AU2021282007B2

AU2021282007B2 - Recovery of critical elements from end-of-life lithium ion batteries with supported membrane solvent extraction

Info

Publication number: AU2021282007B2
Application number: AU2021282007A
Authority: AU
Inventors: Ramesh R. Bhave; Syed Z. Islam; Priyesh A. WAGH
Original assignee: UT Battelle LLC
Current assignee: UT Battelle LLC
Priority date: 2020-05-27
Filing date: 2021-04-15
Publication date: 2024-06-13
Anticipated expiration: 2041-04-15
Also published as: CN115697578A; US20210376400A1; JP2023527386A; AU2021282007A1; CN115697578B; BR112022023627A2; CA3179484A1; KR102885214B1; EP4157558A1; EP4157558A4; JP7620647B2; WO2021242429A1; KR20230016205A; US11811035B2

Abstract

Single-stage and multi-stage systems and methods for the recovery of critical elements in substantially pure form from lithium ion batteries are provided. The systems and methods include supported membrane solvent extraction using an immobilized organic phase within the pores of permeable hollow fibers. The permeable hollow fibers are contacted by a feed solution on one side, and a strip solution on another side, to provide the simultaneous extraction and stripping of elements from dissolved lithium ion cathode materials, while rejecting other elements from the feed solution. The single- and multi-stage systems and methods can selectively recover cobalt, manganese, nickel, lithium, aluminum and other elements from spent battery cathodes and are not limited by equilibrium constraints as compared to traditional solvent extraction processes.

Description

RECOVERY OF CRITICAL ELEMENTS FROM END-OF-LIFE LITHIUM ION BATTERIES WITH SUPPORTED MEMBRANE SOLVENT EXTRACTION

[0001] This invention was made with U.S. government support under Contract No. DE

AC05-000R22725 awarded by the U.S. Department of Energy. The U.S. government has

certain rights in the invention.

FIELD OF THE INVENTION

[0002] The present invention relates to the recovery of critical elements in their pure

form from end-of-life lithium ion batteries, and in particular, the recovery and separation of

cobalt, nickel, manganese, lithium and/or other elements using supported membrane solvent

extraction.

BACKGROUND OF THE INVENTION

[0003] In recent years, lithium ion batteries have drawn significant attention worldwide

due to their widespread use in portable electronics and electric vehicles. Lithium ion batteries

are smaller, lighter, have no memory effect, and provide more energy per unit volume than

conventional nickel-cadmium (Ni-Cd) or nickel-metal hydride (NiMH) batteries.

[0004] Cobalt is deemed a critical material and is substantially and increasingly used

in lithium ion batteries. Currently, the terrestrial cobalt resources in the world are estimated at

approximately 25 million tons. The richest sources of cobalt are primarily in the Democratic

Republic of Congo. Cobalt mining is practiced in Congo, which currently supplies 54% of the

global cobalt demand, while China, Russia, and Australia each contribute approximately 5%

of the global cobalt demand. 30% of the current cobalt supply is consumed by the lithium ion

battery industry. Hence, lithium ion batteries are considered an important secondary resource

for the extraction and recovery of cobalt. Further, the presence of metallic contaminations in the waste generated from spent lithium ion batteries can adversely affect the environment.

[0005] Conventional solvent extraction methods have been employed commercially to

recover cobalt from primary, secondary, and end-of-life battery cathode materials. However,

conventional processes have limitations such as high solvent inventory, emulsion formation,

and multi-step operations including stripping and scrubbing. Non-dispersive solvent extraction

methods using supported liquid membranes with known extractants, such as Cyanex 272 and

Cyanex 301, have been proposed for separating cobalt in the presence of nickel and manganese.

Swain et al (Chemical Engineering Journal, 2015. 271, p. 61-70) investigated the separation of

cobalt by supported hollow fiber and flat sheet liquid membrane solvent extraction using

Cyanex 272 as the extractant. The feed solution used in the study was salts of cobalt and

lithium, such as cobalt sulfate and lithium sulfate dissolved in sulfuric acid. However, the

cobalt chemistry in lithium ion batteries is much more complex than a divalent cobalt salt.

[0006] Accordingly, there remains a need for an improved method and system for the

recovery of cobalt, and other elements, from lithium ion batteries using supported liquid

membrane solvent extraction. In particular, there remains a need for an improved method and

system for the selective recovery of constituent elements in substantially pure form from

LiCoO2 and LiNiCoMnO2 (nickel-manganese-cobalt or NMC) cathodes in spent lithium ion

batteries.

SUMMARY OF THE INVENTION

[0007] Disclosed generally herein is a method and system for the recovery of elements

in substantially pure form from lithium ion batteries are provided. The method and the system

include supported membrane solvent extraction using an immobilized organic phase within the

pores of permeable hollow fibers for selectively extracting elements from a feed solution

having a regulated pH. The permeable hollow fibers are contacted by an aqueous feed solution

on one side, and a strip solution on another side, to provide the simultaneous extraction and stripping of elements from dissolved lithium ion cathode materials, while rejecting other elements from the feed solution.

