WO2025012520A1

WO2025012520A1 - Method and apparatus for recycling battery

Info

Publication number: WO2025012520A1
Application number: PCT/FI2024/050389
Authority: WO
Inventors: Annukka SANTASALO-AARNIO; Neha Garg; Aravindda Swamy VENKATESH
Original assignee: Aalto Korkeakoulusaatio sr
Current assignee: Aalto Korkeakoulusaatio sr
Priority date: 2023-07-13
Filing date: 2024-07-11
Publication date: 2025-01-16
Anticipated expiration: 2026-01-13

Abstract

The application relates to a method and an apparatus for recycling at least one battery. The battery (1) is discharged by treating the battery in an electrolytic bath discharge (3), the battery is dismantled by separating a core of the battery comprising at least one active material from a battery casing, at least one mixture containing the active material is collected from electrodes of the core of the battery, and anode and cathode active materials (11) are separated from the mixture for recovering the active materials.

Description

METHOD AND APPARATUS FOR RECYCLING BATTERY

FIELD

The application relates to a method defined in claim 1 for recycling a battery or batteries and an apparatus defined in claim 12 for recycling a battery or batteries .

BACKGROUND

As the amount of lithium-ion battery consumption increases during this current decade , the requirement for raw material to produce new batteries also increases , and this causes a stress in the supply chain and i s not sustainable . One of the ways to reduce this stress on raw material is to reclaim the materials from used and discarded batteries . There are different recycling methods that are focused on the materials that need to be recovered . The known technique includes melting the cell directly to recover metals that include cobalt , aluminium, and iron, or it may compri se shredding the given cell and separating the required materials through flotation or other separation method . The maj or positive part of these methods , in which of the active materials are recovered from the recycling, is that the active materials are the most expensive and functioning part of the battery and recovering these materials reduces the stress on the environment as they act as a secondary source of raw materials .

The most used current process involves possible discharge of the battery and then shredding or grinding of the entire battery cell and separators . The shredded part is known as a black mass which is a combination of different materials , and which also encompasses the active materials , shell casing and polymer materials . The metals are removed either by a magnetic separation or by other filtration process , and the separation of the active material mixture commonly involves the method of flotation where the materials are separated by the hydrophobic and hydrophilic nature of the active materials in cathode and anode . Even though thi s method would be useful , the materials are not fully liberated from each other that has an impact on the purity of the recovered active materials .

The above-mentioned processes are complicated as they mix different materials that are then more complicated to be further separated in high-quality streams . One of the maj or challenges is that the materials can not be fully liberated from each other and therefore the separation to separate streams is challenging .

Document PCT/ JP2020 / 034780 discloses a method for battery material recovery and recycling where the active material is recovered with the help of heating the electrode , which is a resin current collector, to more than the melting part of the resin . The document also discloses a process of flotation .

Document WO 2022094169 discloses methods and procedures for repurposing and relithiating the batteries . Document PCT/CN2018 / 119992 discloses a battery manufacturing machine .

Document WO 2022142067 aims for recycling, and it discloses the separation of the anode and the cathode materials using an expensive wet ball milling process .

Document US 20220200042 discloses a method to recover lithium metal from lithium-metal alloys , lithium oxides and lithium feedstock through electrodeposition .

Document US 20220029217 discloses a method of extracting the cathode material from the anode and cathode mixture , and it is carried out by a hydrophobicitybased separation process , a filtration separation process based on particle si ze , an eddy current separation and a heat treatment process . Document KR 102201699 discloses a restoration process where the cathode and the anode are disassembled and placed in a restoration solution where the l ithium cations and anions are present .

OBJECTIVE

The obj ective is to solve the above problems . Further, the obj ective is to disclose a new-type process for recycling of different batteries and rechargeable batteries . Further, the obj ective is to recycle the batteries effectively . Further, the obj ective is to provide the recycling of the batteries without shredding them . Further, the obj ective is to recover high-quality active materials from the batteries .

SUMMARY

The method and apparatus are characteri zed by what are presented in the claims .

The method for recycling at least one battery comprising : discharging the battery, dismantling the battery by separating a core of the battery compris ing at least one active material from a battery casing, collecting at least one mixture containing the active material from electrodes of the core of the battery, and separating anode and cathode active materials from the mixture for recovering the active materials .

