurations disclosed herein, LiFePO 4 is precipitated as FePO4 and remains as a by-product, along with graphite and carbon, which are not dissolved into the solution. FePO 4 can be separated from graphite and carbon, FePO 4 can be used to synthesize LiFePO 4 and graphite can be regenerated.
The claimed approach, outlined in more detail below, 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 batteries. Lithium carbonate is introduced and sintered to form cathode materials in the form of LiNi x Co y Al z O 2 . 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.
In the approach disclosed below, 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. It should be noted that although the methods and apparatus disclosed herein employ Li-ion batteries as an example, the principles are intended as illustrative and could be applied to other types of cathode materials suited to other battery chemistries.
In the battery recycling process for acidic leaching of charge materials from a waste stream of crushed and shredded battery contents, a method for recycling lithium iron phosphate from residual iron phosphate after acidic leaching Ni, Mn and Co may include removing solid battery components including casing and electrode materials from exhausted lithium ion batteries (LIBs) by physical separation from the acidic leach solution resulting in a granular mass of exhausted charge materials including carbon, graphite and iron phosphate. An inorganic acid is added to the granular mass to separate graphite and carbon from the iron phosphate to yield a solution of iron chloride and phosphoric acid with undissolved carbon and graphite. Adjusting the pH of the iron chloride and phosphoric acid solution precipitates an iron phosphate precursor. Lithium carbonate may be combined with the precipitated iron phosphate by agitation, and the combined mixture of lithium carbonate and iron phosphate sintered to yield cathode powders adapted for use as charge materials.
In the discussion below, this defines a secondary recycling/leach stream after removing solid battery components including casing and electrode materials from exhausted lithium ion batteries (LIBs) by physical separation resulting in a granular mass of exhausted charge materials including carbon, graphite and residual cathode materials. A first inorganic acid is added to the granular mass for leaching charge materials other than iron phosphate from the exhausted charge materials. A leach solution resulting from the leached charge materials is directed to a recycling stream. A second inorganic acid is added to the remaining granular mass to generate a leach solution including iron chloride and phosphoric acid and leaving carbon and graphite undisturbed. The secondary stream adjusts the pH of the generated leach solution to precipitate an iron phosphate precursor, such that the iron phosphate precursor is responsive to lithium carbonate and sintering for forming lithium iron phosphate.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other features will be apparent from the following description of particular embodiments disclosed herein, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.
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. 9 shows an alternative configuration for processing residual charge material as in FIG. 8 ; and
FIGS. 10 a - b are a flowchart for recycling lithium iron phosphate (LiFePO 4 ) from the residual charge material of FIG. 9 .
DETAILED DESCRIPTION
Depicted below is an example method and apparatus for recycling batteries such as lithium ion batteries. The proposed approach is an example and is applicable to other lithium and non-lithium batteries for recycling spent batteries and recovering active cathode material suitable for use in new batteries. FIG. 1 is a context diagram of a battery recycling environment 100 suitable for use with configurations herein. Referring to FIG. 1 , in the battery recycling environment 100 , 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.
Physical separation is applied to remove the battery cases (plastic) and electrode materials, often via magnetic separation that draws out the magnetic steel. 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 . Referring to FIGS. 1 and 2 , 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 . In the example configuration, the desirable materials include manganese (Mn), cobalt (Co), and nickel (Ni) extracted from cathode material of battery cells. In the solution 141 , the desirable materials remaining commingled during precipitation such that the resulting cathode material 134 has the correct proportion for usage in the new cells 140 .
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 electrochemical reaction that causes an electrical current from the electron flow to provide the electrical power, coupled with a corresponding flow of ions in the battery between an anode and cathode. Referring to FIGS. 1 and 3 , a lithium-ion battery (LIB) 140 â² generates a negative electron flow 150 to power an electrical load 152 in a reversible manner (for recharge), similar to other rechargeable batteries. During charging, a charger 170 provides a voltage source that causes the electron flow 151 â² 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 âshort outâ from contact. The positive electrode 162 half-reaction (cathode reaction), take LiCoO2 as an example:
LiCoO 2
Li 1-x CoO 2 +x Li+ xe â
The negative electrode 160 half-reaction is:
x Li + +xe â +6C
Li x C 6
Overall Cell Reaction:
C+LiCoO 2
Li x C+Li 1-x CoO 2
During charging, 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 . Referring to FIGS. 3 and 4 , the physical structure of the cell 140 is a cylinder encapsulation of rolled sheets defining the negative electrode 160 and the positive electrode 162 .