[0008] In a first aspect, the invention provides a method for the recovery of cobalt from

lithium ion batteries, the method comprising: (i) dissolving a battery material containing Co

and Li within an acid to form a feed solution, the feed solution including Co(II) and Li(I); (ii)

providing a membrane module including a plurality of hollow fibers, the plurality of hollow

fibers including a porous sidewall defining a lumen side spaced apart from a shell side; (iii)

wetting the porous sidewall of the plurality of hollow fibers with an organic phase, the organic

phase including a cationic extractant and an organic solvent; (iv) performing membrane solvent

extraction by moving the feed solution along one of the lumen side or the shell side of the

plurality of hollow fibers and simultaneously moving a strip solution along the other of the

lumen side or the shell side of the plurality of hollow fibers, the strip solution including a pH

that is less than a pH of the aqueous feed solution; and (v) maintaining a pH of the feed solution

within a predetermined range by intermittently introducing a buffer or a base to the feed

solution during membrane solvent extraction; wherein wetting the porous sidewall of the

plurality of hollow fibers with the organic phase is performed prior to moving the feed solution

and moving the strip solution, and wherein the cationic extractant in the porous sidewall

continuously extracts Co(II) from the aqueous feed solution for recovery by the strip solution

while substantially rejecting Li(I).

[0009] In one embodiment, the method includes wetting the pores of the plurality of

hollow fibers with an organic phase having a cationic liquid extractant and an organic solvent.

The method then includes moving an aqueous feed solution along one side of the hollow fibers,

the aqueous feed solution including a dissolved cobalt-containing battery material, for example

LiCoO2 or LiNiCoMnO2. The method includes simultaneously moving a strip solution along

the other side of the hollow fibers, the aqueous feed solution being pressurized with respect to

the strip solution (about 2 psig), such that the ionic liquid extractant in the pores of the plurality of hollow fibers continuously extracts Co(II) from the aqueous feed solution for recovery by the strip solution.

[0010] In another embodiment, the system includes a membrane module, a feed

reservoir, and a strip reservoir. The membrane module includes a plurality of hollow fibers,

and the pores of the hollow fibers are wetted (pre-impregnated) with an immobilized organic

phase. The feed reservoir and the strip reservoir include an aqueous feed solution and a strip

solution, respectively, which are in continuous recirculation through the membrane module.

The aqueous feed solution is directed along the lumen side of the hollow fibers and the strip

solution is directed along the shell side of the hollow fibers, optionally in transverse flow

directions. In other embodiments, the aqueous feed solution is directed along the shell side of

the hollow fibers and the strip solution is directed along the lumen side of the hollow fibers.

The aqueous feed solution includes a cobalt-containing battery material and is pressurized

relative to the strip solution. The organic phase within the pores of the hollow fibers includes

an organic solvent and a cationic extractant, for example Cyanex 272 or Cyanex 301, that is

selected to continuously extract cobalt (e.g., Co(II)) from the aqueous feed solution for

recovery by the strip solution.

[0011] The method and system of the present invention can facilitate the simultaneous

extraction and stripping of cobalt, and other elements, from lithium ion cathode materials using

an immobilized organic phase within the pores of hollow fibers. For example, multi-stage

systems discussed herein can selectively recover cobalt, manganese, nickel, and lithium from

spent battery cathodes. The systems and methods discussed herein are not limited by

equilibrium constraints as compared to traditional solvent extraction processes. Non

dispersive solvent extraction methods using supported liquid membranes with cationic

extractants were demonstrated by the inventors in laboratory examples to recover critical

elements in substantially pure form, and includes the pretreatment of cathodes and anodes prior

to supported membrane solvent extraction.

[0012] These and other features and advantages of the present invention will become

apparent from the following description of the invention, when viewed in accordance with the

accompanying drawings and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 is an illustration of a membrane module in accordance with a system

and a method of the present invention.

[0014] Figure 2 is an illustration of a single-stage system including the membrane

module of Figure 1.

[0015] Figure 3 is an illustration of a dual-stage system including the membrane module

of Figure 1.

[0016] Figure 4 is an illustration of a three-stage system including a pretreatment process

and a membrane solvent extraction process including the membrane module of Figure 1.

[0017] Figure 5 is an illustration of a three-stage system including the membrane module

of Figure 1.

[0018] Figures 6(a) - 6(e) illustrate the recovery of Co from LiCoO2 for Example 1.

Figure 6(a) depicts the concentration of the feed solution; Figure 6(b) depicts the concentration

of the strip solution; Figure 6(c) depicts the purity (%) of Co in the feed and the strip; Figure

6(d) depicts Co recovery over time; and Figure 6(e) depicts Co extraction rate over time.

[0019] Figures 7(a) - 7(e) illustrate the recovery of Co from LiCoO2 for Example 2 at a

higher initial concentration of Co than depicted in Figures 6(a) - 6(f). Figure 7(a) depicts the

concentration of the feed solution; Figure 7(b) depicts the concentration of the strip solution;

Figure 7(c) depicts the purity (%) of Co in the feed and the strip; Figure 7(d) depicts Co

recovery over time; and Figure 7(e) depicts Co extraction rate over time.

[0020] Figures 8(a)- 8(e) illustrate the stage one recovery of Co from NMC for Example

3. Figure 8(a) depicts the concentration of the feed solution; Figure 8(b) depicts the concentration of the strip solution; Figure 8(c) depicts the purity (%) of Co in the feed and the strip; Figure 8(d) depicts Co recovery over time; and Figure 8(e) depicts Co extraction rate over time.

[0021] Figures 9(a) - 9(e) illustrate the stage two recovery of Co from NMC for Example

3. Figure 9(a) depicts the concentration of the feed solution; Figure 9(b) depicts the

concentration of the strip solution; Figure 9(c) depicts the purity (%) of Co in the feed and the

strip; Figure 9(d) depicts Co extraction rate; and Figure 9(e) depicts Co extraction rate over

time.