The apparatus for recycling at least one battery comprises at least one discharge device to discharge at least one battery, at least one separator device to dismantle a core of the battery comprising at least one active material from a battery casing, at least one collector to collect at least one mixture containing the active material from electrodes of the core , and at least one separation device to separate anode and cathode active materials from the mixture . DETAILED DESCRIPTION

In the method for recycl ing at least one battery, at least one battery is discharged by treating the battery in an electrolytic bath discharge , the battery is di smantled by separating a core of the battery comprising at least one active material from a battery casing, at least one mixture containing the active material i s collected from electrodes of the core of the battery, and anode and cathode active materials are separated from the mixture for recovering the active materials .

The apparatus for recycling at least one battery may comprise at least one electrolytic bath discharge device to discharge at least one battery, at least one separator device comprising a plunger or puller system to separate a core of the battery comprising at least one active material from a battery casing, at least one collector, e . g . vessel or other suitable collector, to collect at least one mixture containing the active material from electrodes of the core , and at least one acoustic separation device to separate anode and cathode active materials from the mixture .

Preferably, the maj or step in the recycling of the batteries , e . g . lithium-ion batteries or other batteries , is the separation and recovery of the active materials . The separation of the active materials includes the segregation of the anode and cathode materials .

In this context , the battery means any battery, rechargeable battery, electrochemical cell , or the like . The battery may have any shape . In one embodiment , the battery is a cylindrical battery . In one embodiment , the battery is a torch battery . In one embodiment , the battery is a lithium-ion battery . In one embodiment , the battery is a cylindrical lithium-ion cell . In one embodiment , the battery is an alkaline cell . In one embodiment, the battery is a rechargeable battery. In one embodiment, the battery is a solid-state battery.

In one embodiment, a liquid electrolyte is removed before the separation of the core of the battery from the battery casing.

In one embodiment, the battery is dismantled by cutting off both ends of the battery casing and by separating the core through the opened ends from the battery casing. In one embodiment, the apparatus comprises a cutting device to cut off both ends of the battery casing before the separator device. In one embodiment, the cutting device is a laser cutting device. Alternatively, the cutting device may be other suitable cutting device. In one embodiment, the core is separated from the battery casing through the opened caps on the battery casing by a mechanical, pneumatical and/or electric push mechanism. In one embodiment, the core is separated from the battery casing through the opened caps on the battery casing by a mechanical, pneumatical and/or electric pull mechanism. In one embodiment, an electrolyte or electrolytes are removed during the dismantling. In one embodiment, the dismantling is carried out essentially in dry conditions, preferably with a relative humidity of less than 20 % .

The mixture which contains the active materials, such as anode and cathode active materials, is collected from the electrodes of the core of the battery. The mixture may be collected into any suitable collector, e.g. vessel, container, tank, collector, storage bin, or the like. In one embodiment, an electrolyte or electrolytes are removed during the collection of the mixture. In one embodiment, the collection is carried out in the presence of an acoustic technique and/or chemical reagent (s) . In one embodiment, the collection is carried out using an acoustic treatment. In one embodiment , the collection of the mixture is carried out in a separate step . In one embodi ment , the collection of the mixture is carried out j ust before the separation of the active materials or in the the separation step in which the active materials are separated . In one embodiment , the collection of the mixture is carried out in the dismantling step or in the separator device .

The separation of the active materials from the mixture can be performed through different methods , in one embodiment by using an acoustic separation method . In one embodiment , an electrolyte or electrolytes are removed during the separation of the active materials .

In one embodiment , the mixture collected from the electrodes is mixed to a fluid, e . g . a carrier fluid, before the separation of the anode and cathode active materials . In one embodiment , the acoustic separation is used, and the mixture comprising the active materials is mixed with a carrier fluid that i s chemically inert with the active materials . In one embodiment , a ratio of the active material and fluid is less than 10 : 100 .

In one embodiment, the anode and cathode active materials are separated from the mixture using an acoustic separation, and optionally at least one chemical reagent . In one embodiment , the active materials are separated from the mixture using an ultrasonication . In one embodiment , the acoustic separation device comprises an ultrasonication device to separate the active materials from the mixture . In one embodiment , an indirect ultrasonication treatment is used in the separation . In one embodiment , the acoustic separation device comprises a chamber where the anode and cathode active materials are separated from the mixture , and the chamber comprises at least one inlet to feed the mixture and at least two outlets to discharge the active materials . In one embodiment , the active material is separated from an electrode sheet .

In one embodiment , the electrodes are submerged in de-ioni zed water and subj ected to an ultrasonication to remove the active materials .

In one embodiment , the active material may be any active material , for example the positive electrode may contain metal oxide , lithium-based oxide or the like , e . g . LCO, NCA, NMC, LMO, LMNO, LR-NMC, LFP, or LMFP, and/or the negative electrode may contain graphite , LTO, silicon, or lithium .

