batteries

Review
Direct Recycling Technology for Spent Lithium-Ion Batteries:
Limitations of Current Implementation
Anna Pražanová , Zbyněk Plachý , Jan Kočí, Michael Fridrich and Vaclav Knap *

Department of Electrotechnology, Faculty of Electrical Engineering, Czech Technical University in Prague,

Technická 1902/2, 166 27 Prague, Czech Republic; [email protected] (A.P.); [email protected] (Z.P.);
[email protected] (J.K.); [email protected] (M.F.)
* Correspondence: [email protected]

Abstract: The significant deployment of lithium-ion batteries (LIBs) within a wide application field
covering small consumer electronics, light and heavy means of transport, such as e-bikes, e-scooters,
and electric vehicles (EVs), or energy storage stationary systems will inevitably lead to generating
notable amounts of spent batteries in the coming years. Considering the environmental perspective,
material resource sustainability, and terms of the circular economy, recycling represents a highly
prospective strategy for LIB end-of-life (EOL) management. In contrast with traditional, large-
scale, implemented recycling methods, such as pyrometallurgy or hydrometallurgy, direct recycling
technology constitutes a promising solution for LIB EOL treatment with outstanding environmental
benefits, including reduction of energy consumption and emission footprint, and weighty economic
viability. This work comprehensively assesses the limitations and challenges of state-of-the-art,
implemented direct recycling methods for spent LIB cathode and anode material treatment. The
introduced approaches include solid-state sintering, electrochemical relithiation in organic and
aqueous electrolytes, and ionothermal, solution, and eutectic relithiation methods. Since most direct
recycling techniques are still being developed and implemented primarily on a laboratory scale, this
review identifies and discusses potential areas for optimization to facilitate forthcoming large-scale
industrial implementation.

Keywords: lithium-ion batteries; direct recycling; end-of-life

Citation: Pražanová, A.; Plachý, Z.;
Kočí, J.; Fridrich, M.; Knap, V. Direct
Recycling Technology for Spent
Lithium-Ion Batteries: Limitations of
Current Implementation. Batteries 1. Introduction
2024, 10, 81. https://doi.org/ Lithium-ion batteries (LIBs) stand out as a pivotal technology with numerous advan-
10.3390/batteries10030081 tages compared to other electrochemical storage technologies these days. These include
Academic Editors: Yaocai Bai higher cell voltage, increased energy density, extended lifespan, minimal memory effect,
and Panpan Xu simplicity to charge and maintain, low self-discharge, potential for miniaturization, and
different packaging shapes. Thus, the LIBs set a turning point in the field of power sources,
Received: 8 January 2024 where they are utilized in a variety of applications encompassing small consumer electronic
Revised: 22 February 2024
systems, including watches, smartphones, or laptops; portable power tools, such as drills
Accepted: 26 February 2024
or saws; home or industrial systems for energy storage (BESS); and light or heavy means of
Published: 28 February 2024
transport, including electric bikes, scooters, and electric vehicles (EVs) [1–4].
The typical composition of LIBs predominantly comprises a cathode, anode, separator,
and electrolyte. Ordinarily, batteries also have an electronic control unit, a protective metal
Copyright: © 2024 by the authors.
casing, and plastic coverings according to shape, composition, and structure, as illustrated
Licensee MDPI, Basel, Switzerland. in Figure 1 [5]. Cathodes are predominantly composed of a mixture involving a polyvinyli-
This article is an open access article dene fluoride (PVDF) binder, carbon powder, and lithium (Li) transition metal oxides such
distributed under the terms and as lithium cobalt oxide (LCO or LiCoO2 ), lithium manganese oxide (LMO or LiMn2 O4 ),
conditions of the Creative Commons lithium iron phosphate (LFP or LiFePO4 ), lithium nickel cobalt aluminum oxide (NCA or
Attribution (CC BY) license (https:// LiNix Coy Alz O2 ), and lithium nickel manganese cobalt oxide (NMC or LiNix Coy Mnz O2 ).
creativecommons.org/licenses/by/ These materials are coated onto a current collector, typically an aluminum (Al) foil. Simi-
4.0/). larly, anodes commonly utilize graphite, providing a structure capable of holding Li within

Batteries 2024, 10, 81. https://doi.org/10.3390/batteries10030081 https://www.mdpi.com/journal/batteries

Batteries 2024, 10, x FOR PEER REVIEW 2 of 22

Batteries 2024, 10, 81

LiNixCoyMnzO2). These materials are coated onto a current collector, typically an alumi-
2 of 20
num (Al) foil. Similarly, anodes commonly utilize graphite, providing a structure capable
of holding Li within its layers. The active carbon material is attached to a copper (Cu)
conductor plate using a PVDF binder. Electrolytes consist of a solution containing a lith-
its layers. The active carbon material is attached to a copper (Cu) conductor plate using a
ium-containing salt, such as lithium perchlorate (LiClO4), lithium tetrafluoroborate
PVDF binder. Electrolytes consist of a solution containing a lithium-containing salt, such as
(LiBF4), or lithium hexafluorophosphate (LiPF6), dissolved in an organic solvent like di-
lithium perchlorate (LiClO4 ), lithium tetrafluoroborate (LiBF4 ), or lithium hexafluorophos-
methyl carbonate (DMC) or ethylene carbonate (EC). As a medium, the electrolyte facili-
phate (LiPF6 ), dissolved in an organic solvent like dimethyl carbonate (DMC) or ethylene
tates the transport of ions between battery electrodes. A separator, crafted from polymeric
carbonate (EC). As a medium, the electrolyte facilitates the transport of ions between battery
materials such
electrodes. as polypropylene
A separator, crafted from(PP) or polyethylene
polymeric materials(PE),
suchacts as a non-conductor
as polypropylene (PP) or or
barrier; thus, it is inserted between the anode and cathode to eliminate the risk
polyethylene (PE), acts as a non-conductor or barrier; thus, it is inserted between the anodeof short-
circuiting
and cathode caused by direct
to eliminate thecontact
risk ofbetween the electrodes
short-circuiting caused[1,6,7]. Thecontact
by direct composition of LIBs
between the
slightly differs between manufacturers and commonly consists of 5–20%
electrodes [1,6,7]. The composition of LIBs slightly differs between manufacturers andCo, 5–20% Mn,
5–30% Ni, 5–10% Li, 5–40% of other metals, 10–15% organic chemicals, and
commonly consists of 5–20% Co, 5–20% Mn, 5–30% Ni, 5–10% Li, 5–40% of other metals, 3–10% plastics
[8–10]. organic chemicals, and 3–10% plastics [8–10].
10–15%

Figure1.1.Schematic
Figure Schematicdrawing
drawingshowing
showingthe the shape
shape and
and components
components of of various
various Li-ion
Li-ion battery
battery configu-
configura-
rations:
tions: (a) (a) cylindrical;
cylindrical; (b) (b) coin;
coin; (c) prismatic;
(c) prismatic; andand (d) thin
(d) thin and and
flat. flat. Reprinted
Reprinted fromfrom [5], with
[5], with permis-
permission
sion Springer
from from Springer
Nature,Nature, Copyright
Copyright (2001).(2001).

