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org/journal/ascecg Research Article

Electrochemically Assisted (Bio)leaching of End-of-Life Lithium-Ion

Batteries for Critical Metals Recovery
Arindam Mukhopadhyay, Majid Alipanah, Luis A. Diaz, Hongyue Jin, Caitlin Barboza, Catherine House,
Yoshiko Fujita, Vicki S. Thompson, and David W. Reed*
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ABSTRACT: Reclaiming critical metals from end-of-life (EOL) lithium-ion

batteries (LIBs) is necessary for achieving global decarbonization goals. We
Downloaded via PALACKY UNIV on September 17, 2024 at 21:56:15 (UTC).

evaluated a novel recycling strategy that combines the advantages of electrochemi-

cally assisted leaching and organic acid leaching to recover critical metals from EOL
LIBs. A gluconic acid (GA)-containing solution produced by the bacterium
Gluconobacter oxydans was used as the electrolyte and lixiviant in an electrochemical
system, wherein a reducing agent, ferrous iron, was continuously regenerated. A
reductant is necessary for efficient solubilization of the LIB cathode metals (Co, Ni,
and Mn) under acidic conditions. GA avoids some of the chemical neutralization
and disposition issues associated with more corrosive mineral acids. Design of
experiments modeling revealed the relative impacts of temperature, pulp density,
and GA concentration on metal extraction efficiencies and predicted the net present value (NPV) of a LIB recycling operation based
on the approach. While metal extraction efficiency was governed by the GA concentration, NPV was most reliant on the LIB pulp
density. Although under today’s market conditions, the current iteration of the integrated approach is not predicted to be profitable,
our efforts to find an optimal balance between the extraction efficiency and NPV offer a template for improving the economic
viability of critical metal recycling approaches.
KEYWORDS: sustainability, end-of-life recycling, bioleaching, electrochemistry, lithium-ion battery, critical metals, design of experiments,
modeling optimization

■ INTRODUCTION
Achievement of the United Nations’ goal of transitioning into a
tallurgical recycling processes are known to be inefficient (low
metal recovery) and energy-consuming (high carbon foot-
carbon-neutral world by 2050 will require massive trans- print).8−12 In contrast, hydrometallurgical recycling offers
higher metal extraction efficiency (>90%) while requiring less
formation of the global transportation sector and the adoption
energy.13−15 Hydrometallurgical LIB recycling conventionally
of electric vehicles (EVs).1,2 Due to their light weight,
leverages a strong mineral acid, (e.g., sulfuric acid, H2SO4) and
structural robustness, superior potentiometric properties, high
a sacrificial reducing agent (e.g., hydrogen peroxide,
energy density, low self-discharging rate, and longevity,
H2O2).13−15 The reducing agent converts higher-valent metals
lithium-ion batteries (LIBs) are key to modern EVs.1,2 The
(Co3+, Ni3+, and Mn4+) to their more soluble divalent forms.
past decade has witnessed a rapid increase in the global
This strategy, however, has drawbacks including corrosive
demand for LIBs, which is projected to outstrip supplies of
mineral acid usage, high neutralization and disposal costs, toxic
lithium (Li), cobalt (Co), nickel (Ni), and manganese (Mn)
gas emissions, and energy-intensive synthesis, transport, and
(i.e., LNMC) by 2030 and global reserves in the coming
storage of H2O2.16−18 To help mitigate these challenges, we
years.3−6 The main secondary source of LNMC, end-of-life
have previously developed alternative hydrometallurgical
(EOL) LIBs, are forecasted to increase from ∼0.3 million
methodologies for recycling EOL LIBs described below.
tonnes in 2020 to ∼1.6 million tonnes in 2030.7 To circumvent
Electrochemically Assisted Leaching (EC-L). EC-L
supply chain risks in the near future and divert these toxic
employs electrons as “green reagents” to decrease the chemical
metals from landfill, interest has recently surged in the
development of cost-effective, energy-efficient, and environ-
mentally friendly strategies to recycle EOL LIBs and recover Received: July 23, 2024
these critical metals.8−12 Revised: August 22, 2024
Other than the direct reuse of battery components, the state- Accepted: August 23, 2024
of-the-art for EOL LIB cathode recycling encompasses two key Published: September 3, 2024
approaches: pyrometallurgical and hydrometallurgical recy-
cling, with components that can be integrated.8−12 Pyrome-

© 2024 American Chemical Society https://doi.org/10.1021/acssuschemeng.4c06090

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Figure 1. Simplified representation of the EC-Bio-OA-L strategy and process optimization for recovering critical metals from EOL LIB (LNMC)
black mass in the current study.