The active materials can be divided between the anode and cathode materials . In one embodiment , the division of the active materials between the anode and cathode i s based on density or mass dif ference . In one embodiment , the active material of the cathode has higher density than the anode material for the efficient functioning of the separation . In one embodiment , the active material of the anode has higher density than the cathode material , wherein the difference in the density is at least 1 g/cc ( 1000 kg/m³ ) . In one embodiment, the separation process by the acoustic is not limited to the particular sequence of process steps but can be used in the battery recycling process in which the mass difference exists in the active materials .

In one embodiment , a heat treatment is used as a pre-process ing step before the separation of the active materials , and the separation is carried by the acoustic force .

In one embodiment , the collecting of the mixture from the electrodes and/or the separating of the anode and cathode active materials take place in an oxygen-free atmosphere or in an oxygen-depleted atmosphere . Then fire risks associated with the oxidation of the electrolyte in the batteries can be mitigated during the process . In one embodiment , the separated active material particles are treated in a further purification process to be reused in the batteries , e . g . lithium-ion batteries . In one embodiment , the active material is purified using a filtration . In one embodiment , the active material is purified by a filtration using the acoustics .

In one embodiment , the s i ze of the active material is limited to the maximum si ze of 100 microns .

In a preferred embodiment , the removal of the active material from the electrodes , along with or without the binder, is performed without breaking the electrode into multiple parts .

In one embodiment, the method of recycling cylindrical cells comprises the separation of j elly rolls from the batteries , and the collection the active material mixture and the separation of the active materials , as disclosed in this description .

In one embodiment , the method comprises separating the j elly rolls from the cylindrical cells through the opened caps on the cylindrical cells by a process of mechanical , pneumatical or electric push or a pull mechanism .

Thanks to the invention, the batteries can be recycled effectively . By means of the invention, cleaner and less energy consuming process for the recovery of the active materials from the battery, e . g . cylindrical battery cells , can be provided . Especially, the batteries can be recycled without shredding them . For example , the recycling of lithium-ion cells without shredding them can be performed easily and effectively .

Further, high-quality active materials can be recovered from the batteries effectively . In the present invention, the acoustic separation is used for recovering the active materials . Further, a melting step which is an uneconomical and expensive process step is not needed in the present invention. Thus, the recovery and reclamation of the active materials from the used battery can be performed effectively.

The method offers a possibility to recycle the batteries easily, and energy- and cost-effectively. The present invention provides an industrially applicable, simple and affordable way to recycle the different batteries. The method and apparatus is easy and simple to realize in connection with different production processes.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are included to provide a further understanding of the invention and constitute a part of this specification, illustrate some embodiments of the invention and together with the description help to explain the principles of the invention. In the drawings:

Fig. 1 presents the electrolytic bath to discharge the batteries of the residual charge.

Fig. 2 presents the battery cap cutter and jelly roll separator machine.

Fig. 3 presents a simple representation of the acoustic separation device.

EXAMPLES

The batteries, such as cylindrical batteries, is recycled, and an acoustic separation is used.

According to the example, the cylindrical cells are discharged using an electrolytic bath discharge. Ends of the cylindrical cells are cut off without damaging jelly rolls, and the jelly rolls are separated from casings. The separated jelly rolls undergo a separation step, where the active materials and electrolytes are removed, and the separation of the active materials is performed by the non-contact method consisting of ultrasonics treatment, and optionally an addition of a chemical reagent.

A black mass that contains the mixture of the active material can be separated by using various techniques, which preferably include an acoustic manipulation technique.

According to the example, the removal of the jelly roll from the battery casing can be performed using the following devices: an eletrolytic bath, and a separator device comprising a laser cutting device, a next part for separating the jelly roll from the casing and collector and separate bins.

The electrolytic bath (3) comprising an electrolyte (2) , as presented in Fig. 1, discharges the batteries (1) from the residual charge. Fig. 2 presents the separator device. The laser cutting device (4) cuts both ends of the batteries, and the caps are separated, and the electrolyte if in liquid form is drained in the collector bins (5) . The batteries without the both ends are taken to the next part of device, where a plunger or puller system (7) which may use either a pneumatic force or a fluidic or mechanical force removes the jelly rolls from the casings and the removed jelly rolls are collected in the separate bin(s) (6) .

The separator device of Fig. 2 comprises the cutter (4) , such as a laser cutter mechanism, powered by an actuator, motor or the like, which cuts the ends of the batteries, and another actuating mechanism (7) , such as a plunging mechanism, e.g. a pneumatic plunger mechanism, that pushes the jelly rolls into the collector ( 6) .