[0022] Figures 10(a) - 10(e) illustrate stage one separation of Co and Mn from Ni and

Li for Example 4. Figure 10(a) depicts the concentration of the strip solution over time; Figure

10(b) depicts the concentration of the feed solution over time; Figure 10(c) depicts the purity

(%) of Co in the feed and the strip solution over time; Figure 10(d) depicts Co recovery over

time; and Figure 10(e) depicts Co extraction rate over time.

[0023] Figures 11(a) - 11(e) illustrate stage two separation of Co from Mn for Example

4. Figure 11(a) depicts the concentration of the strip solution over time; Figure 11(b) depicts

the concentration of the feed solution over time; Figure 11(c) depicts the purity (%) of Co in

the feed and the strip solution over time; Figure 11(d) depicts Co recovery over time; and

Figure 10(e) depicts Co extraction rate over time.

[0024] Figures 12(a) - 12(e) illustrate stage three separation of Ni from Li for Example

4. Figure 12(a) depicts the concentration of the strip solution over time; Figure 12(b) depicts

the concentration of the feed solution over time; Figure 12(c) depicts the purity (%) of Ni in

the feed and the strip solution over time; Figure 12(d) depicts Ni recovery over time; and Figure

10(e) depicts Ni extraction rate over time.

[0025] Figure 13 includes scanning electron microscopy (SEM) images of cobalt oxide

separated from cathode materials in Example 4.

[0026] Figure 14 includes the energy-dispersive x-ray spectroscopy (EDS) of cobalt oxide separated from cathode materials in Example 4.

[0027] Figure 15 includes the X-ray diffraction (XRD) of cobalt oxide separated from

cathode materials in Example 4.

DETAILED DESCRIPTION OF THE CURRENT EMBODIMENTS

[0028] The invention as contemplated and disclosed herein includes methods and

systems for the recovery of constituent elements from lithium ion batteries through membrane

assisted solvent extraction. In general terms, the method include the following steps for single

or multi-stage extraction of one or more constituent elements: a) providing a membrane module

including a plurality of porous hollow fibers, b) wetting the plurality of porous hollow fibers

with an organic phase including a cationic extractant and an organic solvent, c) applying a

continuous flow rate of an acidic aqueous feed solution, at a predetermined pH, along the lumen

side or the shell side of the plurality of porous hollow fibers, and d) applying a continuous flow

rate of an acidic strip solution, at a predetermined pH, along the other of the lumen side or the

shell side of the plurality of porous hollow fibers. The step of wetting the plurality of porous

hollow fibers (step (b)) is performed prior to the steps of applying a flow rate of feed solution

and a flow rate of strip solution (steps (c) and (d)). The steps of applying a flow rate of feed

solution and a flow rate of strip solution are generally simultaneous. These steps are discussed

below in connection with single-stage separation (Part I) and multi-stage separation (Part II).

I. Single-Stage Separation

[0029] Providing a membrane module generally includes providing a plurality of

hollow or tube-like fibers extending between opposing tubesheets. By way of illustration, a

membrane module containing a fiber bundle is illustrated in Figure 1 and generally designated

10. The membrane module 10 includes an outer casing 12 including a feed input port 14, a

feed output port 16, a strip input port 18, and a strip output port 20. A suitable membrane

module can include a hydrophobic polypropylene membrane module (MicroModule® by

Membrana GmbH or MiniModule* by Membrana-Charlotte, LLC) with a membrane module

area of 1.4 in 2 . The plurality of hollow fibers 22 are potted to first and second tubesheets 24,

26 at opposing ends thereof, such that the fibers 22 extending in a common direction. Each

fiber 22 includes a lumen side 28 and a shell side 30. The lumen side 28 is illustrated in Figure

1 as being exposed to the feed solution, however in other embodiments the lumen side 28 is

exposed to the strip solution. Similarly, the shell side 30 is illustrated in Figure 1 as being

exposed to the strip solution, however in other embodiments the shell side 30 is exposed to the

feed solution. As used herein, the "lumen side" includes the interior surface that defines a

channel extending longitudinally through the length of the hollow fiber, and the "shell side"

includes the exterior surface of the fiber, such that the lumen side and the shell side are spaced

apart from each other by the thickness of the membrane sidewall. The side in contact with the

feed solution defines the "feed interface," and the side in contact with the strip solution defines

the "strip interface." The lumen side is the feed interface in some embodiments and is the strip

interface in other embodiments. Similarly, the shell side is the strip interface in some

embodiments and is the feed interface in other embodiments.

[0030] The hollow fibers 22 are porous to retain an organic phase therein and are

formed of a material that is able to withstand the acidic conditions in the feed solution and the

strip solution. The hollow fibers 22 can be formed from a hydrophobic material, which assists

in preventing the wetting of the fibers by the aqueous feed solution and which can also prevent

the displacement of the organic phase into the strip solution. Hydrophobic materials can

include, for example, polypropylene, polyethylene, polyvinylidene fluoride, polyether ether

ketone, polysulfone, or polyethersulfone. The pore size is selected such that the organic phase

containing the extractant is not displaced by contact with a pressurized feed solution at

pressures of about 2 psi higher than the pressure on the strip side of the fibers, optionally less

than 5 psi higher than the pressure of the strip solution. The hollow fibers include a mean pore

size of less than 0.1 micron in some embodiments, while in other embodiments the mean pore size is between 0.01 micron and 0.1 micron inclusive. The hollow fibers include a mean inner diameter of between 0.1 mm and 1.0 mm inclusive, further optionally between 0.2 mm and 0.3 mm inclusive. The hollow fibers include a mean outer diameter of between 0.1 mm and 1.0 mm inclusive, further optionally between 0.6 mm and 0.7 mm inclusive. The hollow fibers have a mean sidewall thickness of between 0.01 mm and 0.1 mm inclusive, further optionally between 0.02 mm and 0.03 mm inclusive.