consumption of conventional hydrometallurgy.19−21 In addi- by the bacterium Gluconobacter oxydans) and Fe2+ as the
tion to high metal extraction efficiencies (>96%), EC-L reducing agent to leach LNMC from black mass of EOL LIB.35
requires lower concentrations of acids compared to conven- Fe2+ was confirmed to be critical for extraction of the metals,
tional hydrometallurgical approaches due to electrochemical although its presence in the leachate increases the complexity
generation of H+. Ferrous iron (Fe2+) can be used as the of downstream separations for the metals and increases costs
reducing agent, which can be regenerated electrochemically in for wastewater treatment and disposal.22,35,36 Technoeconomic
acidic aqueous media.20 EC-L may enable >80% decrease in analysis (TEA) estimated that Fe2+ is responsible for ∼12% of
total energy consumption and chemical cost compared to the total cost of the overall process.35 Our work also included
traditional H2O2-based hydrometallurgical leaching.20,21 De- thermodynamic modeling to better understand the limitations
spite these benefits, there is still room for further improve- on metal solubility imposed by the system chemical
ments in terms of environmental and economic sustainability. composition and the role of Fe2+ in enhancing solubility of
For instance, EC-L still relies on corrosive mineral acids, albeit the transition metals.36
at lower concentrations (e.g., 0.5−2 M H2SO4; typical Besides Fe2+, one major challenge of Bio-OA-L is the pulp
hydrometallurgy employs 1−4 M H2SO413−15). Furthermore, density. Bioleaching studies on EOL LIBs in academic
the acidity (pH ∼ 1) and presence of Fe2+ in the leachate literature are typically carried out with low pulp densities
necessitate substantial energy and chemical consumption for (e.g., ∼1−2%) in order to attain high metal extraction
downstream separations of the metal ions and the treatment efficiencies.34,36 This is because higher pulp densities usually
and disposal of wastewater.22 compromise metal extraction efficiencies via metal toxicity to
Microbiologically Produced Organic Acid Leaching microorganisms and consumption of acids by alkaline wastes,
(Bio-OA-L). The strategy of using microbially produced leading to an increase in the pH and a corresponding decrease
organic acids (OAs), as opposed to chemoautotrophic (i.e., in the metals solubility.26,27,29,32,34,35 However, low pulp
H2SO4) bioleaching mediated by iron- and sulfur-oxidizing densities result in the production of large volumes of aqueous
organisms,23−25 has attracted significant scientific attention in leachate, the handling, treatment, and disposal of which
recent years for its potential environmental benefits when substantially increase the overall cost of the process. Increasing
recovering diverse critical metals from ores and industrial waste the pulp density would decrease the cost and environmental
materials under more benign conditions.26−33 Bio-OA-L impact of Bio-OA-L by decreasing the volume of the OA-
harnesses the natural capability of microorganisms to produce containing lixiviant.26,27,29,32,34,35,37 Another major challenge
biodegradable OAs that can facilitate solubilization of metal for Bio-OA-L is that the leaching kinetics can be slow (days to
ions from waste materials.26−33 Furthermore, the OAs present weeks) compared to traditional hydrometallurgical leaching
in the lixiviant can be generated by microbially mediated (hours). For example, Bio-OA-L of EOL LIBs (1% pulp
conversion of agricultural wastes, which improves the density), facilitated by Aspergillus niger, took up to 14 days to
economics and lowers the environmental footprint.33 Because achieve extraction efficiencies of 95% for Li, 45% for Co, and
Bio-OA-L leachates are less acidic than traditional hydro- 38% for Ni at room temperature,26 and our own optimized
metallurgical mineral acid leachates, downstream neutralization conditions, as noted earlier, called for a 30 h leaching time.36
requirements are significantly diminished. Furthermore, OAs Such long operational time scales increase the energy cost and
offer the potential to form coordination complexes with the environmental footprint of Bio-OA-L.
metal ions, which can enhance solubility beyond just the low Goal of the Current Study. To address some of the above
pH effect, thereby facilitating improved leaching effi- cited challenges and develop an improved hydrometallurgical
ciency.26−33 critical material recovery process, this study examined the
The advantages of Bio-OA-L for critical metals recovery potential for integrating EC-L and Bio-OA-L to take advantage
from EOL LIBs have been highlighted by a number of of their respective strengths to recover critical metals from
studies.26,27,29,32,34,35 Our group has been evaluating Bio-OA-L EOL LIB black mass. The combined strategy is termed EC-
using a gluconic acid (GA)-dominant biolixiviant (generated Bio-OA-L (Figure 1). EC-Bio-OA-L combines the advantages
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of two different recycling techniques, EC-L and Bio-OA-L,