Thelifespan
The lifespanofofLIBs
LIBsvaries
variesaccording
accordingtototheir
theirapplication
applicationfield;field;ininaasmall
smallelectronic
electronic
device,ititcan
device, canlast
lastbetween
between22and and55years,
years,whereas
whereasininEVsEVsor orBESSs,
BESSs,ititmay mayrange
rangefromfrom88toto
15
15years
years[1,11].
[1,11].Considering
Consideringthe thesignificant
significantdifference
differencebetween
betweenthe theutilization
utilizationofofLIBLIBwithin
within
small
small portable electronic devices and longer-life applications, currently standing 80:20
portable electronic devices and longer-life applications, currently standing at an at an
ratio,
80:20the annual
ratio, increaseincrease
the annual in end-of-life (EOL) batteries
in end-of-life is evident
(EOL) batteries [12]. Projections
is evident of trendsof
[12]. Projections
have
trendsbecome a focal point
have become a focalinpoint
numerous predictions;
in numerous according
predictions; to them,
according tothe estimation
them, of
the estima-
spent LIBs
tion of spentwillLIBs
increase to 464,000
will increase tonnes by
to 464,000 2025 by
tonnes [13].
2025In [13].
response to the challenges
In response of the
to the challenges
battery raw material
of the battery supply chain
raw material supply and environmental
chain footprint footprint
and environmental reduction,reduction,
a series of aglobal
series
or European initiatives have been implemented. The simplified hierarchy
of global or European initiatives have been implemented. The simplified hierarchy for for EOL battery
management
EOL battery is outlined as is
management follows [1,14]:
outlined as follows [1,14]:
•• Prevention:designing
Prevention: designingLIBs
LIBswith
withless-critical
less-criticalmaterials
materialsand
andcreating
creatingelectronic
electronicdevices
devices
withsmaller/lighter
with smaller/lighterLIBs
LIBsto
toprevent
preventandandminimize
minimizewaste
wastegeneration.
generation.
•• Re-use:entailing
Re-use: entailingsecondary
secondaryusage
usageofofLIBs
LIBstotoprolong
prolongtheir
theirservice
servicelife,
life,especially
especiallyfor
for
EV
EVbatteries.
batteries.
• Recycling: involving the recovery of valuable materials from spent LIBs and their
return to the value chain.
Batteries 2024, 10, 81 3 of 20

• Recovery: considering using certain materials from spent LIBs as fuel in processes like
pyrometallurgy to extract energy from waste.
• Disposal: discarding spent LIBs without recovered value, directing them to specialized
landfills or municipal waste combustion facilities for incineration.
Given the LIBs’ toxic content, which can cause severe environmental pollution risks
and pose a threat to human health, and the significant quantities of valuable and other
essential metals, such as Li, Co, Ni, Mn, Cu, Al, and Fe, recycling emerges as an up-and-
coming technology for managing waste LIBs. This approach, covering suitable flue gas
treatment, mitigates the pollution from hazardous materials and offers alternative sources
of essential metals, particularly Li and Co, while reducing emissions associated with mining
and post-processing activities [2,15].
Commonly implemented methods to recycle appealing components of spent LIBs are
either based on pyrometallurgical or hydrometallurgical methods. The pyrometallurgical
procedure, rooted in metal smelting, is a well-established practice based on separation
and high-temperature treatment [16]. While the process is energy-intensive and emission-
productive, it proves relatively efficient as it yields the most valuable metal resources (e.g.,
Co or Ni) via metal alloys. However, portions of Li end up in slags, which are not typically
recovered [17]. Conversely, hydrometallurgical techniques allow the recovery of all metal
elements in their salt states with a higher purity [17,18]. This approach serves at the expense
of consuming significant chemical reagents, resulting in elevated costs and environmental
concerns related to waste pollution [1,2,19].
These methods represent quick and sufficient solutions for current recycling pressure,
but they cannot realize a closed-loop economy in future years without the necessary
optimization steps. Therefore, there is a high demand for alternative recycling technologies
that can directly reuse degraded energy storage materials for battery manufacturing from
an economically and environmentally sustainable perspective. The most promising of them
is direct recycling technology [7,20,21].
Lately, direct recycling processes have surfaced as a sustainable recycling technology
renowned for healing compositional and structural defects [7]. By preserving the original
crystal structure and avoiding the breakdown of electroactive materials into their elemental
states, it contrasts conventional recycling methods (pyrometallurgy, hydrometallurgy) [2].
A comparison of the general pros, cons, and challenges of the mentioned recycling processes
is shown in Table 1.
Although hydrometallurgy is known for its high process efficiency, which can reach
up to 76–98.2%, and the purity of obtained materials between 96.5–99.7%, low energy
consumption is typically only observed during the recovery phase [2]. However, when
considering additional processes such as wastewater treatment, energy consumption can
equal or surpass that of pyrometallurgy [22]. Due to the inherent nature of hydrometallur-
gical processing, this method requires more water than other techniques. Thus, optimized
approaches that minimize water usage can yield significant additional benefits for this
recycling method [20].
Despite the advantages of pyrometallurgy, which include process simplicity and speed
compared to multi-step chemical leaching processes that span several hours, the energy
consumption during the recovery phase is notably high due to the requirement of operating
at high temperatures [20]. Moreover, the process leads to significant emission production.
Thanks to high-thermal processing, recovering certain materials like Li, Al, and organic
compounds is impossible. Although pyrometallurgical processing does not restrict input
size, it cannot be used to treat some LIB types, such as LFP. Therefore, the method is
often combined with hydrometallurgical recycling steps to enhance efficiency and product
quality [2].
Consequently, direct recovery holds considerable promise in delivering recycled elec-
troactive materials to battery manufacturers with heightened sustainability, characterized
by decreased energy consumption and limited dependence on chemical agents [20,21].
Batteries 2024, 10, x FOR PEER REVIEW 4 of 22

characterized by decreased energy consumption and limited dependence on chemical

Batteries 2024, 10, 81 4 of 20
agents [20,21]. Nevertheless, it is currently necessary to optimize established techniques
to reduce costs and further optimize product performance.

Nevertheless,
Table it is currently
1. Comparisons necessary
of advantages to optimize established
and disadvantages techniques
and challenges to methods.
for different reduce costs
Re-
and further
printed optimize
from [23] under product
the termsperformance.
and conditions of the CC BY 4.0 license, Copyright (2020).

Process Advantages
Table 1. Comparisons of advantagesDisadvantages
and disadvantages and challengesChallenge
for different methods.
High recovery rate
Reprinted from [23] under the terms and conditions of the CC BY 4.0 license, Copyright (2020).
High-purity product
Hydrometallurgical
Process More wastewater Wastewater treatment
Low energyAdvantages
consumption Disadvantages Challenge
process High recovery Long process Optimize the process
Less waste gas rate
High-purity product
Hydrometallurgical HighLowselectivity
energy consumption More wastewater Wastewater treatment
process Less waste gas LiLong
and process
Mn are not recovered Optimize the process
Reduce energy consumption
Simple operation and short flow
High selectivity High energy consumption and pollution emissions
Pyrometallurgical No requirement for categories or Li and Mn are not recovered
Simple operation and short flow Low recovery efficiency Reduceenergy
Reduce environ. hazards and
consumption
process size of inputs High energy consumption
Pyrometallurgical No requirement for categories or More waste gas and the cost of pollution
Low recovery efficiency
Combineemissions
hydrometallurgy
High efficiency
process size of inputs waste gas treatment
More waste gas and the cost well
Reduce environ. hazards
High efficiency of waste gas treatment Combine hydrometallurgy
Reduce recovery costs well
Short recovery route
High operation and Lower the
Reduce requirements
recovery costs for
Direct LowShort recovery
energy route
consumption High operation
equipment and
requirements Lower the requirements
categories
Direct
recycling Low energy consumption
process Environmentally friendly for categories
equipment requirements
recycling process Environmentally friendly Incomplete recovery Furtheroptimize
Further optimize product per-
High recovery rate
High recovery rate
Incomplete recovery
formance
product performance

This work examines the current direct recycling procedures for spent LIB materials,
This work examines the current direct recycling procedures for spent LIB materials,
including common cathode (NMC, LFP, LCO, and LMO) and graphite anode treatment.
including common cathode (NMC, LFP, LCO, and LMO) and graphite anode treatment.
The
The review
review introduces
introduces the
the technical
technical challenges,
challenges, limitations,
limitations, and
and barriers
barriers ofof five
five different
different
direct recycling methods (solid-state sintering, electrochemical, ionothermal,
direct recycling methods (solid-state sintering, electrochemical, ionothermal, solution, solution,
and
and eutectic
eutectic relithiation),
relithiation), as illustrated
as illustrated in in Figure
Figure 2. 2.Although
Althoughthese
these methods
methods provide
provide highhigh
efficiency
efficiency inin restoring
restoring the
the properties
properties of of regenerated
regenerated materials
materials to
to aa level
level comparable
comparable to to
pristine, the critical challenge in direct recycling revolves around the processing
pristine, the critical challenge in direct recycling revolves around the processing of black of black
mass
mass and
and the
thenecessity
necessityofofrecycling
recyclingpre-treatment
pre-treatment within
withinthetheEOL
EOLprocess
processscenario.
scenario.Thus,
Thus,
this work discusses potential optimization options that could lead to
this work discusses potential optimization options that could lead to the industrially the industrially
scaled
scaled implementation
implementation of recycling.
of direct direct recycling.