[0031] Wetting the plurality of porous fibers with an organic phase generally includes

directing the organic phase through the feed input port 14 for a predetermined period (e.g., one

hour) to saturate the fibers with the organic phase. The flow of organic phase is stopped after

a sufficient period has elapsed, resulting in an immobilized organic phase within the pores of

the plurality of fibers. After wetting, the distilled water is circulated through both input ports

14, 18 to wash out excess organic phase from the membrane module 10. The immobilized

organic phase includes a cationic extractant (discussed below) and an organic solvent. The

organic solvent includes a synthetic isoparaffinic hydrocarbon solvent, for example Isopar-L

(Exxon Mobile Corporation). Other immobilized organic phases can be used in other

embodiments where desired. Optionally, the immobilized organic phase includes tributyl

phosphate (TBP), however TBP is not required, and in some embodiments the immobilized

organic phase is free from TBP. This is because TBP is conventionally used in solvent

extraction processes to prevent the formation of third phase, which is the separation of the

organic phase into two liquids as observed in the form of an emulsion. Third phase is generally

attributed to the limited solubility of the extractant in the organic diluent and high acid strength

used in the feed and stripping solutions. There is no third phase formation in the present

membrane solvent extraction process because the amount of organic phase imbedded in each

pore of the hollow fiber membrane is very low. Additionally, dilute acid solutions are used in

membrane solvent extraction process which prevent emulsion formation. Hence, the organic

phase is not required to include TBP, and in many embodiments no TBP is used.

[0032] The extractant can be selected to recover certain elements while rejecting others

when used according to the systems and methods described herein. For example, the extractant

can include bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272, Cytec Inc.) or

methylpentylphosphinodithioic acid (Cyanex 301, Cytec Inc.). The extractant can include

Cyanex 272 to extract Co and Mn from a feed solution with pH of between 4.0 and 6.0,

inclusive, further optionally 5.0 to 6.0, inclusive, while substantially rejecting Ni and Li. Also

by example, the extractant can include Cyanex 272 to extract Co from a feed solution having

a pH between 5.0 and 6.0 inclusive, more specifically about 5.9, while substantially rejecting

Li. Also by example, the extractant can include Cyanex 272 to extract Ni from a feed solution

having a pH between 6.0 and 7.5 inclusive, more specifically 6.0 to 6.5, inclusive, while

substantially rejecting Li. Also by example, the extractant can include Cyanex 301 to extract

Co from a feed solution having a pH of 1.5 or less while substantially rejecting Mn. Also by

example, the extractant can include Cyanex 301 to extract Co and Ni from a feed solution

having a pH of between 1.0 and 3.0, inclusive, while substantially rejecting Li. The addition

of an acetate buffer during the extraction process, for example sodium acetate, maintains a high

extraction rate by controlling the decrease in pH in the feed solution. As used herein,

"substantially rejecting" means the elemental molarity (moles per liter of solution) of the

receiving solution is less than 1% of the elemental molarity (moles per liter of solution) of the

donating solution for the rejected element after membrane solvent extraction of one hour,

unless otherwise stated.

[0033] Directing a continuous flow rate of an acidic aqueous feed solution along the

lumen side or the shell side of the plurality of porous hollow fibers includes directing an acidic

aqueous feed solution through the feed input port 14. The acidic aqueous feed solution includes

dissolved cathode material from post-consumer lithium ion batteries, for example LiCoO2

cathode material and LiNiCoMnO2 (NMC)cathode material. The feed solution has a pH that

is selected based on the extractant. For Cyanex 272, the feed solution can have a pH of 5.5 to

- In -

6.0, inclusive, which can be achieved by dissolving the cathode material in 0.2-4 M H2 SO4

with up to 5 vol. % of H 2 0 2 as a reducing agent to convert Co(III) to Co(II), which is more

soluble than Co(III). For Cyanex 301, the feed solution can have a pH of 1.2 to 3.0, inclusive,

which can be achieved by dissolving the cathode material in 0.2-4 M H2 SO4 with up to 5 vol.

% of H 2 0 2 as a reducing agent to convert Co(III) to Co(II). The addition of an acetate buffer,

for example sodium acetate, maintains a high extraction rate by setting the initial pH of the

feed solution, which is regulated during membrane solvent extraction to be within a

predetermined range with the intermittent addition of a buffer, for example sodium acetate

and/or base, for example ammonium hydroxide. The feed solution can alternatively include

cathode material dissolved in HNO3 or HCl at the desired molar concentration. The feed

solution can be directed through the module 10 along the lumen side 28 of each of the plurality

of porous hollow fibers 22 as shown in Figure 1. Alternatively, the feed solution can be

directed through the module 10 along the shell side 30 of each of the plurality of fibers 22.

[0034] Directing a continuous flow rate of an acidic aqueous strip solution along the

lumen side or the shell side of the plurality of permeable fibers for back-extraction includes

directing a strip solution through the strip input port. The strip solution as adapted to strip

Co(II), or other constituent elements, that have diffused from the feed interface to the strip

interface. The strip solution can include H2 SO 4 , HNO3 , or HCl, for example, at a higher molar

concentration than in the feed solution. That is, a concentration gradient and hence a chemical

potential gradient is generally formed between feed solution and the strip solution. The strip

solution is directed through the module 10 along the shell side 30 of each of the plurality of

fibers 22 as shown in Figure 1 above, optionally in a direction generally transverse to the flow

of the feed solution within the fibers 22. Alternatively, the strip solution can be directed

through the interior of the hollow fibers 22 to contact the lumen side 28 thereof.