while simultaneously alleviating their individual setbacks. For
instance, EC-Bio-OA-L aims at (i) increasing the efficiency of
Bio-OA-L by increasing H+ production, decreasing the
operational time scale, and lowering the requirement for Fe2+
(indeed, initial Bio-OA-L experiments confirmed that when Fe
was limited, leaching was improved by utilizing electrochemical
regeneration of ferrous iron) and (ii) eliminating the major
challenge of EC-L in terms of environmental sustainability, i.e.,
the use of corrosive mineral acids (e.g., H2SO4), by replacing
them with lower concentrations of less corrosive biodegradable
acids that are biologically produced.
Design of Experiments (DOE) Modeling. Herein, we
demonstrate a proof-of-concept for EC-Bio-OA-L recycling of Figure 2. Schematic representation of the experimental setup and
EOL LIBs to maximize metal recovery with economic pertinent reactions of EC-Bio-OA-L in this study.
competitiveness. Our goal was also to determine the optimal
operational conditions via process optimization (Figure 1)
using DOE modeling and TEA. DOE modeling used the net
present value (NPV) as the success metric for defining optimal contained a mixture of black mass, FeSO4·7H2O, and GA biolixiviant,
conditions for recovering the metals from LIBs using the EC- while the anolyte contained 1 M KOH. The cathodic process
Bio-OA-L approach. DOE enables evaluation when multiple consisted of three correlated redox reactions, as shown in Figure 2: (i)
process variables are varied simultaneously.38 Modeling for LIB Fe2+-assisted reduction of higher-valent transition metals into their
recovery process optimization39 has been applied successfully divalent forms (e.g., eq 2), (ii) oxidation of Fe2+ to Fe3+ (eq 3), and
elsewhere.36,40−42 (iii) electrochemical reduction of Fe3+ to Fe2+ (eq 4), leading to the
regeneration of Fe2+.20 The anodic oxidation resulted in oxygen

■ MATERIALS AND METHODS

Materials. EOL LIB Black Mass. LNMC-based black mass was
evolution (eq 5). The catholyte and anolyte were separated by a
bipolar membrane (Fumasep FBM-PK), which allowed for water
ionization (eq 6) at the interface of the bonded cation- and anion-
obtained from Cirba Solutions (Charlotte, NC). Black mass is exchange membranes under the applied cell voltage of 2.1 V and
generated by mechanical preprocessing of EOL LIBs and is the most maintained the catholyte (acidic) and anolyte (alkaline) pH while
common feedstock for EOL LIB recycling.43 The chemical formula of precluding material crossover during the leaching process, as
the cathode-derived portion of LNMC in black mass can be established in our previous study.20 The continuous supply of H+
represented as LiNixMnyCozO2 (x + y + z = 1). Li (3.26% by to the catholyte (via water ionization) allowed the leaching process to
mass), Co (13.13%), Ni (8.38%), and Mn (4.95%) were the main be operated at much lower concentrations of acid (e.g., 75−300 mM
components of the black mass used in the experiments, while other GA) compared to the concentrations of H2SO4 used in EC-L (e.g.,
metals were minor components, e.g., Al (0.51%), Fe (0.48%), Cu 0.5−2 M) or conventional hydrometallurgical methods for LIB
(0.41%), and Zn (0.08%). recycling (1−4 M).
GA Biolixiviant. GA biolixiviant was prepared by growth of the G.
oxydans bacterium (B58 strain) in a glucose-amended Pikovskaya Co3 + + e Co2 + (2)
phosphate-modified medium at 30 °C for 42 h with 150 rpm shaking
as described previously.33,44 Filtered (0.22 μm) biolixiviant (pH ∼
2.2) was diluted with nanopure water (NP-W) to obtain the desired Fe2 + e Fe 3 + (3)
GA concentration in the final solution.
Leaching Studies. Bio-OA-L. Bioleaching of LNMC from EOL Fe3 + + e Fe 2 + (4)
LIB black mass with Fe2+ (FeSO4·7H2O) as the reducing agent was
conducted as reported by us recently.35,36 A mixture of black mass and 4OH 4e O2 + 2H 2O (5)
FeSO4·7H2O was treated with GA biolixiviant and allowed to react in
a sealed flask on an orbital shaker (150 rpm) at the intended
temperature, and the leachate was collected by centrifugation (6000g, H 2O H+ + OH (6)
30 min) and filtration (PES, 0.22 μm). The pulp density (%) was
calculated as a percentage of the black mass weight with respect to the The mesh electrodes were inserted into the cathode and anode
total slurry weight.35,36 The required molar equivalent of Fe2+ was compartments, and the electrochemical connection was established.
calculated from eq 1, representing the overall dissolution To facilitate the reaction in the nonhomogeneous mixture, an
reaction.20,35,36 immersion mechanical stirrer was used (600 rpm). An immersion
heater and a temperature probe connected to a programmable logic
LiNixMnyCozO2 (solid) + Fe 2 +(aq) + 4H+(aq) controller were used to maintain the intended reaction temperature.
The progress of the reaction with time was monitored by following
Li+(aq) + x Ni2 +(aq) + y Mn 2 + (aq) + zCo2 +(aq) the current profiles (Section S1, Figures S2-S3).20
+ Fe3 +(aq) + 2H 2O; where x + y + z = 1 (1) At the end of each experimental run, the cathode compartment was
washed thoroughly with NP-W to minimize material loss. The
EC-Bio-OA-L. EC-Bio-OA-L experiments were carried out under combined catholyte and washings were vacuum-filtered (Fisher
open-air conditions using a custom-made two-compartment electro- Scientific P8 filter paper; 20 μm). The residue was rinsed with NP-
chemical cell (Figure 2) as previously reported.20 For this study, W, and the rinse was combined with the filtrate. The combined filtrate
stainless steel and iridium oxide-coated titanium (both with 80 × 80 was considered to be the leachate that contained the recovered
mesh) were used as the cathode and anode, respectively. An EG&G- soluble metals. The residual black mass was dried (80 °C for 12 h)
263A potentiostat (Princeton Applied Research) was used to apply a and digested in aqua regia to dissolve the remaining insoluble metals.
constant cell voltage of 2.1 V, which was the average operational cell The extraction (or recovery) efficiencies of the metals were
voltage measured through EC-L in a previous work.20 The catholyte determined via eq 7. Details are provided in Section S1.