Figure 2.
Figure Overviewof
2. Overview ofthe
thecurrent
current direct
direct recycling
recycling approach,
approach, covering
covering the
the relithiation techniques.

2. Direct Recycling Technology

In the realm of recycling spent LIBs, the technological processes are divided into two
separate routes: recycling pre-treatment and the subsequent material recovery, i.e., the
recycling procedure [2]. The battery pre-treatment precedes further recycling treatment
and can improve the efficiency of valuable material recovery, process safety, or lower
Batteries 2024, 10, 81 5 of 20

energy consumption. These processes primarily separate the active electrode materials
from the current buses, separators, electrolytes, and covers or connections. Presently,
the pre-treatment process lacks a well-defined design, leading to the adoption of various
approaches in recent years. Typically, the process can be outlined through the following
seven-step procedure; the short-cuts of the individual steps’ details are given in Table 2,
and the review work by Kim et al. [19] provides a comprehensive description.
• Discharging;
• Dismantling;
• Comminution;
• Classification;
• Separation;
• Dissolution;
• Thermal treatment.

The main aim of the recycling pre-treatment phase is to eliminate impurities and
achieve the highest possible quality in the output product, the so-called “black mass”. This
finely ground fraction predominantly comprises cathode materials (cathode black mass,
also known as CBM) and serves as the input material for the subsequent stages of recycling
processing [2,22].

Table 2. Summary of recycling pre-treatment process steps [2,19].

Recycling
Step Characterization
Pre-Treatment Step
Discharge systems with electric (active or passive) loads,
Discharging
deep discharging < 1 V.
Manual disassembly from battery (pack)
Dismantling
to the module or cell level.
Crushing active electrode materials into fine fractions,
Comminution
implemented by dry or wet procedures.
Categorization according to the fraction product size,
Classification
typically applies by sieving.
Specialized separation methods, including magnetic,
Separation
eddy current, or electrostatic techniques.
Dissolution Chemical separation of active cathode materials from Al foils.
Complete removal of the organic parts, such as binders,
Thermal treatment additives, plastics, or carbon black.
Final product: black mass.

Following pre-treatment, the black mass, primarily comprising the gathered spent
cathode materials, undergoes regeneration through either pyrometallurgical, hydrometal-
lurgical, or direct recycling methods. A complex overview of the implemented pyrometal-
lurgy or hydrometallurgy techniques, including a detailed examination of their advantages
and disadvantages, along with considerations of economic and environmental perspectives,
can be found in works by Pražanová et al. [20], or Lander et al. [24].
Regarding direct recovery pathways, the CBM is set for regeneration, encompassing
the restoration of the crystal structure while concurrently mitigating the loss of Li electroac-
tivity at its original location—a process commonly referred to as “in situ” electroactivity
offsetting. This healing methodology is introduced in response to the common issues of
inactive Li supply and the degradation of battery performance resulting from irreversible
structural transitions, such as the formation of the solid electrolyte interphase (SEI) layer
on the anode surface; changes in volume and crystal phase; structural stress; mechanical
strains; and micro-cracks between/in the particles. A detailed description of the struc-
inactive Li supply and the degradation of battery performance resulting from irreversible
inactive Litransitions,
structural supply andsuch the degradation
as the formation of battery
of theperformance
solid electrolyteresulting from irreversible
interphase (SEI) layer
structural transitions, such as the formation of the solid electrolyte
on the anode surface; changes in volume and crystal phase; structural stress; mechanical interphase (SEI) layer
Batteries 2024, 10, 81 on the anode surface; changes in volume and crystal phase; structural
strains; and micro-cracks between/in the particles. A detailed description of the structural stress; mechanical
6 of 20
strains; and
changes withinmicro-cracks between/in
the LIB cells, which lead the to
particles. A detailed
a performance description
decrease and Li oflosses,
the structural
is pre-
changes
sented in within
work by the LIB [22]
Wu’s cells,andwhich
Xu’slead to a performance
[7] research groups. decrease and Li losses, is pre-
sented
tural in work
changes
Thus, directbyrecycling
within Wu’s
the [22] and Xu’s
LIBemerges
cells, as[7]alead
which research groups.
to a performance
promising technique decrease and Li losses,
within currently imple- is
Thus,
presented
mented direct recycling
in work methodologies.
recycling emerges
by Wu’s [22] andIt Xu’s as a promising
[7] research
possesses technique
groups.
considerable within
potential forcurrently
reinstating imple-
the
mented
Thus, recycling
electrochemical methodologies.
directperformance
recycling emerges It apossesses
as
of cathode promising
materials considerable
technique potential
and their within fortoreinstating
currently
rejuvenation implemented
reach qualitythe
electrochemical
recycling
levels performance
methodologies.
similar of cathode
It possesses
to those of fresh materials
considerable
materials. and their rejuvenation
potentialinvolves
This regeneration for reinstating to reach quality
the electrochem-
restoring entire struc-
tures, not the recovery of individual valuable metals, as illustrated in Figure 3.entire
levels
ical similar
performance to those
of of
cathodefresh materials.
materials and This
theirregeneration
rejuvenation involves
to reach restoring
quality levels struc-
similar
A notable
tures,
to those
advantagenot
of the
of recovery
fresh
this method of individual
materials. isThis valuable
thatregeneration
it reduces metals, as
involves
environmental illustrated
restoring
impacts in Figure
entire
and 3. economic
structures,
lowers A not
notable
the
advantage
recovery
costs of this method is that it reduces environmental impacts and
[22].of individual valuable metals, as illustrated in Figure 3. A notable advantage of lowers economic
costs
this [22]. is that it reduces environmental impacts and lowers economic costs [22].
method

Figure 3. Example of the main direct recycling steps; comparison with pyro-/hydrometallurgy [22].
Figure3.3.Example
Figure Exampleof
ofthe
themain
maindirect
directrecycling
recyclingsteps;
steps;comparison
comparisonwith
withpyro-/hydrometallurgy
pyro-/hydrometallurgy[22].
[22].
The example of the cost, energy consumption, and environmental impacts compari-
son of The
The example1of
example
producing of the
kgthe cost, energy
cost,
of NMC111 energy consumption,
cathode and environmental
environmental
(nickel manganese impacts
impacts
cobalt oxide compari-
compar-
in a 1:1:1 mass
son
ison of
of producing
producing 1 kg
1 kgof NMC111
of NMC111 cathode
cathode (nickel manganese
(nickel manganese cobalt oxide
cobalt in
oxide
ratio for Ni:Mn:Co) and recycling them with different technologies (namely, pyro-/hydro- a 1:1:1
in a mass
1:1:1
ratio for
mass
metallurgy Ni:Mn:Co)
ratio for and
andNi:Mn:Co)
direct recyclingis them
and recycling
recovery) shown with
them different technologies
with 4different
in Figure [22]. (namely,
technologies pyro-/hydro-
(namely, pyro-
metallurgy and direct
/hydrometallurgy and recovery) is shown
direct recovery) in Figure
is shown 4 [22]. 4 [22].
in Figure