[0035] To further illustrate the circulation of the feed solution and the strip solution, a

system for membrane assisted solvent extraction is illustrated in Figure 2 and generally designated 40. The system 40 includes a feed reservoir 42, a strip reservoir 44, a membrane module 10, a feed line 46, a feed return line 48, a strip line 50, and a strip return line 52. The feed solution is contained within the feed reservoir 42 and kept under constant agitation with a mechanical stirrer to ensure a uniform concentration. The feed line 46 includes a pump 54, for example a peristaltic pump, to ensure the feed line pressure is slightly greater than the strip line pressure. In some applications the feed can be pressurized up to and including 2 psig, optionally less than 5 psig, while the strip can be maintained at atmospheric pressure. The strip line 50 also includes a pump 56, for example a peristaltic pump, to ensure a continuous flow of strip solution through the module 10. The feed solution and the strip solution are in continuous recirculation. However, in other embodiments the feed line and/or the strip line form an open circuit.

[0036] The method can also include filtering, drying and/or annealing the strip solution

to recover highly pure cobalt. For example, the strip solution can be precipitated out with

oxalic acid or ammonium hydroxide, followed by filtration, drying at room temperature, and

annealing. An optional annealing profile can include 750°C for two hours. The step of

filtering, drying, and annealing the strip solution is optional, however, and can be replaced or

modified as desired depending on the intended use of the recovered cobalt. The strip solution

can alternatively be recycled through the supported membrane solvent extraction module 10 or

a second supported membrane solvent extraction module.

II. Multi-Stage Separation

[0037] A two-stage system for the recovery of cobalt is shown in Figure 3 and generally

designated 60. In this system, a first stage recovery of Co and Mn is performed by using a first

membrane module 10, and a second stage recovery of Co is performed by a second membrane

module 10'. The first stage recovery includes a first feed reservoir 62, a first membrane module

10, a feed pump 64, a strip pump 66, and afirst strip reservoir 66. The second stage recovery

includes a second feed reservoir 70, a second membrane module 10', a feed pump 72, a strip pump 74, and a second strip reservoir 76. The first membrane module 10 includes hollow fibers that are pre-impregnated with a first immobilized organic phase adapted to recover Co and Mn from dissolved NMC cathode materials, for example Cyanex 272. The second membrane module 10' includes a second immobilized organic phase that is adapted to recover

Co from the second feed solution. The second feed solution contains Co and Mn from the first

strip solution. More specifically, the first membrane module 10 includes an immobilized

organic phase including Cyanex 272 in Isopar-L, while the second membrane module 10'

includes an immobilized organic phase including Cyanex 301 in Isopar-L. In the current

embodiment, the pH of the first feed solution is between 5.5 and 6.0, and the pH of the second

feed solution is optionally adjusted with ammonium hydroxide to be approximately 2.0.

[0038] A three-stage method for the recovery and separation of Li, Ni, Co, and Mn

from spent cathode material is shown in Figure 4 and includes a pretreatment process 100 and

a multi-stage membrane solvent extraction process 102. The spent cathode material 104 in this

embodiment includes active material and an aluminum support. The active material typically

contains Li, Ni, Co, and Mn in the form of afine powder. The fine powder is aggregated with

a polyvinylidene fluoride (PVDF) binder and a carbon additive. Cathode material is then

pressed together on the Al support before being incorporated into a lithium ion battery. Though

not shown, the present method can also be used to recover copper (Cu) from the battery anode,

which typically includes an active material on a copper support. Additionally, Cu and Al

present in the cathode material can also be separated and recovered using supported membrane

solvent extraction using extractants such as ACORGA M5640 and Cyanex 801.

[0039] To first remove the PVDF binder and the carbon additive, the cathode sheets

are subject to thermal treatment 106, acid dissolution 108, and vacuum filtration 110. Cathode

sheets are heated to a temperature above 500°C in an inert atmosphere to decompose PVDF to

permit easy removal of the cathode material from the Al support. In addition, carbon black,

which is present in the cathode material to increase the conductivity of oxide cathodes, undergoes redox reactions with active cathode material around 550°C. This causes a partial reduction of transition metals present in the cathode powder, thereby reducing the amount of

H2 0 2 required during acid dissolution 108. Because the melting point of Al is about 650°C,

thermal treatment 106 includes a temperature range of between 550°C-650°C, inclusive

("inclusive" as used in this disclosure includes both lower and upper values). More

specifically, the cathodes sheets are heated to 570°C in a nitrogen atmosphere by gradually

ramping up the temperature at a rate of10°C/min, held at 570°C for 25 minutes, and gradually

reduced to room temperature. The cathode sheets are then washed with water to separate the

Al support from the cathode powder. After acid dissolution of the cathode powder, the carbon

additive present in the cathode material is removed using vacuumfiltration 110.

[0040] The multi-stage recovery membrane solvent extraction process 102 is illustrated

in Figure 5 and includes a first stage separation of Co and Mn from Li and Ni, a second stage

separation of Co from Mn, and a third stage separation ofNi from Li. Thefirst stage separation

includes a first feed reservoir 112, a first membrane module 114, and afirst strip reservoir 116.