Primary functional parts of the lithium- ion battery 140 are the anode 160 , cathode, 162 electrolyte 168 , and separator 172 . LIBs use an intercalated lithium compound as the electrode materials. The most commercially popular 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. Alternatively, the disclosed approach for recycling cathode material may be applied to other materials in various battery components, such as anodic and electrolyte components. 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 â², coupled to the anode tab 161 , and the top cap 163 â² connects to the cathode tab 163 . A gasket 174 and bottom insulator 176 maintains electrical separation between the polarized components.
Conventional approaches for recycling focus on LiCoO 2 in spent LIBs. However, with the development of lithium ion battery technologies, different cathode materials are now being used to produce lithium ion batteries such as LiCoO 2 , LiFePO4, LiMnO 2 , LiNi x Co y Al z O 2 and LiNi x Mn y Co z O 2 . It can be complex to sort out lithium ion batteries based on the battery chemistry and conventional methods cannot effectively recycle lithium ion batteries with mixed chemistries because different procedures are required to separate the respective compounds for reuse as active cathode material.
The cathode materials widely used in commercial lithium ion batteries include LiCoO 2 , LiMn 2 O 4 , LiNiO 2 , LiNi x Co y Al z O 2 , LiNi x Mn y Co z O 2 and LiFePO 4 . In order to recycle lithium ion batteries effectively, it is beneficial to consider all the various battery chemistries. Thus, it is beneficial to develop a simpler and environmentally acceptable recycling process generally applicable to various widely used LIBs used widely. 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 crushed/shredded. Mechanical separation processes are applied as a pretreatment to separate the outer cases and shells and the plastic fraction, as shown at step 1 a.
The sieved cathode powder will be leached by 4M sulfuric acid (H 2 SO 4 ) and 29-32% hydrogen peroxide for about 2-3 hours at 70-80° C., as depicted at step 2 . Other concentrations of sulfuric acid may also be employed. Addition of hydrogen peroxide H 2 O 2 changes not only Fe2+ to Fe3+, but also other metal ions Mn, Ni, Co to 2+, thus leading to separate iron by controlling pH of the solution in step 3 . After filtration, residual LiFeO4 and carbon can be separated by centrifugation, as shown at step 2 a . Other impurities are also removed from the surface of the solution, as shown at step 2 b.
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 . This includes the desirable materials of Co (cobalt), Ni (nickel), Mn (manganese), and Li (lithium in the example shown; other desirable materials may be employed using the present approach with alternate battery chemistries. 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. Accordingly, 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. It should be noted that 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.
The desirable materials are now dissolved in the solution 141 . Based on the predetermined target ratio of the desirable materials, the solution is adjusted to achieve the predetermined ratio of desirable materials. In the example approach, this is a 1:1:1 combination of cobalt, manganese and nickel, although any suitable ratio could be employed. Therefore, 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 configuration, selected metallic elements can be separated from the solution, which can be used to synthesize particular cathode materials. Therefore, 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.
Rather, 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 CoSO 4 , NiSO 4 , MnSO 4 . 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. Ni 1/3 Mn 1/3 Co 1/3 (OH) 2 or Ni 1/3 Mn 1/3 Co 1/3 O(OH) or a mixture thereof can be coprecipitated such that the respective mole ratio is 1:1:1, as depicted at step 4 . Ni x Mn y Co z (OH) 2 or Ni x Mn y Co z O(OH) or a mixture with different ratios of x, y, and z can also be precipitated. Na 2 CO 3 is added in the solution to deposit Li 2 CO 3 , as depicted at step 5 . Finally, the recovered Ni 1/3 Mn 1/3 Co 1/3 (OH) 2 and Li 2 CO 3 are sintered to produce the cathode material.
In the example arrangement, 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. The end result is that 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. C., avoiding high heat required in conventional approaches. It should be further noted that, in contrast to conventional approaches, the desirable materials remain commingled during precipitation as a combined hydroxide (OH), (OH) 2 or carbonate (CO 3 ). The addition of the additional charge materials for adjusting the ratio achieves the desired molar ratio for the resulting recycled battery. The intermediate, or precursor form will result in a lithium oxide form following sintering with lithium carbonate Li 2 CO 3 .