Figure 4. The comparison of the cost, energy consumption, and environmental impacts of producing
Figure 4. The comparison
1 kg of NMC111 of the
cathode and cost, energy
recycling it withconsumption, and environmental
different technologies impacts of producing
(namely, pyro-/hydrometallurgy
1Figure 4. The comparison
kg of NMC111 of the
cathode and cost, energy
recycling consumption,
it with and environmental
different technologies (namely,impacts of producing
pyro-/hydrometal-
and
1 kgdirect
of recovery).
NMC111 Reprinted
cathode and from [22],itwith
recycling withpermission
different from Elsevier,
technologies Copyright
(namely, (2023).
pyro-/hydrometal-
lurgy and direct recovery). Reprinted from [22], with permission from Elsevier, Copyright (2023).
lurgy and direct recovery). Reprinted from [22], with permission from Elsevier, Copyright (2023).
However, for quality and highly representative results, evaluating each established
process individually with all its technological aspects or additional steps is necessary.
While the work by Wu et al. [22] lacks specific compared-process details, the research-based
trends can be observed through selected categories [20,25–28]. Generally, hydrometallurgy
exhibits the highest energy consumption due to its intricate and energetically demanding
steps, particularly in the purification of waste products, notably water. Consequently,
Batteries 2024, 10, 81 7 of 20

water consumption is the most significant via hydrometallurgical processes. Conversely,

pyrometallurgy, characterized by high-temperature processing, contributes significantly to
greenhouse gas (GHG) emissions, although sulfur oxide (SOx ) emissions predominantly
stem from chemical (hydrometallurgical) processing. Economic evaluations commonly
depend on the accuracy of process characterizations. However, given the high technol-
ogy costs associated with high-temperature processing, pyrometallurgical processes are
presumed to incur substantial expenses in terms of investment and operation. Moreover,
this comparison underscores the primary objectives of direct recycling, which entail low
operating costs and minimal environmental impact.
The direct recycling process can be generally called “relithiation” [29]. These ap-
proaches mainly include solid-state sintering, electrochemical relithiation in organic and
aqueous electrolytes, ionothermal relithiation, solution relithiation, and eutectic relithiation,
whose advantages and challenges are summarized in Table 3 [7].

Table 3. The advantages and challenges of different direct recycling technologies. Reprinted from [7],
with permission from Wiley-VCH GmbH, Copyright (2023).

Direct Recycling Method Advantages Challenges

Pre-determination
Solid-state One-step regeneration; of Li deficiencies;
relithiation Simple operation Phase impurity
Pre-determination
of Li deficiencies;
Low energy consumption; Removal of current collector,
Electrochemical relithiation binders, . . .
Low cost
Phase impurity;
Scalability issue
Ionic liquids High cost of ionic liquid;
Self-saturation relithiation
relithiation Scalability issue
Removal of solidified salts;
Eutectic salt Self-saturation relithiation; mixture after regeneration;
relithiation Low energy consumption Scalability issue
Self-saturation relithiation; Safety concern related
Solution based
Wide applicability; to elevated temperature
relithiation
Low cost and pressure

Within solid-state sintering regeneration, spent cathode materials are firstly mixed
with Li salts, and subsequently, they are treated through different temperature levels in
ranges of 600–900 ◦ C. The stoichiometric ratio of Li is reinstalled by adding a supplementary
Li source, and the particle bonding is indurated with high-temperature treatment [30,31].
Electrochemical relithiation is typically mediated in a three-electrode station; a spent
cathode electrode stands as the working electrode, a platinum plate as the anode electrode,
and one Ag/AgCl as the reference electrode with a Li-based solution. Optimal regeneration
efficacy can be attained by tuning the concentration of the Li solution and changing the
cathodic current. Nevertheless, this method cannot completely restore the cathode crystal
structure, and additional temperature treatment is needed [7,32].
Ionothermal relithiation is a form of synthesis where ionic liquid solutions are simul-
taneously used as both the solvent and potential template or structure-directing agent in
forming solids. This approach from the solution-based relithiation field evolves defect-
targeted healing and homogeneous Li distribution inside cathode particles [33].
Eutectic molten salts establish a homogeneous environment during re-crystallization
and particle growth stages of direct recovery at a eutectic temperature at ambient pressure.
Initially, spent cathode materials are blended with Li-based eutectic molten salts; then, the
resulting mixture is heated to the eutectic melting point, where re-lithiation and crystal
rearrangement occur. Contrary to the previous methods, this approach reduces both the
Batteries 2024, 10, 81 8 of 20

holding time and annealing temperature without compromising the restored material’s
crystallinity [7,34].
The selection of the optimal relithiation process depends on several crucial factors.
These include not only the chemical composition of the active material but also the intensity
and nature of defects present in the cathode structures, desired recovery efficiency, along
with evaluations of investment and operating costs.

3. Limitation of Implemented Direct Recycling Procedures

Recycling of LIBs stands as a high-perspective strategy of their waste management,
which addresses environmental concerns, marking a crucial step toward the sustainable
development of energy storage technologies and the circular economy. In comparison to
conventional hydrometallurgical and pyrometallurgical recycling methods, direct recycling
serves several benefits in terms of process simplicity, low energy consumption, reduced
secondary environmental pollution, and potential higher cost return [1,20,24].
While direct recycling has shown initial success within laboratory-scale settings, re-
covering a diverse array of cathode and anode materials, its transition to the industrial
sector remains impeded. The practical application of this technology encounters significant
challenges, signaling the need for further advancements in the research area [20].
The dominant limitation of currently implemented technologies resides in the pro-
cessing of high-quality CBM or anode materials (black mass form) derived from the LIBs
recycling pre-treatment, as shown in Table 4. The demand for ensuring high quality and
uniformity in the resulting product increases the complexity of the entire technology and
costs, thereby substantially diminishing the number of industrial implementations [1].

Table 4. Overview of the main limitations of currently implemented direct recycling techniques [1].

Limitation Description
The current approaches predominantly target the
cathode and anode materials,
Limited applicability to whole neglecting other components of spent LIBs; thus, the potential
spent LIB systems for achieving a closed-loop circular economy for LIBs
is not fully harnessed.
The standard black mass, comprising a mixture of several
Black mass processing materials, introduces technical barriers to the direct
implementation of direct recycling techniques.
Before direct recycling, LIBs undergo recycling pre-treatment
processes involving high-temperature treatments and
Energy-intensive
chemical interventions, which result in high energy
recycling pre-treatment
consumption, emissions, and intricacies in the process of
wastewater treatment.

Considering the commonly implemented LIBs recycling pre-treatment processes,

whose output products consist of a mixed material output based on cathode and anode
materials, conductive agents, PVDF binder, and other residual impurities from a current
collector, or battery casings (Al, Cu, Fe, etc.) from a single type or different battery chemistry
mixture [6], they pose significant technical obstacles, especially from the perspective of
material separation or process efficiency, hindering the immediate progression of the direct
recycling method [22]. A comparison of currently treated materials within direct recycling
and the future strategy of this method is presented in Figure 5 from a comprehensive review
work by Xu et al. [7].
The direct recycling methods are generally individually customized for various ma-
terial treatments. They are accompanied by a range of limitations influenced by process
complexity, readiness, and research status [7,22]. Thus, the direct recovery strategies, limi-
tations, advantages, and disadvantages for crystal structure rearrangements for different
types of cathode and anode graphite materials are discussed in the following sections.
Batteries 2024, 10, x FOR PEER REVIEW 9 of 22

Batteries 2024, 10, 81 9 of 20

recycling and the future strategy of this method is presented in Figure 5 from a compre-
hensive review work by Xu et al. [7].