The first feed reservoir 112 includes a feed solution, and the feed solution includes cathode

material 104 from the pretreatment process 100 dissolved in a strong acid, for example H 2 SO 4

with a reducing agent, for example up to 5 vol. % H 2 0 2 . The feed solution is pH-stabilized ,

between 4.0 and 6.0, inclusive, and includes an acetate buffer, for example sodium acetate

buffer solution. The first membrane module 114 includes hollow fibers that are pre

impregnated with a first immobilized organic phase including a cationic extractant, for example

IM Cyanex 272, and an organic solvent, for example Isopar-L. The organic phase can include

33 vol. % Cyanex 272, 5 vol. % TBP, and balance Isopar-L, however TBP can be omitted

without affecting stage-one separation and recovery. For back extraction, the first strip

reservoir 116 includes a strong acid, for example 0.75M H 2 SO 4 , moving continuously through

the first membrane module 114. As a result of the transfer of H' ions from the strip solution,

the pH of the feed solution decreases, which is abated with the intermittent addition of buffer,

- lid- for example sodium acetate and/or base, for example ammonium hydroxide to regulate the pH of the feed solution to between 4.0 and 6.0 inclusive, further optionally 5.5. Co and Mn concentration increases in the strip solution over time, with a negligible transfer of Li and Ni.

[0041] The second stage separation includes a second feed reservoir 118, a second

membrane module 120, and a second strip reservoir 122. The second feed reservoir 118

includes a second feed solution containing a concentration of Co and Mn recovered from the

first strip reservoir 116. The second membrane module 120 includes a second immobilized

organic phase that is adapted to recover Co from the second feed solution while substantially

rejecting Mn. The feed solution is pH-stabilized at 1.5 or less, for example 1.2, with the

addition of buffer, for example sodium acetate and/or base, for example ammonium hydroxide.

The second membrane module 120 includes hollow fibers that are pre-impregnated with a

second immobilized organic phase including a cationic extractant, for example IM Cyanex

301, and an organic solvent, for example Isopar-L. The second strip reservoir 122 includes a

strong acid, for example IM H2 SO 4 , moving continuously through the second membrane

module 120 to back extract Co from the organic phase. Co concentration in the strip solution

increases over time, with a negligible transfer of Mn.

[0042] The third stage separation includes a third feed reservoir 124, a third membrane

module 126, and a third strip reservoir 130. The third feed reservoir 124 includes a third feed

solution containing a concentration of Li and Ni recovered from the first feed reservoir 112.

The third membrane module 126 includes a third immobilized organic phase that is adapted to

recover Ni from the first feed solution, while substantially rejecting Li. The feed solution is

pH-stabilized to between 6.0 and 6.5, with the addition of buffer, for example sodium acetate

and/or base, for example ammonium hydroxide. The third membrane module 126 includes

hollow fibers that are pre-impregnated with a third immobilized organic phase including a

cationic extractant, for example IM Cyanex 272, and an organic solvent, for example Isopar

L. The third strip reservoir 130 includes a strong acid, for example 0.75M H 2 SO 4 , moving

- isN- continuously through the third membrane module 126 to back extract Ni from the organic phase. Ni concentration in the strip solution increases over time, with a negligible transfer of

Li.

[0043] The method and system therefore provide the recovery and separation of

substantially pure cobalt, manganese, nickel, and lithium as part of a continuous and scalable

recovery process. The method and system can overcome removal limitations caused by

equilibrium effects and can recover critical elements in a highly pure form as demonstrated by

the following examples, which are intended to be non-limiting.

EXAMPLE 1

[0044] In one example, an aqueous feed solution was prepared by dissolving 10 gm

LiCoO2 (Li = 663.86 ppm; Co = 5826.06 ppm) in 750 mL of 0.2 M H 2 SO 4 , and 2 vol. % H 2 0 2

was used as a reducing agent. 250 mL of 3M sodium acetate buffer solution at a pH of 5.2 was

used to stabilize the pH of the feed solution and to make the final feed solution concentration

of 10 gm/L of LiCoO2. The organic phase was 33 vol. % (1 M) Cyanex 272, 5 vol. % tributyl

phosphate (TBP), and balance Isopar-L. The strip solution was 1 L of 0.75 M H 2 SO 4. Initial

pH of the feed was adjusted to 5.02 using ammonium hydroxide. The separation performance

of Co is presented in Figures 6(a) - 6(e). The Co content in the strip solution increased with

time and 92% recovery of Co was achieved while maintaining a minimal passage of Li into the

strip solution (see Figure 6(b)). 99.6 wt. % pure Co was recovered from membrane solvent

extraction using Cyanex 272 as the extractant in organic phase contained in the porous

membrane support (see Figure 6(d)). As a result of the transfer of H' ions from the strip

solution, the pH of the feed solution decreased from 5.02 to 4.66. Extraction rate of Co

decreased over time, with a decrease in the concentration of Co in the feed solution (see Figures

6(a), 6(c), and 6(e)).

EXAMPLE2

[0045] In another example, the feed solution included a higher initial concentration of

LiCoO2. In particular, the feed solution included 20,000 ppm LiCoO2 (Li = 1486.25 ppm; Co

= 11532.325 ppm) dissolved in 0.5 M H 2 SO4 and 2.5 vol. % H2 0 2 . The strip solution included

0.75 M H 2 SO 4 . 250 mL sodium acetate buffer was added to the feed solution for pH

stabilization. Initial pH of the feed solution was adjusted to 5.5. In order to prevent the

reduction in extraction rate with a decrease in pH during experiment, ammonium hydroxide

was added to the feed solution intermittently to maintain a pH in the range of 5.5 to 6.0. The

separation performance of Co is presented in Figures 7(a) - 7(e). Co concentration increased

in the strip solution with a negligible transfer of Li, and 91% recovery of Co was achieved (see

Figures 7(b) and 7(d)). 99.5 wt. % pure Co was recovered from membrane solvent extraction

using Cyanex 272 as the extractant in the organic phase (see Figure 7(c)).