The black mass which contains the active material is collected from the jelly rolls. The collection of the black mass is performed without shredding. The collection may comprise acoustic technique and/or chemical reagents. The collected black mass can be separated into anode and cathode active materials using different methods, such as an acoustic manipulation which is describer hereinafter.

The collected black mass is treated using an acoustic separation device according to Fig. 3. The collected black mass is mixed to a fluid which preferably, but not limited, have a density greater than the anode active material and less than the cathode active material. The formed fluid (8) is fed into a chamber which has inlets and outlets, e.g. a single channel inlet and a dual channel outlet as presented in Fig. 3. The formed composition of the black mass and the fluid can have the ratio less than 10:100 of the black mass and the fluid. An acoustic transducer (9) emits acoustic waves and a reflector (10) makes standing waves form. This is used to separate the particles based on their densities and their Young' s modulus which influences the amount of the acoustic forces. The segregated anode and cathode active materials (11) are discharged from the device. In one example, the particle size of the active materials should be less than 100 microns to be more efficient in a reuse or in a post-treatment .

Example 1

In the test of this example, the active materials of the electrodes were removed from the electrode sheets, i.e. metal foils, using an ultrasonication. The active materials used in the test were LMNO (lithium manganese nickel oxide) and graphite.

The process was conducted under atmospheric pressure .

It was observed that significant material removal using the ultrasonication can be achieved from the electrode sheets. The devices and techniques of the process used in the examples are known per se in the art , and therefore they are not described in any more detai l in this context . The method and apparatus are suitable in different embodiments for recycling different batteries .

The invention is not limited merely to the examples referred to above ; instead many variations are possible within the scope of the inventive idea defined by the claims .

Claims

1 . A method for recycling at least one battery, wherein the method comprises

- discharging at least one battery by treating the battery in an electrolytic bath discharge ,

- dismantling the battery by separating a core of the battery comprising at least one active material from a battery casing,

- collecting at least one mixture containing the active material from electrodes of the core of the battery, and

- separating anode and cathode active materials from the mixture for recovering the active materials .

2 . The method according to claim 1 , wherein the battery is a lithium-ion battery .

3 . The method according to claim 1 or 2 , wherein the anode and cathode active materials are separated from the mixture using an acoustic separation, and optionally at least one chemical reagent .

4 . The method according to any one of claims 1 to 3 , wherein the active materials are separated from the mixture using an ultrasonication .

5 . The method according to any one of claims 1 to 4 , wherein the active material is separated from an electrode sheet .

6 . The method according to any one of claims 1 to 5 , wherein the mixture collected from the electrodes is mixed to a fluid before the separation of the anode and cathode active materials .

7 . The method according to any one of claims 1 to 6 , wherein the electrodes are submerged in de-ionized water and subj ected to an ultrasonication to remove the active materials .

8 . The method according to any one of claims 1 to 7 , wherein the collecting of the mixture from electrodes and the separating of the anode and cathode active materials take place in an oxygen-free atmosphere .

9 . The method according to any one of claims 1 to 8 , wherein the battery is dismantled by cutting off both ends of the battery casing and by separating the core through the opened ends from the battery casing .

10 . The method according to any one of claims 1 to 9 , wherein a liquid electrolyte is removed before the separation of the core of the battery from the battery casing .

11 . The method according to any one of claims 1 to 10 , wherein the active material is purified using a filtration .

12 . An apparatus for recycling at least one battery, wherein the apparatus comprises

- at least one electrolytic bath discharge device ( 3 ) to discharge at least one battery ( 1 ) ,

- at least one separator device comprising a plunger or puller system ( 7 ) to dismantle a core of the battery comprising at least one active material from a battery casing,

- at least one collector to collect at least one mixture containing the active material from electrodes of the core , and

- at least one acoustic separation device to separate anode and cathode active materials ( 11 ) from the mixture .

13 . The apparatus according to claim 12 , wherein the apparatus comprises a cutting device ( 4 ) to cut off both ends of the battery casing before the separator device .

14 . The apparatus according to claim 12 or 13 , wherein the acoustic separation device comprises an ultrasonication device to separate the active materials from the mixture .

15 . The apparatus according to any one of claims 12 to 14 , wherein the acoustic separation device comprises a chamber where the anode and cathode active materials (11) are separated from the mixture, and the chamber comprises at least one inlet to feed the mixture and at least two outlets to discharge the active materials.