Figure5.5.Current
Figure Currentchallenges
challenges (a)
(a) and
and future
future solutions
solutions(b)
(b)toward
towardspent
spentbattery pre-treatment,
battery as well
pre-treatment, as well
as future development directions of electrode material regeneration (c) and upcycling (d) technolo-
as future development directions of electrode material regeneration (c) and upcycling (d) technologies.
gies. Reprinted from [7], with permission from Wiley-VCH GmbH, Copyright (2023).
Reprinted from [7], with permission from Wiley-VCH GmbH, Copyright (2023).
The direct
3.1. Direct recycling
Recycling methods
Treatment are Cathode
of Spent generally individually customized for various ma-
Materials
terial treatments. They are accompanied by a range of limitations influenced by process
As a critical component of the battery, cathode materials play a crucial role in determin-
complexity, readiness, and research status [7,22]. Thus, the direct recovery strategies, lim-
ing the overall performance, energy density, and efficiency of LIBs, where their differences
Batteries 2024, 10, x FOR PEER REVIEW itations, advantages, and disadvantages for crystal structure rearrangements for10 different
of 22
within specific energy (capacity), specific power, safety, performance, lifespan, and cost are
types of cathode and anode graphite materials are discussed in the following sections.
illustrated in Figure 6 [35].
3.1. Direct Recycling Treatment of Spent Cathode Materials
As a critical component of the battery, cathode materials play a crucial role in deter-
mining the overall performance, energy density, and efficiency of LIBs, where their differ-
ences within specific energy (capacity), specific power, safety, performance, lifespan, and
cost are illustrated in Figure 6 [35].
The demand for efficient energy storage systems has propelled research into enhanc-
ing the performance of LIBs and their suitable usage within selected application fields
[36,37]. Considering the current implementation stage and ratios between spent LIBs de-
signed for EOL treatment, the spent NMC, LFP, LCO, and LMO cathode material treat-
ments were described. More details about spent NCA materials’ direct regeneration are
provided, for example, in the study by Elmaataouy et al. [38].

Comparison
Figure6.6.Comparison
Figure between
between different
different types
types of cathodes.
of cathodes. Reprinted
Reprinted fromfrom [35] under
[35] under the terms
the terms and and
conditions of the CC BY 4.0 license, Copyright (2021).
conditions of the CC BY 4.0 license, Copyright (2021).

The demand for efficient energy

3.1.1. Nickel-Manganese-Cobalt storage systems has propelled research into enhancing
Oxide (NMC)
the performance of LIBs and their suitable usage within
In the realm of electric vehicle (EV) applications, selected
there application
is a distinct fieldsfor
preference [36,37].
battery technologies that offer higher energy density at reduced costs. Consequently, al-
ternative ternary transition metal oxides incorporating Ni and Mn within LIBs, such as
LiNi0.33Co0.33Mn0.33O2 (NCM111), LiNi0.5Co0.2Mn0.3O2 (NCM523), LiNi0.6Co0.2Mn0.2O2
(NCM622), and LiNi0.8Co0.1Mn0.1O2 (NCM811), have garnered widespread adoption and
usage via different battery formats [6,39].
Batteries 2024, 10, 81 10 of 20

Considering the current implementation stage and ratios between spent LIBs designed for
EOL treatment, the spent NMC, LFP, LCO, and LMO cathode material treatments were
described. More details about spent NCA materials’ direct regeneration are provided, for
example, in the study by Elmaataouy et al. [38].

3.1.1. Nickel-Manganese-Cobalt Oxide (NMC)

In the realm of electric vehicle (EV) applications, there is a distinct preference for
battery technologies that offer higher energy density at reduced costs. Consequently,
alternative ternary transition metal oxides incorporating Ni and Mn within LIBs, such as
LiNi0.33 Co0.33 Mn0.33 O2 (NCM111), LiNi0.5 Co0.2 Mn0.3 O2 (NCM523), LiNi0.6 Co0.2 Mn0.2 O2
(NCM622), and LiNi0.8 Co0.1 Mn0.1 O2 (NCM811), have garnered widespread adoption and
usage via different battery formats [6,39].
Spent battery cells of the NMC type commonly undergo severe phase transformations
that result in the loss of Li-ions. The degraded cathode materials exhibit transformations
involving spinel and rock salt phases on the surface of the particles. Thus, considering the
relithiation techniques, short annealing is required within the treating processes to transfer
spinel and rock phases back to a layered structure [7].
In the context of solid-state regeneration of NMC structures, layered cathode materials
can be efficiently treated through standard sintering methods. Meng et al. [30] discovered
that, before annealing NMC111 materials, milling plays a crucial role in enhancing the
efficiency of electrochemical performance recovery by promoting uniform Li diffusion.
The sintering properties vary based on the materials’ constituents and crystallinity. As
demonstrated by Shi et al. [40], polycrystalline NMC523 requires a sintering temperature
within the range of 850 ◦ C to 920 ◦ C, while Gao et al. [41] recommend maintaining a
temperature around 950 ◦ C for single-crystal NCM523. For materials with a high Ni content,
such as NMC622, Jin et al. [42] emphasize the necessity of a pre-oxidation treatment step
before sintering. Additionally, higher Ni ratios demand increased oxygen pressure levels
for effective treatment.
Within solution/hydrothermal-based relithiation, Shi’s group [40] conducted com-
prehensive research on NMC523 recovery, achieving a recovered cathode material quality
comparable to pristine conditions. The process involved a high-temperature short anneal-
ing (HT-SA) technique designed to suppress Li/Ni mixing and executed under specific
oxygen atmosphere levels, as described in detail in the work by Gao et al. [41]. The re-
installed materials are subjected to minimal temperature and pressure loads, capped at
220 ◦ C and 25 bar. Ongoing optimization efforts, such as those by Yu et al. [43], involve
the introduction of redox mediation in the hydrothermal Li-bearing solution, resulting in
a temperature decrease to 100 ◦ C. In the context of NMC622 material regeneration, Sloop
et al. [44] favored treatment with LiOH solutions. However, the efficiency encountered a
setback due to the formation of a Li+ and Ni2+ mixture.
The eutectic-mixture-based regeneration method for NMC materials has shown promis-
ing results. Shi et al. [34] utilized a eutectic solution consisting of lithium hydroxide (LiOH)
and lithium nitrate (LiNO3 ) to relithiate spent NCM523, successfully reverting the surface
salt phase to its original layered structure, comparable to its pristine state. Fan et al. [45]
also demonstrated effective regeneration of spent NCM523 using the LiOH and lithium
carbonate (Li2 CO3 ) system, which forms a molten salt. However, it has been observed that
for highly degraded materials, this relithiation may not be optimal and might not fully
recover destructed materials. New approaches are being explored, such as the solution
proposed by Ma et al. [46], which involves adding cobalt(III) oxide (Co2 O3 ) and man-
ganese dioxide (MnO2 ) to the eutectic solution to compensate for transition metal loss in
cathode materials.
The research on ionic liquids for recovery faces significant limitations, primarily due to
high implementation costs. However, as demonstrated by the results of Parnham et al. [47],
the method can be effective and lead to full recovery, as shown in the case of NMC111,
Batteries 2024, 10, 81 11 of 20

where an ionic liquid was served as the flux solvent, accompanied by LiBr as the Li source
and ionothermal treatment.
The direct recycling technique for spent NMC materials can be considered an effective
method for pristine-like cathode material recovery, with the possibility of using standard
sintering methods and a lower environmental impact. However, it serves some notable
limitations according to the applied relithiation technique, summarized in Table 5.

Table 5. Limitations and challenges of implemented direct recycling techniques focus on recycling
spent cathode (NMC, LFP, LCO, and LMO) and anode graphite materials. “Pre-development phase”
refers to an area that has not yet been thoroughly characterized by research. “Development phase”
denotes a pilot research area with insufficient readiness for practical industrial application.