EXAMPLE 3

[0046] In this example, a two stage membrane solvent extraction process was used to

separate and recover Co from NMC. In the first stage (Module 1 of Figure 3), Cyanex 272 was

used to separate Co and Mn as it favors the selective extraction of Co and Mn within a pH

range of5.5 to 6.0. In the second stage (Module 2 of Figure 3), Cyanex 301 was used to separate

Co and Mn at a feed pH value less than 2.

[0047] NMC with a Ni:Co:Mn ratio of 1:1:1 was used as feedstock for the membrane

solvent extraction process. 20 gm NMC (Li = 1402.89 ppm; Co = 3698.89 ppm; Mn = 3626.08

ppm; Ni = 3630.82 ppm) dissolved in 750 mL of 0.5 M H2 SO4 was used and 2 vol. % H 2 0 2

was used as a reducing agent to convert the insoluble Co 3to the soluble Co2+ valence state.

250 mL solution of 3 M sodium acetate buffer solution at a pH of 5.2 was used to stabilize the

pH of the feed solution and to make the final feed solution concentration of 20 gm/L NMC

cathode material. The extractant used in the first stage was 1 M Cyanex 272 in Isopar L. The

strip solution used was 1 L of 0.75 M H 2 SO 4. Initial pH of the feed solution was adjusted to

5.5 using ammonium hydroxide. The Co and Mn content in the strip solution increased with

time and 92% recovery of Co was achieved while maintaining a minimal passage of Ni and no passage of Li (complete rejection) into the strip solution (see Figure 8(b)). In order to prevent the decrease in extraction rate over time with a decrease in pH, ammonium hydroxide was added to the feed solution intermittently to maintain a pH range of 5.0 to 5.5. The separation and recovery of Co in the first stage is presented in Figures 8(a) - 8(e).

[0048] For the further purification of Co, a second stage of separation was conducted

using the final strip solution obtained in the first stage as the feed solution for the second stage.

The pH of the feed solution for the second stage was adjusted to 1.34 using ammonium

hydroxide. The extractant used in this stage was 1 M Cyanex 301 in Isopar-L. The strip

solution used was 1 L of 1 M H2 SO 4. Cyanex 301 selectively extracts both Co and Ni while

minimizing the co-extraction of Mn at a feed pH value < 2. However, the concentration of Ni

in the feed solution prepared from the strip solution was negligible. Hence, the second stage

was used in order to separate and recover Co from a solution of Co and Mn. The Co content

in the strip increased with time and 54% recovery of Co was achieved in two hours while

maintaining a minimal passage of Mn into the strip solution. 99.12% pure Co was recovered

from membrane solvent extraction using Cyanex 301 as the extractant in the organic phase

contained in the membrane support. Feed pH value decreased to 1.04 during the experiment,

however the extraction rate of Co was not affected by this change in the pH value. The

separation performance of Co in this second stage is presented in Figures 9(a) - 9(e).

EXAMPLE4

[0049] In this example, a three-stage membrane solvent extraction process was used to

recover substantially pure Ni, Li, Co, and Mn from a spent Chevrolet Volt lithium ion battery.

About 60 gm of cathode powder mixed with partially oxidized carbon black was obtained using

thermal treatment. The stage-one feed solution was prepared by dissolving 40 gm of cathode

material in 750 mL of 4M H 2 SO 4. Undissolved carbon black was separated from the feed

solution using vacuum filtration. 2 vol. % H 2 0 2 was used as a reducing agent to convert

partially reduced Co(III) to the soluble Co(II) valence state. The carbon additive present in the cathode material is insoluble in H 2 SO4 . A 250 mL solution of 3M sodium acetate buffer solution at a pH of 5.6 was used to stabilize the pH of the feed solution. A feed solution concentration of approximately 30 gm/L spent cathode material was obtained. The feed solution included IL of 30,000 ppm spent cathode in 4M H 2 SO 4 , 2 vol.% H2 0 2 , and 250 mL

3M sodium acetate buffer solution. The initial composition of the feed solution included Li

(1005.0 ppm), Co (3663.9 ppm), Ni (4363.7 ppm), and Mn (9721.2 ppm), with no Al detected.

The cationic extractant included IM Cyanex 272 in Isopar-L. The strip solution included 1 L

of 0.75M H 2 SO4. Initial pH of the feed solution was adjusted to 4.9 using ammonium

hydroxide. To prevent the decrease in extraction rate over time with a decrease in pH,

ammonium hydroxide was added to the feed solution intermittently to maintain a pH range of

4.5 to 5.0 inclusive over the duration of the run. Within this feed pH, Cyanex 272 extracted

both Co and Mn while preventing the co-extraction of Ni and Li. The Co and the Mn content

in the strip solution increased with time and 98.4% recovery of Co was achieved while

preventing the passage of Ni and Li into the strip solution. The separation and recovery of Co

in stage 1 is presented in Figure 10(a) to Figure 10(e).

[0050] For further purification of Co from Mn, a stage-two separation was conducted

using the final strip solution from the stage-one separation as the feed solution. The pH of the

feed solution was adjusted to 1.2 using ammonium hydroxide. The composition of the feed

solution for stage-two included Co (2853.6 ppm) and Mn (7844.3), with no Li or Ni detected.