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Table 1. Critical Metals Recovery via EC-Bio-OA-L Recycling of EOL LIB Black Mass: CCD and Response Variablesa
process parameters extraction efficiency (%)
design point Fe:Co molar temperature pulp density GA concentration time leachate NPV ($
set type ratio (°C) (%) (mM) (h) pH Li Co Ni Mn M)
1 FP 1:8 25 1 75 4 4.5 19 7 6 9 −988
2 FP 1:8 25 1 275 8 3.5 25 15 18 23 −2086
3 FP 1:8 25 4 75 8 9.9 18 8 7 11 −583
4 FP 1:8 25 4 275 4 4.5 31 20 27 38 −667
5 CP 1:8 40 2.5 175 6 6.4 31 21 31 33 −670
6 FP 1:8 55 1 75 8 9.5 30 17 21 21 −902
7 FP 1:8 55 1 275 4 3.6 32 21 32 38 −1996
8 FP 1:8 55 4 75 4 8.3 21 10 8 13 −548
9 FP 1:8 55 4 275 8 7.7 39 26 32 41 −580
10 SP 1:8 25 2.5 175 4 4.7 26 17 25 30 −710
11 SP 1:8 55 2.5 175 4 7.2 32 20 32 36 −661
12 SP 1:8 40 1 175 4 3.8 22 16 20 23 −1458
13 SP 1:8 40 4 175 4 6.5 26 17 24 26 −550
14 SP 1:8 40 2.5 75 4 7.3 19 11 12 15 −680
15 SP 1:8 40 2.5 275 4 4.6 39 27 45 46 −763
a
In each case, the extraction efficiency is reported based on a leaching experiment wherein the whole amounts of both Fe2+ and GA biolixiviant
were added directly in a single portion (i.e., no partitioning of the reagents for three sequential additions similar to that in Table S1). The extraction
efficiency and NPV values are average numbers obtained from triplicate results in each set.