Spent Solid-State Electrochemical Ionic Liquids Eutectic Salt Solution Based

Material Relithiation Relithiation Relithiation Relithiation Relithiation
Necessity of milling before sintering; Formation of a Li+ and
Destructed materials
Long sintering time at Ni2+ mixture;
Pre-development High may not be
NMC high temperature; HT-SA technique;
phase implementation costs fully recovered;
Pre-oxidation treatment procedures; Needs for oxygen
Development phase
Process complexity atmosphere levels
High temperature treatment; Development phase;
Requisite of carbon and PVDF Integration of
Pre-development Development
LFP binders’ removal from LFP particles; pre-lithiated graphite; Process complexity
phase phase
Structural stability; Poor industrial
Sensitivity to sintering atmosphere scalability
Process complexity;
Undescribed:
Requirement for
Necessity of optimal Li/Co ratio; Pre-development Development thermodynamics and
LCO high-quality
High energy process consumption phase phase kinetics of
delamination and
implemented processes
purification steps
High environmental demand; Necessity of optimal
Best results: balanced molar ratio of Pre-development Pre-development Pre-development LiOH solution
LMO
LiOH and LMO, phase phase phase concentration;
dependent on SOH Not dependent on SOH
Necessity of
impurities removal;
High temperature treatment;
Pre-development Pre-development Pre-development Sensitivity to process
Graphite Combined process (annealing,
phase phase phase atmosphere;
chemical leaching)
High demand for
wastewater treatment

3.1.2. Lithium Iron Phosphate (LFP)

Due to its good thermal stability, cost-effectiveness, and long cycle life, LFP technology
plays a pivotal role in the LIB market, particularly in applications like portable electronics,
grid energy storage systems, and EVs [48]. The absence of valuable metals, such as Co and
Ni, in LFP cells reduces the economic motivation of their EOL treatment via conventional
recycling methods [1]. Thus, implementing direct recycling methods with reduced energy-
consumptive processes has the potential for wide-range extension in waste management [7].
The primary cause of capacity decay in LFP cells is the loss of Li inventory within
the crystal structure while maintaining material stoichiometry. The regeneration process
involves supplementing Li ions into the crystal structure. Familiar Li sources include
inorganic Li, such as Li2 CO3 or LiOH, lithium halides like lithium iodide (LiI) or lithium
bromide (LiBr), and organic lithium salts, such as polycyclic aryl-lithium compounds [7].
The solid-state regeneration of LFP involves reloading the lost Li+ ions in the cathode
during cycling by annealing a mixture of Li-containing salt and spent cathodes at high
temperatures between 350 and 700 ◦ C [49]. However, the complete removal of conductive
carbon and PVDF binder from LFP particles while preserving structural stability poses
a challenge, affecting the quality of defect restoration and material purity. Research con-
ducted by Li et al. [50] and Sun et al. [51] has demonstrated that the regenerated product is
highly sensitive to the sintering atmosphere, where the inert or reductive atmosphere is
preferred to prevent LFP oxidation, which can impact the final product quality.
Current research on electrochemical regeneration indicates that the electrochemical
properties of the regenerated LFP are comparable to those of commercial materials. For
Batteries 2024, 10, 81 12 of 20

instance, the study by Peng et al. [52] demonstrated that the recovered structure exhibited
a discharge capacity of 135.2 mAh g−1 at 1 C, with a capacity retention of 95.3% after
500 cycles. However, the processes involve integration with a pre-lithiated graphite anode
or separator, which may impose limitations on the industrial scalability of the process.
The solution-based recovery method for LFP materials holds promise for restoring
both Li losses and the formation of Fe-Li defects, particularly in cases of severe degradation
and substantial capacity decay [53]. The revival of these defects is crucial for achieving
complete material recovery and optimal performance. However, the complexity of this
method is a limitation, as demonstrated in the work by Panpan et al. [54], where a procedure
involving strong electrostatic repulsion with various reduction agents was employed in a
LiOH solution.
The main benefit of eutectic solution regeneration is that it covers relatively low-
temperature treatment primarily via a reductive atmosphere, which increases the possibility
of an LFP structure oxidation decrease [7]. Nevertheless, the crucial results of this method
are under investigation in ongoing research.
The LFP direct regeneration covers several benefits, such as the recovery of high-
quality materials with comparable electrochemical properties to commercial materials;
nevertheless, the procedure covers some of its limitations, which are shown in Table 5.

3.1.3. Lithium Cobalt Oxide (LCO)

Batteries based on LCO structures find extensive applications, especially within the
portable electronic field, due to their high energy density and compact size [6]. A notable
reduction in Li content within the bulk crystal structures occurs throughout the degradation
process, accompanied by significant damage to the surface of spinel phases. Consequently,
recovery efforts focus on replenishing Li deficiencies and restoring degraded spinel phases
to their original layered form. The relithiation process typically initiates in a solid or
aqueous medium and progresses through annealing treatments [7].
Solid-state regeneration of LCO involves directly mixing degraded cathode materials
with solid lithium sources, such as Li2 CO3 or LiOH, followed by thermal treatment within
the range of 800–950 ◦ C. According to findings by Gao et al. [55] and Chen et al. [56],
successful repair of material composition and structural defects occurs when the Li/Co
ratio falls within the range of 1.0–1.2. A lower ratio results in incomplete structural repair,
while a higher ratio introduces Li2 O impurities, negatively impacting the final performance.
The electrochemical relithiation approach for LCO materials encompasses several
highly efficient procedures, with the primary drawbacks residing in process complexity
and higher cost. Yang et al. [57] outlined a regeneration technique for cycled LCO in
their work. The spent cathode material (working electrode) was paired with a new LCO
electrode, the electron donor, and the Ag/AgCl reference electrode. During discharge, ions
from the Li2 SO4 electrolyte infiltrate damaged structures, reinstating Li deficiencies. A
notable advantage was the absence of observed Al corrosion on the working electrode. After
a brief annealing process, the cathode structure fully recovered, exhibiting capacity and
cycle performance on par with the pristine commercial batch. However, a key limitation
of this method is the necessity for high-quality delamination and purification steps in
regenerating materials.
The solution-based regeneration of spent LCO requires further exploration, partic-
ularly regarding microstructure revitalization and the Li+ replenishment process in an
aqueous solution. Current results, as presented in the work by Kim et al. [58], describe
a regeneration conducted at 200 ◦ C for 20 h in a LiOH solution. The resulting structure
of LCO demonstrated a capacity of 144 mAh g−1 with 92.2% retention after 40 cycles.
Additionally, Shi et al. [59] conducted experiments involving highly effective hydrothermal
relithiation, followed by post-sintering; however, the thermodynamics and kinetics of these
steps remain uncharacterized.
The eutectic solvent regeneration offers several advantages, including non-toxicity,
low cost, and recyclability. However, these procedures are primarily in the development
Batteries 2024, 10, 81 13 of 20

phase. As an illustration, Wang et al. [60] present a well-designed procedure using the
lithium chloride (LiCl) and urea (CH4 N2 O) eutectic system, which features a reduced
eutectic point to below 120 ◦ C, for the direct regeneration of degraded LCO.
Compared to other recovery techniques, direct recycling of spent LCO materials serves
several advantages, such as low environmental impact and the absence of Al corrosion.
However, they are connected to the limitations summarized in Table 5.

3.1.4. Lithium Manganese Oxide (LMO)

The prominence of LIBs with Mn-rich cathodes is increasing in EVs and large-scale
energy storage due to their stable performance and cost-effectiveness [7]. This trend is
particularly notable in scenarios where high energy density is not the primary consideration.
Likewise, for LFP recycling, the economic viability of traditional pyrometallurgical and
hydrometallurgical recycling methods for recovering Mn compounds from spent LMO
cathode materials is constrained by their relatively low market value [24]. Consequently,
the economic motivation for the recycling of LMO is circumscribed. In this context, direct
recycling emerges as a pertinent and economically viable strategy for effectively managing
spent LMO cathode materials [5].
The deterioration of LMO materials is due to Mn2+ dissolution [61], resulting from the
disproportionation of Mn3+ [62]. In the initial charge, Mn3+ undergoes a reaction, forming
spinel-type Li4 Mn5 O12 and soluble trimanganese tetraoxide (Mn3 O4 ). During discharge,
Li2 Mn2 O4 spinels are generated with Jahn–Teller distortion. As a benefit, cycled LMO
retains the spent spinel LMO phase without impurities [7].
Regarding the recovery of spent LMO materials, solid-state and electrochemical (aque-
ous) relithiation regeneration are the preferred methods. Typically, LiOH solutions in
various concentrations are utilized to treat structural defects. However, as demonstrated in
review work by Panpan et al. [7], highly concentrated solutions exceeding 0.4 M induce the
formation of Li-rich phase lithium manganite (Li2 MnO3 ) impurities during the recovery
process. Wang et al. [63] have shown that hydrothermal methods yield superior recovery
results compared to solid-state sintering in terms of phase purity and electrochemical
capacity of the treated LMO. Solid-state techniques restore the lost capacity by maintaining
a well-balanced molar ratio of LiOH and aged LMO, dependent on the degraded materials’
state of health (SOH). In contrast, hydrothermally recycled products recover lost capacity
irrespective of the SOH of the spent LMO. The primary difference among these approaches
is reflected in their energy and environmental implications, with hydrothermal processes
demonstrating markedly reduced energy consumption compared to solid-state sintering,
as provided in the LCA study by Xio et al. [64].
Although the direct recycling of spent LCO cathodes offers low energy consumption,
it also has some limitations, as detailed in Table 5.