The decrease in the concentration of Co and Mn was due to the addition of ammonium

hydroxide to the feed solution for pH adjustment. The extractant used in this stage was IM

Cyanex 301 in Isopar-L (50% v/v). The membrane module area was 1.4 m 2 . The strip solution

used was IL ofIM H2 SO4. Cyanex 301 selectively extracts both Co and Ni while minimizing

the co-extraction of Mn at a feed pH of less than 1.5. However, the concentration of Ni in the

feed solution prepared from the strip solution of stage-one was nearly zero, indicating there

was no extraction of Ni by the organic phase. Hence, stage-two was used to separate and recover Co from a solution of both Co and Mn. The Co content in the strip increased with time and 94.3% cumulative recovery of Co was achieved in four hours while preventing the passage of Mn into the strip solution. 100% pure Co was recovered from membrane solvent extraction using Cyanex as the extractant in organic phase contained in the membrane pores. Feed pH decreased to 1.13 during this experiment. However, the extraction rate of Co was not affected by this change in pH. The separation performance of stage-two is presented in Figure 11(a) to

Figure 11(e).

[0051] To separate Ni and Li present in the stage-one feed solution, a third stage of

separation was conducted using the same feed solution remaining after stage-one. The pH of

the feed solution for stage-three was adjusted to 6.3 using ammonium hydroxide. The

composition of the feed solution included Li (744.5 ppm) and Ni (3467.1 ppm), with no Co,

Mn, or Al detected. The decrease in concentration of Ni and Li was due to the addition of

ammonium hydroxide to the feed solution for pH adjustment. The extractant used in this stage

was IM Cyanex 272 in Isopar-L (50% v/v). The strip solution included IL 0.75M H 2 SO 4 . The

membrane module area was 1.4 m2 . Cyanex 272 selective extracts Ni while minimizing the

co-extraction of Li in the feed pH range of 6.0 to 6.5. The Ni content in the strip solution

increased with time and 89.7% cumulative recover of Ni was achieved in six hours with a

minimal transfer of Li into the strip solution. 96.1% pure Ni was recovered from membrane

solvent extraction using Cyanex 272 as the extractant in organic phase contained in membrane

pores. The feed pH value was maintained in the range of 6.0 to 6.5 during the test run. The

separation performance of stage-three is presented in Figure 12(a) to Figure12(e).

[0052] Recovered cobalt was precipitated using oxalic acid and annealed at 760°C.

The cobalt oxide was then characterized using scanning electron microscopy (SEM) and

energy-dispersive x-ray spectroscopy (EDS). Figure 13 shows the SEM images of the C030 4

powders. The C030 4 powders contain rod-shaped particles that are 20-40 m in size. The EDS

spectrum of the C030 4 recovered from cathode materials is shown in Figure 14. The

- M - characteristic peaks for only C0304 were observed in the EDS spectrum. Other than cobalt, peaks for any other constituent element of the cathode materials were not observed, which strongly suggests that the cobalt separated from other constituent elements of a cathode material (Li, Ni, Mn) is in pure form. Lastly, Figure 15 includes the X-ray diffraction (XRD) of C0304 separated from cathode materials.

[0053] The above description is that of current embodiments of the invention. Various

alterations and changes can be made without departing from the spirit and broader aspects of

the invention as defined in the appended claims, which are to be interpreted in accordance with

the principles of patent law including the doctrine of equivalents. Any reference to elements

in the singular, for example, using the articles "a "an," "the," or "said," is not to be construed

as limiting the element to the singular.

[0054] Throughout this specification and the claims which follow, unless the context

requires otherwise, the word 'comprise', and variations such as 'comprises' and 'comprising',

will be understood to imply the inclusion of a stated integer or step or group of integers or steps

but not the exclusion of any other integer or step or group of integers or steps.

[0055] The reference in this specification to any prior publication (or information

derived from it), or to any matter which is known, is not, and should not be taken as an

acknowledgment or admission or any form of suggestion that that prior publication (or

information derived from it) or known matter forms part of the common general knowledge in

the field of endeavor to which this specification relates.

§?1 -

Claims

1. A method for the recovery of cobalt from lithium ion batteries, the method comprising:

dissolving a battery material containing Co and Li within an acid to form a feed

solution, the feed solution including Co(II) and Li(I);

providing a membrane module including a plurality of hollow fibers, the plurality of

hollow fibers including a porous sidewall defining a lumen side spaced apart from a shell side;

wetting the porous sidewall of the plurality of hollow fibers with an organic phase, the

organic phase including a cationic extractant and an organic solvent;

performing membrane solvent extraction by moving the feed solution along one of the

lumen side or the shell side of the plurality of hollow fibers and simultaneously moving a strip

solution along the other of the lumen side or the shell side of the plurality of hollow fibers, the

strip solution including a pH that is less than a pH of the aqueous feed solution;

maintaining a pH of the feed solution within a predetermined range by intermittently

introducing a buffer or a base to the feed solution during membrane solvent extraction;

wherein wetting the porous sidewall of the plurality of hollow fibers with the organic

phase is performed prior to moving the feed solution and moving the strip solution, and wherein

the cationic extractant in the porous sidewall continuously extracts Co(II) from the aqueous

feed solution for recovery by the strip solution while substantially rejecting Li(I).

2. The method of claim 1, wherein the feed solution includes a positive pressure

differential with respect to the strip solution of between 1 psi and 5 psi.

3. The method of claim 1 or claim 2, wherein the feed solution and the strip solution are

moving in continuous recirculation through the membrane module for at least thirty minutes.

4. The method of any one of claims 1 to 3, further including separating the battery material

from a spent battery cathode, wherein separating the battery material from a spent battery

cathode includes subjecting the spent battery cathode to a thermal treatment, acid dissolution,

and vacuum filtration.

5. The method of any one of claims 1 to 4, wherein the organic phase contained within

the porous sidewall of the plurality of hollow fibers is substantially free of tributyl phosphate.