extraction efficiency (%) served as the response variable to assess the economic competence of
the process. NPV was calculated using eq 8.35
= (amount of recovered soluble metal in leachate)
n
NCFt
/(sum of the amounts of recovered soluble metal in leachate NPV =
t=0
(1 + i)t (8)
and insoluble metal in residual black mass) × 100% (7)
wherein NCFt is net cash flow over time t and i is the discount rate
Analytical Methods. The concentration of GA was determined via (8%) over n periods (30 years). Details are provided in Section S2.
high-performance liquid chromatography (HPLC) as described Life Cycle Assessment (LCA). To assess the potential environ-
previously.44 The metal concentrations were determined with atomic mental impacts of the proposed EC-Bio-OA-L, a cradle-to-gate LCA
absorption spectroscopy (AAS; Agilent 240FS 200 Series) as was conducted for a system boundary ending with leachate
described previously.45 production. The functional unit was defined as 1 kg of black mass
DOE Modeling for EC-Bio-OA-L Optimization, TEA, and LCA. recycled. Table S8 shows the life cycle inventory. The ecoinvent 3.10
EC-Bio-OA-L Optimization. For the experiments reported here, GA database49 was used whenever possible, as shown in Table S8, and the
biolixiviant was produced by growing G. oxydans on refined glucose, Tool for Reduction and Assessment of Chemicals and Other
but TEA assumed GA production by G. oxydans grown on agricultural Environmental Impacts (TRACI)50 was used to classify and
wastes (e.g., corn stover); we previously determined that biolixiviant characterize environmental impacts in the United States, using
produced from corn stover demonstrates improved economic and SimaPro software version 9.6.
environmental sustainability while maintaining the same or better
leaching performance as GA produced from glucose.33
A fractional factorial design, which is a classical DOE, was first
conducted to screen factors for their significance. Center points were
■ RESULTS AND DISCUSSION
Initial Validation of EC-Bio-OA-L for Critical Metals
added to check the presence of the curvature. Based on the leaching
Recovery from EOL LIBs. We showed that using less than
experimental results, analysis of variance (ANOVA) was conducted, the stoichiometric molar ratio of 1:1 of Fe:Co (where Co
and insignificant factors were dropped to reduce the number of represents the sum of Co, Ni, and Mn in the black mass) could
follow-up experiments. Then the design was upgraded to central result in effective leaching when Fe2+ was regenerated
composite design (CCD) when a significant curvature was electrochemically. Table S1 shows the results for an initial
observed.12,36,46−48 Again, the experimental results were analyzed comparison of Bio-OA-L at 1:1 and 1:4 and EC-Bio-OA-L at
using ANOVA and response surface methodology (RSM)12,36,46−48 to 1:4 Fe:Co molar ratio for recovering critical metals from black
optimize EC-Bio-OA-L. Two second-order response models were mass at 55 °C. The extraction efficiencies of LNMC via Bio-
developed by using the temperature, pulp density, and GA OA-L decreased significantly at the lower Fe:Co molar ratio
concentration as the main process parameters and the metal (e.g., Li and Co dropped from 100% and 86% to 66% and 28%,
extraction efficiency and economic value (Section S2) as the two respectively), even though the pulp density was lower and the
response variables. Details of the modeling and ANOVA are provided GA concentration was higher. However, upon moving from
in Section S3. The surface optimizer in MiniTab V.21.1 was used to
Bio-OA-L to EC-Bio-OA-L, the Li and Co extraction
find the optimal settings. As multiple metals were extracted through
this process, Co was the target for extraction efficiency because it is
efficiencies increased from 66% and 28% to 100% and 73%,
the most valuable metal in LNMC, whereas all four metals (LNMC) respectively.
were considered for TEA. Optimization of EC-Bio-OA-L via DOE with RSM. In
TEA. EC-Bio-OA-L experiments were carried out under the our recent study on Bio-OA-L, we employed a 30 h leaching
designed conditions, and the metal extraction efficiencies were used time35 but recognized that a shorter leaching duration would
as inputs for TEA.35 The costs and revenues pertinent to each reduce the overall costs and increase the economic viability.
experimental condition were estimated to determine the NPV.35 NPV We therefore conducted preliminary EC-Bio-OA-L experi-
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Figure 3. Pareto charts derived from fitted second-order models of CCD based on EC-Bio-OA-L recycling of the EOL LIB black mass with (A) Co
extraction efficiency and (B) NPV as the response variables.

ments to examine leaching over time using a surrogate material extraction efficiency conform to the order GA concentration >
for black mass, namely, lithium cobalt oxide. To optimize temperature > pulp density.
experiments with black mass, a 1:8 molar ratio of Fe:Co was These relationships can be represented in a Pareto chart
used. Figure S1 shows the recovery of soluble Li, Co, and Fe (Figure 3A) derived from a second-order model of the Co
using EC-Bio-OA-L at 25 °C as a function of time (range of extraction efficiency as the response variable and the uncoded
0−10 h). The recovery molar ratios of Li:Fe and Co:Fe were regression model shown in eq 9, wherein A, B, and C represent
highest around 8 and 4 h, respectively. Therefore, for EC-Bio- temperature, pulp density, and GA concentration, respectively.
OA-L of black mass, we sought to vary the leaching time Details are provided in Section S3.1. The observed trend can
between 4 and 8 h. be rationalized by the consideration that the extraction
We designed operational conditions (Table 1) by using four efficiency of Co relies solely on its aqueous solubility.
process parameters�temperature (A; range of 25−55 °C),
pulp density (B; range of 1−4%), GA concentration (C; range Co extraction efficiency (%)
of 75−275 mM), and time (D; range of 4−8 h)�for the EC- = 0.1435 + 0.00621A + 0.0647B + 0.000547C
Bio-OA-L experiments. The initial fractional factorial design
consisted of experimental sets 1−9 in Table 1, and the 0.000049AA 0.0129BB 0.000001CC
ANOVA results showed an insignificant impact of time (Table 0.000337AB + 0.000002AC + 0.0001BC (9)
S9). Because longer leaching times equate to higher costs, the
leaching time was dropped from further investigation and kept In addition to providing the acidity required for dissolving
constant at 4 h. With a significant curvature effect shown in the basic metal oxides, GA further enhances solubilization of the
ANOVA results (Table S9), the design was upgraded into a transition-metal ions including Co (Co3+ and Co2+) via the
face-centered CCD with 15 points including eight factorial formation of thermodynamically stable metal-gluconate
points (FPs; sets 1−4 and 6−9), one central point (CP; set 5), complexes.26−33,35,36,51 The impact of the temperature can be
and six-star points (SPs; sets 10−15). Accordingly, the rationalized based on the fact that higher temperature
influence of the three main parameters, A−C, on the EC- facilitates faster kinetics of dissolution of Co and less
Bio-OA-L process outcomes was more fully examined. The two reprecipitation.52 Results reveal that the Co extraction
response variables, the metal extraction efficiency and NPV, efficiency is inversely correlated to the pulp density, which
were optimized by developing two second-order models. makes sense because Co leaching is less likely to be
constrained by the Co solubility limit and Co-gluconate
Impacts of the Process Parameters on the Metal
complex formation is favored due to the presence of excess
Extraction Efficiencies. Table 1 shows that the metal
GA.
extraction efficiencies were highest in sets 9 and 15, while
Impacts of Process Parameters on the NPV. NPV was
they were lowest in sets 1 and 3. This suggests that a higher negative under all operational conditions (Table 1), suggesting
GA concentration is beneficial for metal extraction. For that the overall EC-Bio-OA-L process is not likely to be
example, a comparison between sets 3 and 4, sets 8 and 9, profitable at the current state of development and market
or sets 14 and 15 reveals that an increase in the GA conditions. Notwithstanding this notion, we sought to examine
concentration from 75 to 275 mM manifests in a >150% the relative influences of different process parameters on the
increase in the Co extraction efficiency. Compared to GA NPV to identify the factors to focus on to improve the process
concentration, temperature had a much lower effect on the in future work.
metal extraction efficiency. For instance, a comparison between NPV was the highest (least negative) and lowest (most
sets 4 and 9 or sets 10 and 11 shows that an increase in negative) in sets 8 and 2, respectively. This suggests that higher
temperature from 25 to 55 °C results in only a 20−30% pulp density (4% compared to 1%) and lower GA
increase in the Co extraction efficiency. The pulp density had concentration (75 mM compared to 275 mM) are beneficial
the least impact on the metal extraction efficiency. For in improving the NPV. For instance, a comparison between
instance, a comparison between sets 1 and 3 or sets 12 and 13 sets 2 and 4 or sets 7 and 9 reveals that an increase in the pulp
shows that, upon an increase in the pulp density from 1% to density from 1% to 4% results in a ∼3-fold increase in NPV. In
4%, the Co extraction efficiency remains virtually unaltered. contrast, a comparison between sets 1 and 2 or sets 6 and 7
Therefore, the magnitudes by which the three process reveals that an increase in the GA concentration from 75 to
parameters (within the range tested for each) impact the Co 275 mM leads to a ∼2-fold decrease in NPV. Temperature had
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Figure 4. Optimal conditions derived from second-order CCD models of EC-Bio-OA-L of black mass for maximum Co extraction efficiency and
NPV. The contour plots for (A) Co extraction efficiency and (B) NPV show the optimal settings for maximum response (darkest green areas).