Na 2 CO 3 is added in the solution to deposit Li 2 CO 3 at about 40° C. After filtrating, Li 2 CO 3 can be recycled as the starting material to synthesis the active cathode material LiNi 1/3 Mn 1/3 Co 1/3 O 2 , as shown at steps
5 and 5 a . 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 Ni 1/3 Mn 1/3 Co 1/3 (OH) 2 or Ni 1/3 Mn 1/3 Co 1/3 O(OH) or their mixture and recovered Li 2 CO 3 , with additional Li 2 CO 3 in molar ratio 1.1 of Li versus M (M=Ni 1/3 Mn 1/3 Co 1/3 ), 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 . In the example approach, 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 LiNi 1/3 Mn 1/3 Co 1/3 O 2 is sintered by a high temperature solid-state method at 900° C. for 15 hours.
Battery chemistries including aluminum (Al) are becoming popular for applications such as electric vehicles, using chemistry such as LiNiCoAlO 2 . Conventional approaches for recovering active materials from lithium ion batteries with chemistry LiNiCoAlO 2 in a manner that can be used to make new active materials for new lithium ion batteries have been met with several shortcomings. Conventional processes cannot recover transition metals from LiNiCoAlO 2 in such a form that they can be used to make new cathode materials for LNiCoO 2 or LiNiCoAlO 2 batteries without using expensive organic reagents. The recovered precursor material NiCoAl(OH) 2 or NiCo(OH) 2 can be used for making new LiNiCoAlO 2 or LiNiCoO 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. One specific example is that solution of nickel and cobalt sulfates was from recycled material. Al 2 (SO 4 ) 3 .18H 2 O as Al starting material was dissolved in distilled water. Subsequently, 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 temperature was controlled in 30-60° C. After the reaction, 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 4-6 h in air, and then sintered at 750-850° C. for 15-20 h in an oxygen atmosphere or air to obtain LiNi x Co y Al z O2 powder to form charge material suitable for use in new batteries.
For such a recycling operation, it is desirable that the batteries be of a single stream chemistry (LiNiCoAlO 2 ) however if there are other chemistries present in the LiMO 2 (where M is manganese, as well as Ni, Al and Co), the manganese can be removed from solution. Ni, Co and Al can be used to precipitate precursor and synthesize cathode materials.
For the recovery and synthesis of LiNiCoAlO 2 there are at least two approaches. 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.
Referring to FIG. 6 , 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 combination of sulfuric acid and hydrogen peroxide, thus 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. At step 603 , 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. This includes adding at least one of Ni, Co and aluminum salts based on a desired composition of resulting recovered charge materials, as depicted at step 604 . It may be desirable to increase the pH above 7 prior to adding Al(SO4) 3 or Al(OH) 3 or other aluminum salts to the solution. 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 LiNiCoAlO 2 .
In an alternate configuration, depicted in FIG. 7 , no aluminum is added to solution and Al(OH) 3 is added to the material after precipitation, after mixing it is sintered with lithium carbonate to form the active material. Therefore, referring to FIG. 7 , steps 701 - 703 proceed as their counterparts in FIG. 6 . If it is desirable to recover LiNiCoO 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. 6 and 7 , active charge material formed includes LiNixCoxAlzO2 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
In an alternate arrangement, 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.
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:
1. Both LiNi x Mn y Co z O 2 and LiNi x Co y Al z O 2 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.
2. In the flow chart of FIG. 8 , bo
CLAIMS
Claims ( 18 )
What is claimed is:
1. In a battery recycling process for acidic leaching of charge materials from a waste stream of crushed and shredded battery contents, aA method for recycling lithium iron phosphate from residual iron phosphate after acidic leaching, comprising:
removing solid battery components including casing and electrode materials from exhausted lithium ion batteries (LIBs) by physical separation from an acidic leach solution resulting in a granular mass of exhausted charge materials including carbon, graphite and iron phosphate;
adding hydrochloric acid to the granular mass to separate graphite and carbon from the iron phosphate to yield a solution of iron chloride and phosphoric acid with undissolved carbon and graphite;
adjust the pH of the solution of iron chloride and phosphoric acid to precipitate iron phosphate;
combining and agitating lithium carbonate with the precipitated iron phosphate; and
sintering the combined and agitated lithium carbonate and iron phosphate to yield cathode powder.