3.2. Direct Recycling Treatment of Spent Anode Materials

Graphite stands out as a frequently used anode material in LIBs [65], attributed to its
excellent electrical conductivity, high thermal and mechanical stability, prolonged cycle
life, good capacity, and low working voltage. Nevertheless, the recycling of spent graphite
anodes received comparatively less focus due to the absence of transition metals. Thus,
spent anodes are either incinerated or disposed of in landfills. Considering the potential
demand for graphite minerals, which is projected to be approximately 13 times higher
than the demand for Li minerals, especially in the context of the 2025 EV market, there is a
critical need to streamline and enhance the recycling processes for these materials [66].
Several research groups have devoted their work to graphite direct regeneration [67,68].
Yang et al. [69] introduced a comprehensive direct recycling perspective for all anode ma-
terial recovery, including graphite, Cu foil, aluminium hydroxide (Al(OH)3 ), and Li2 CO3 .
This approach combines heating and leaching treatment steps and leads to the recovery
of 99.9% pure graphite with significantly improved specific capacity and excellent cycling
performance. The anode materials may contain impurities such as transition metals, which,
Batteries 2024, 10, 81 14 of 20

as demonstrated by Ma et al. [70], can be effectively treated and removed through sulfuric
acid (H2 SO4 ) and hydrogen peroxide (H2 O2 ) leaching. However, this approach increases
the complexity of wastewater treatment, posing a limitation to full-scale industrial applica-
tions. In response, Wu’s [71] and Wang’s [72] research groups focused on cleaner methods,
leveraging the highly reactive properties of LiCx in spent anode materials with water,
enabling the removal of residual Li from graphite particles. The oxidation degradation of
LiCx is mitigated by an inert atmosphere, albeit resulting in higher costs.
Acid or water treatments prove effective in eliminating impurities from spent graphite
anodes. However, subsequent high-temperature annealing steps become imperative to
attain the complete recovery of graphite anodes. A review by Panpan et al. [7] reveals
atom rearrangement and structural recovery after a 6 h treatment at 3000 ◦ C in an N2
environment. Nevertheless, the primary limitation lies in their high energy consumption.
The EOL processing of spent anode graphite-based materials is currently in the devel-
opmental stage and requires further optimization, as current approaches indicate. However,
the limitations of the implemented direct recycling methods for treating spent graphite
anode materials are outlined in Table 5.

4. Discussion
Recycling spent LIBs represents an effective waste-management strategy that miti-
gates the environmental impacts by preserving raw resources, especially valuable metals,
reducing the emission footprint of mining and post-processing, and fostering the prin-
ciples of a circular economy. Given the prevalent global practices in recycling, such as
pyrometallurgy or hydrometallurgy, which often entail high energy consumption, emis-
sions, or the extensive use of chemicals, a pressing need arises for alternative recycling
technologies. These alternatives should enable the direct reutilization of deteriorated energy
storage materials in battery manufacturing, aligning with economic and environmental
sustainability objectives.
The currently employed direct recycling methods focus on treating high-quality cath-
ode or anode materials obtained through the recycling pre-treatment of the same type
or different types of LIBs. Consequently, these direct regeneration approaches do not
encompass the treatment of entire spent LIB systems; instead, they specifically target the
most economically valuable products in the EOL treatment chain, commonly referred to as
the black mass. During the recycling pre-treatment phase, materials are subjected to high-
temperature treatments, incurring substantial operating costs and emissions. Moreover,
these materials may undergo treatment with various chemicals, introducing complexities
to wastewater treatment or necessitating specialized equipment to ensure compliance with
safety regulations and produce high-quality end products. The combined approach of
pre-recycling and the selective recycling of specific materials, as illustrated in Figure 7,
significantly influences the operation’s environmental and economic aspects, impacting the
overall motivation for the industrial implementation of direct recycling techniques.
Direct recycling methods are typically customized for specific material treatments.
Presently, “relithiation” techniques, encompassing solid-state sintering, electrochemical
relithiation in organic and aqueous electrolytes, ionothermal relithiation, solution relithia-
tion, and eutectic relithiation, are predominantly utilized for the regeneration of cathode
materials. This review provides an overview of the direct recycling of LIB cathode types,
including NMC, LFP, LCO, and LMO, and graphite anodes generally in laboratory scaled-
up treatments. Nevertheless, significant challenges persist in applying these techniques on
a larger industrial scale.
While individual methods exhibit high efficiency in restoring the properties of re-
generated materials, bringing them to a comparable level with pristine ones, the primary
challenge in direct recycling lies in processing black mass obtained from different LIB
types. The product typically consists of shredded cathode and anode materials, conductive
agents, PVDF binder, and various residual impurities (Al, Cu, Fe, etc.). Material diversity
sets several technical burdens for subsequent processing, such as product separation or
pass the treatment of entire spent LIB systems; instead, they specifically target the most
economically valuable products in the EOL treatment chain, commonly referred to as the
black mass. During the recycling pre-treatment phase, materials are subjected to high-
temperature treatments, incurring substantial operating costs and emissions. Moreover,
Batteries 2024, 10, 81 these materials may undergo treatment with various chemicals, introducing complexities 15 of 20
to wastewater treatment or necessitating specialized equipment to ensure compliance
with safety regulations and produce high-quality end products. The combined approach
of pre-recycling and
implementation the selective
complexity. recycling
These of specific
additional materials,
treatments as illustrated
represent in Figure
a vital process stage7,
significantly
in the currentinfluences the operation’s
research state. They aim toenvironmental
achieve highlyand economic
efficient directaspects, impacting
recycling results
the overall
while motivation
increasing for the
economic industrial
demands andimplementation of direct recycling techniques.
environmental burdens.

Figure
Figure 7. Current
Current direct
direct recycling
recycling process,
process, including
including recycling
recycling pre-treatment
pre-treatment and
and recycling
recycling steps,
steps,
covering application of different relithiation techniques.
covering application of different relithiation techniques.