the least influence on NPV. For example, a comparison function of the GA concentration and temperature at constant
between sets 1 and 6 or sets 2 and 7 shows that NPV remains pulp density. These plots predict that the optimal extraction
virtually unaffected upon an increase in temperature from 25 to conditions are 55 °C temperature, 2.8% pulp density, and 275
55 °C. Essentially, the relative impact of the process mM GA concentration. This optimal condition can offer a
parameters (within the range tested for each) in increasing maximum of a 27% Co extraction efficiency. For the objective
NPV follows the order pulp density > GA concentration > of maximizing NPV, Figures 4B and S7 represent a contour
temperature. and a surface plot, respectively, of NPV as functions of the pulp
Figure 3B is a Pareto chart derived from a second-order density and GA concentration at constant temperature. These
model using the NPV as the response variable. It represents the plots suggest that the optimal NPV conditions are a 50 °C
relative standardized effects (statistical significances) of the temperature, 2.9% pulp density, and 75 mM GA concentration,
three process parameters A−C on NPV. The uncoded which can offer a maximum of −$404 M NPV at current metal
regression model based on the main, quadratic, and interaction prices.
terms of the parameters is shown in eq 10. Details are provided LCA Results. The potential environmental impacts of
in Section S3.2. recycling 1 kg of black mass are shown in Table 2, which are