2. The method of claim 1 further comprising sintering the combined mixture to generate LiFePO 4 .
3. The method of claim 1 further comprising precipitating the iron phosphate by circulating and heating a reactor containing the iron chloride and phosphoric acid solution to precipitate iron phosphate in a powder form.
4. The method of claim 1 further comprising combining a carbon source and lithium carbonate with the precipitated iron phosphate, the carbon source including at least glucose or sucrose.
5. The method of claim 4 further comprising adding the carbon source in an amount based on 20% by weight of the iron phosphate.
6. The method of claim 1 wherein the hydrochloric acid acid is 5M hydrochloric acid.
7. The method of claim 1 further comprising adding ammonium hydroxide to the solution of iron chloride and phosphoric acid for maintaining the pH substantially at 2 .
8. The method of claim 7 further comprising controlling the pH in a range between 1.5-4.5.
9. The method of claim 1 further comprising adding a stoichiometric amount of lithium carbonate to the yield the lithium iron phosphate.
10. The method of claim 1 further comprising acid leaching charge material compounds other than iron phosphate from the granular mass prior to adding the inorganic acid.
11. The method of claim 1 further comprising adjusting the pH by adding ammonium hydroxide or sodium hydroxide.
12. A method for recycling lithium iron phosphate batteries, comprising
removing solid battery components including casing and electrode materials from exhausted lithium ion batteries (LIBs) by physical separation resulting in a granular mass, the granular mass having exhausted charge materials including carbon, graphite and residual cathode materials;
adding a first inorganic acid to the granular mass for leaching charge materials other than iron phosphate from the exhausted charge materials;
directing a first leach solution resulting from the leached charge materials to a recycling stream;
adding hydrochloric acid to the granular mass remaining after directing the first leach solution to the recycling stream to generate a second leach solution including iron chloride and phosphoric acid;
adjusting the pH of the generated leach solution to precipitate iron phosphate for adding lithium carbonate and sintering for forming lithium iron phosphate.
13. The method of claim 12 wherein the first inorganic acid is sulfuric acid, and the leached charge materials include nickel, manganese and cobalt.
14. The method of claim 12 wherein the physical separation includes:
agitation and crushing to separate casing and containment materials;
sorting and magnetic separation to remove casing and current collector metals from the charge material.
15. The method of claim 12 further comprising removing exhausted charge materials including nickel, manganese and cobalt from dissolution in the leached charge materials.
16. The method of claim 12 further comprising forming the first leach solution by adding an inorganic acid to crushed battery materials defining the granular mass to form a leach solution including compounds of nickel, manganese and cobalt reacted with the inorganic acid.
17. The method of claim 16 further comprising processing the leach solution for forming a parallel recycling stream for recycling the leached charge materials.
18. The method of claim 12 wherein the first inorganic acid dissolves at least one of nickel, manganese and cobalt charge materials and is substantially nonreactive with the iron phosphate.
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2012-04-04
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Worcester Polytechnic Institute
Method and apparatus for recycling lithium-ion batteries
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2017-12-05
Worcester Polytechnic Institute
Method and apparatus for recycling lithium-ion batteries
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Method for recycling lithium carbonate from lithium iron phosphate waste material
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2017-09-21
Keliber Oy
Method of producing lithium metal phosphates
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2016-09-28
åè¥å½è½©é«ç§å¨åè½æºæéå ¬å¸
Method for preparing lithium ferrous phosphate by utilizing lithium ferrous phosphate waste
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Anode recovery in regenerated batteries
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Recovery of anodes in regenerated batteries
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Green Li-Ion Pte. Ltd.
Process for removing impurities in the recycling of lithium-ion batteries
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Process for removing impurities in the recycling of lithium-ion batteries
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Process for recycling lithium iron phosphate batteries
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Processes and systems for purifying and recycling lithium-ion battery waste streams
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Process and system for recovering lithium from lithium-ion batteries
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Processes for recycling spent catalysts, recycling rechargeable batteries, and integrated processes thereof
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Adaptable processes and systems for purifying co-precipitated or independent streams of manganese, nickel, and cobalt from lithium-ion battery waste streams
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