NPV ($) = 1,454,560,486 + 9,172,509A Table 2. LCA Results for Recycling 1 kg of Black Mass
+ 759,545,713B 6,297,575C 86,987AA impact category total impact unit
150,095,351BB 1937CC 291,479AB ozone depletion 2.50 × 10−7 kg of CFC-11 equiv
global warming 2.03 × 100 kg of CO2 equiv
+ 4692AC + 1,729,763BC (10) smog 1.37 × 10−1 kg of O3 equiv
acidification 9.38 × 10−3 kg of SO2 equiv
The observed order is a consequence of the relative impacts
eutrophication 8.62 × 10−3 kg of N equiv
of the process parameters on the overall EC-Bio-OA-L
carcinogenics 1.72 × 10−7 CTUh
economics. The highest influence of pulp density on NPV
noncarcinogenics 7.91 × 10−7 CTUh
can be explained by the consideration that higher pulp
respiratory effects 2.53 × 10−3 kg of PM2.5 equiv
densities are associated with lower reaction volumes for
ecotoxicity 1.68 × 101 CTUe
processing the same amount of black mass, decreasing, thereby,
fossil fuel depletion 3.08 × 100 MJ surplus
all pertinent costs and improving profitability. In contrast,
lower pulp densities may offer better revenues with higher
metal extraction efficiencies but incur significant processing
costs that decrease profitability. The GA concentration is the calculated based on the life cycle inventory shown in Table S8,
second most important parameter, albeit via an inverse representing the highest NPV condition (experimental set 8
correlation. This can be rationalized by the fact that a higher shown in Table 1). Black mass, GA, and electricity were
GA concentration necessitates greater bioproduction of GA. identified as the key environmental hotspots. For example, 33%
GA is a major cost driver (i.e., >15% of the total cost), so the of the total global warming impact was due to black mass, 36%
increased recovered metal revenue from using more GA is not was due to GA, and 29% was due to electricity. Adopting solar
worth the additional incurred costs. energy could reduce the total global warming potential from
Optimal Conditions for Maximum Extraction Efficiency the current 2.03 kg of CO2 equivalent to 1.5 kg of CO2
and NPV. The optimal operational conditions for EC-Bio-OA- equivalent.
L, at which the highest values of Co extraction efficiency and Future Directions for Improving the EC-Bio-OA-L Out-
NPV can be achieved, were determined from surface comes. Upon optimization with the three main process
optimization using the fitted second-order models, as discussed parameters, extraction efficiency was revealed to be a major
above. For the objective of maximizing Co extraction bottleneck (e.g., maximum of 27% for Co), indicating that it is
efficiency, Figures 4A and S6 represent a contour and a a prime target for future research. Promising directions include
surface plot, respectively, of the Co extraction efficiency as a the following:
14124 https://doi.org/10.1021/acssuschemeng.4c06090
ACS Sustainable Chem. Eng. 2024, 12, 14119−14127
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

(1) Employing biolixiviants containing OAs with greater concept of EC-Bio-OA-L, the approach of systematic
complexation properties would increase the solubilization and optimization presented here will be useful for supporting the
stabilization of metals in leachates, increasing the extraction development of more sustainable technologies for the recovery
efficiency and NPV. Furthermore, identifying cheaper growth of critical materials from secondary sources to be ready for
substrates and production methods for OAs can improve NPV deployment under more favorable market conditions.
(e.g., we have recently shown that nonrecyclable paper is more
economically viable and effective as a feedstock for biolixiviant
production than corn stover, for which Bio-OA-L had a 21%
■ ASSOCIATED CONTENT
* Supporting Information
sı
average profit margin processing 10000 tons of black mass per
The Supporting Information is available free of charge at
year and $110 M NPV over 30 years).53
https://pubs.acs.org/doi/10.1021/acssuschemeng.4c06090.
(2) For the electrochemical process, employing membranes
with better ion-transport properties, varying the chemical Details of process optimization via DOE and RSM and
composition of the anolyte solution, and improving the cell CCD modeling for the metal extraction efficiency and
design could increase the extraction efficiency and NPV. As a NPV (PDF)
preliminary test of this idea, we carried out an EC-Bio-OA-L
experiment under the same conditions as those in set 3 of
Table 1 except that we replaced the bipolar membrane with a
cation-exchange membrane and the alkaline anolyte (1 M
■ AUTHOR INFORMATION
Corresponding Author
KOH) with an acidic anolyte (1 M H2SO4). Details are David W. Reed − Critical Materials Innovation Hub (CMI),
provided in Section S4. Compared to the previous electro- Energy and Environment Science and Technology Division,
chemical system, this modified design produced a 3−4-fold Idaho National Laboratory, Idaho Falls, Idaho 83415,
increase in the extraction efficiencies of Co (from 8% to 23%), United States; orcid.org/0000-0003-4877-776X;
Ni (from 7% to 26%), and Mn (from 11% to 43%) and a 2-fold Phone: +1-208-526-7788; Email: [email protected]
increase in NPV (from −$583 M to −$292 M).
(3) To further facilitate faster leaching kinetics and Authors
increased extraction efficiency, the heterogeneous reaction Arindam Mukhopadhyay − Critical Materials Innovation
mixture in the electrochemical cell can be subjected to Hub (CMI), Energy and Environment Science and
ultrasonication during the leaching process to decrease the Technology Division, Idaho National Laboratory, Idaho
particle size of the black mass and better homogenize the Falls, Idaho 83415, United States; orcid.org/0000-0002-
contents, minimizing the limitations caused by mass transfer 0620-4157
and boundary layers. Majid Alipanah − Critical Materials Innovation Hub (CMI),
(4) Another pathway to improve NPV can be using EOL Department of Systems and Industrial Engineering, University
LIBs without the magnetic separation step during preprocess- of Arizona, Tucson, Arizona 85721, United States
ing (designed to remove iron). This will allow for procuring Luis A. Diaz − Critical Materials Innovation Hub (CMI),
black mass at a cheaper price (58% of the total cost) and Energy and Environment Science and Technology Division,
lowering chemical costs for the reducing agent (Fe2+) by using Idaho National Laboratory, Idaho Falls, Idaho 83415,
the iron content in the LIB itself. United States; orcid.org/0000-0003-4895-464X
Hongyue Jin − Critical Materials Innovation Hub (CMI),
■ CONCLUSIONS
Recycling EOL LIBs to recover critical clean energy metals is
Department of Systems and Industrial Engineering, University
of Arizona, Tucson, Arizona 85721, United States
crucial from both economic and environmental standpoints. Caitlin Barboza − Critical Materials Innovation Hub (CMI),
This study reported and evaluated a novel EC-Bio-OA-L Energy and Environment Science and Technology Division,
recycling strategy to recover critical energy metals from the Idaho National Laboratory, Idaho Falls, Idaho 83415,
LNMC-based black mass of EOL LIBs. The strategy leverages United States
the combined advantages of EC-L and Bio-OA-L while Catherine House − Critical Materials Innovation Hub
simultaneously addressing their individual drawbacks. To (CMI), Energy and Environment Science and Technology
maximize the metal extraction efficiencies and economic Division, Idaho National Laboratory, Idaho Falls, Idaho
returns of EC-Bio-OA-L, this study applied DOE with a 83415, United States
RSM as the optimization approach. Second-order modeling Yoshiko Fujita − Critical Materials Innovation Hub (CMI),
with CCD offered insights regarding the relative influences of Energy and Environment Science and Technology Division,
the main process parameters�temperature, pulp density, and Idaho National Laboratory, Idaho Falls, Idaho 83415,
GA concentration�on the Co extraction efficiency and NPV. United States; orcid.org/0000-0002-4472-4102
The GA concentration played the most decisive role in Vicki S. Thompson − Critical Materials Innovation Hub
increasing the metal extraction efficiency. In contrast, the pulp (CMI), Energy and Environment Science and Technology
density played the most important role in improving the NPV. Division, Idaho National Laboratory, Idaho Falls, Idaho
The NPVs of EC-Bio-OA-L turned out to be negative under 83415, United States; orcid.org/0000-0003-4975-392X
all conditions examined, indicating that, under current market Complete contact information is available at:
conditions, the overall process may not be profitable. We also https://pubs.acs.org/10.1021/acssuschemeng.4c06090
demonstrated that there is a trade-off between the metal
recovery efficiency and economic return. Finding an optimal Author Contributions
balance between these two outcomes will require an The manuscript was written through contributions of all
investigation beyond the three process parameters studied authors. All authors have given approval to the final version of
herein. We believe that, aside from introducing the novel the manuscript.
14125 https://doi.org/10.1021/acssuschemeng.4c06090
ACS Sustainable Chem. Eng. 2024, 12, 14119−14127
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Notes (15) Chernyaev, A.; Zou, Y.; Wilson, B. P.; Lundström, M. The
The authors declare no competing financial interest. Interference of Copper, Iron and Aluminum with Hydrogen Peroxide
and its Effects on Reductive Leaching of LiNi1/3Mn1/3Co1/3O2.
■ ACKNOWLEDGMENTS
This project was funded by the CMI Hub, an Energy
Sep. Purif. Technol. 2022, 281, No. 119903.
(16) Li, Z.; Diaz, L. A.; Yang, Z.; Jin, H.; Lister, T. E.; Vahidi, E.;
Zhao, F. Comparative Life Cycle Analysis for Value Recovery of
Innovation Hub led by the U.S. Department of Energy Precious Metals and Rare Earth Elements from Electronic Waste.
(DOE), Ames Laboratory, and supported by the DOE’s Office Resour. Conserv. Recycl. 2019, 149, 20−30.
of Energy Efficiency and Renewable Energy, Advanced (17) Pagliaro, M.; Meneguzzo, F. Lithium Battery Reusing and
Materials & Manufacturing Technologies Office. The research Recycling: A Circular Economy Insight. Heliyon 2019, 5, No. e01866.
was conducted under the DOE, Idaho Operations Office, (18) Moreira, F. C.; Boaventura, R. A.; Brillas, E.; Vilar, V. J.
under Contract DE-AC07-05ID14517 and the University of Electrochemical Advanced Oxidation Processes: A Review on their
Arizona Subcontract SC-21-556 with Ames Laboratory. The Application to Synthetic and Real Wastewaters. Appl. Catal. B:
Environ. 2017, 202, 217−261.
U.S. Government retains a nonexclusive, royalty-free, license to (19) Maes, S.; Zhuang, W.-Q.; Rabaey, K.; Alvarez-Cohen, L.;
publish or reproduce the published form of this research Hennebel, T. Concomitant Leaching and Electrochemical Extraction
contribution, and allow others to do so, for U.S. Government of Rare Earth Elements from Monazite. Environ. Sci. Technol. 2017,
purposes only. We thank INL scientists Meng Shi and Kastli 51, 1654−1661.
Schaller for assistance with AAS and HPLC, respectively. (20) Diaz, L. A.; Strauss, M. L.; Adhikari, B.; Klaehn, J. R.; McNally,

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