Furthermore, it is essential to consider the potential application field of regenerated

materials. When considering currently common optimizations, covering alterations in
material ratios or substitutions of utilized compounds, it is crucial to assess the potential
of complex regeneration processes compared to the regeneration of chemical compounds
individually. The introduction of direct recycling processes should be up-to-date and fully
respect the demand of the battery market. If the current development trend continues to be
maintained, regenerating outdated battery structures would not be an advantage and, on
the contrary, could bring significant economic losses.
Before full-scale industrial implementation, careful consideration of the mentioned
factors is imperative. Presently, direct recycling remains in its beginning stages. Research
predominantly revolves around simplified models, focusing on single-type materials or
black mass sourced from specific battery types. Most processing occurs at a laboratory
scale, with pilot operations representing the extent of practical application thus far. Only
through more thorough evaluations can it be determined whether direct recycling will
emerge as a distinct, standalone recycling approach for managing waste LIBs or whether it
will function as an adjunct process alongside established techniques.
An overview of the limitations of selected direct recycling techniques identified within
this work, depending on the processed material, is shown in Table 5. Besides these summa-
rized limitations for common cathode and anode materials, state-of-the-art direct regen-
eration technologies need more exploration and optimization within the following areas,
which are discussed point-to-point subsequently.
• Direct recycling pre-treatment;
• Complex material composition;
• Black mass processing;
• Environmental and economic impact;
• Perspective of industrial scale.
Batteries 2024, 10, 81 16 of 20

4.1. Direct Recycling Pre-Treatment

Current direct recycling methods mainly focus on high-quality cathode or anode ma-
terials (black mass) derived from recycling pre-treatment steps, which ensure the removal
of unsolicited materials. Thus, integrating recycling pre-treatment into the EOL process is
essential; however, it leads to the non-recovery of selected material groups and significant
process losses. Furthermore, the procedures become increasingly technologically complex
when considering the simultaneous processing of various chemical types of batteries, a sce-
nario that is quite common across other recycling techniques. The pre-treatment commonly
consists of complex chemical treatment followed by energy- and emission-demanding steps,
which decrease the environmental and economic benefits of direct recycling procedures.
Therefore, future optimization should involve comprehensive treatments suitable for the
entire battery system, ensuring a closed-loop circular economy for LIBs, and maximizing
material recovery and process efficiency.

4.2. Complex Material Composition

Current methods commonly deal with the processing of single-type materials or the
processing of cathodes and anodes of one type of battery. However, conventional recycling
often involves processing various battery types, producing multi-material black mass.
If it is not technologically possible to process this type of product via direct recycling,
it would be necessary to extend the recycling pre-preparation by, e.g., a sorting step,
where the batteries would be classified according to their chemistry type. In this context,
leveraging the Battery Passport system would be feasible and logistically appropriate.
Otherwise, processing and sorting the black mass would be necessary by implementing
proper separation techniques. Moreover, it is imperative to consider the advantages of
recovering entire cathode structures, while also accounting for technological advancements
and preferences within changes in material ratios. This includes exploring optimal methods
for industrial-scale recycling, considering the aging of technology and new possibilities for
their utilization.

4.3. Black Mass Processing

Although high-quality black mass can be obtained as a typical product of recycling
pre-treatment, there is a high possibility that it will contain impurities in the form of
residual current collectors, organic materials, system casings, or anode/cathode materials
in the scenario of direct processing of spent cathodes/anodes. Thus, before the direct
recycling procedure itself, it is necessary to add a series of additional treatment steps,
such as high-temperature annealing, chemical leaching, or precipitation post-treating, to
remove impurities and achieve the desired high efficiency of the process. Nevertheless, this
sequence of procedures is characterized by high energy consumption, significant emissions,
and the generation of additional waste products, all of which contribute to elevated process
costs and a larger overall environmental footprint. Thus, future optimization efforts should
still be focused on developing effective methods to separate and treat black mass, ensuring
the recovery of valuable materials, minimizing impurities, and achieving as high a purity
level in regenerated materials as possible. Nevertheless, the processing and purification
of black mass present a drawback inherent in currently implemented procedures, mainly
for the pre-recycling lines, with the output product constituting black mass, whose quality
directly influences its market value. Mitigating energy consumption and minimizing the
environmental impact of these procedures would benefit all waste LIB recycling processes.

4.4. Environmental and Economic Impact

Direct recycling methods should be optimized to minimize energy consumption, eco-
nomic demands, and environmental impact. Current direct recycling processes involve
high-temperature treatments, such as annealing, smelting, or roasting, and chemical in-
terventions, leading to elevated energy consumption, emissions, and complications in
wastewater treatment, mainly as part of recycling pre-treatment or additional separation
Batteries 2024, 10, 81 17 of 20

procedures as part of black mass post-processing. Future optimization efforts should pri-
oritize environmentally sustainable practices and ensure an eco-friendlier approach. The
incorporation of environmentally friendly processes has the potential not only to contribute
to sustainability but also to impact operational costs positively over subsequent years. By
adopting eco-friendly practices, companies can anticipate reducing the required investment,
for example, through specialized equipment prices. This dual benefit—environmental sus-
tainability and cost effectiveness—creates a favorable environment for the advancement
and widespread adoption of these processes.

4.5. Perspective of Industrial Scale

At present, direct recycling is primarily encountered at the laboratory level. The
introduction of effective procedures on this smaller-scale level represents an initial step that
can ensure fewer demanding processes from environmental and economic perspectives
when fully implemented on the industrial level. To ensure effective EOL management,
especially of LIBs, it will be necessary to evaluate the possibilities offered by direct recycling
and to focus on pilot projects and recycling plants, where processing at the industrial
scale level is presented. Based on that, decisions can be made regarding whether direct
recycling will be replaced or implemented as a supplemental procedure to the currently
established methods.
Considering current results and the wide range of optimization possibilities, there
is a high potential for global and large-scale implementation of direct recycling as the
major or supplementary EOL treatment technique for spent LIBs. Moreover, it can be
perceived as a sustainable and eco-friendly alternative to conventional recycling processes
because it complies with crucial environmental, economic, and technological factors. By
minimizing the use of harsh chemicals and reducing energy consumption and emissions
of high-temperature treatments, these methods contribute to a smaller carbon footprint
and align with global efforts toward environmental sustainability. Regarding the increase
in environmental legislative restrictions, LIB’s waste management requests, and market
trends that prioritize sustainability, the demand for eco-friendly battery recycling methods
grows. Thus, direct recycling can be positioned as a key player in addressing these evolving
dynamics and fostering a more sustainable future. Nevertheless, the significant short-
comings of current direct recycling processes must be considered and addressed before
full-scale implementation.

5. Conclusions
This review outlines the limitations of current direct recycling methods for common
cathode materials (NMC, LFP, LCO, and LMO) and anode graphite in spent LIBs, mainly
from a laboratory-scale perspective. The work points out the main limitations of state-
of-the-art direct recycling technologies, including solid-state sintering, electrochemical
relithiation, ionothermal relithiation, solution relithiation, and the eutectic relithiation
method, which are typically used for highly effective regeneration of spent materials, in-
cluding the restoration of their electrochemical and structural properties. Additionally,
this work summarizes the main challenges of selected direct recycling methods, which are
essential for potential optimization steps leading to larger-scale (fully industrial) appli-
cations. The current techniques of direct recycling typically treat the output of recycling
pre-treatment, the black mass. The necessity of energy-demanding pre-treatment steps
impairs the perspective of subsequent, direct regeneration techniques and is the dominant
limitation of current industrial implementation. Thus, this review emphasizes the critical
constraints and the need for further optimization within direct recycling, representing a
promising EOL treatment for spent LIBs in future years.

Author Contributions: Conceptualization, A.P. and Z.P.; methodology, A.P.; formal analysis, J.K. and
V.K.; investigation, V.K.; resources, M.F.; data curation, M.F.; writing—original draft preparation,
A.P. and Z.P.; writing—review and editing, A.P., Z.P., J.K., M.F. and V.K.; visualization, A.P., Z.P. and
Batteries 2024, 10, 81 18 of 20

V.K.; supervision, A.P. and V.K.; project administration, A.P. All authors have read and agreed to the
published version of the manuscript.
Funding: This work was supported by the Grant Agency of the CTU in Prague, grant No. SGS23/067/
OHK3/1T/13, and by the project “The Energy Conversion and Storage”, funded as project No.
CZ.02.01.01/00/22_008/0004617 by Programme Johannes Amos Comenius, call Excellent Research.
Data Availability Statement: Data are contained within the article.
Acknowledgments: During the preparation of this work, the authors used ChatGPT 3.5 to generate
coherent and articulate summaries of complex ideas, aiding in the initial drafting process. After
utilizing this tool, the authors thoroughly reviewed and edited the content, ensuring accuracy and
coherence, and take full responsibility for the final publication’s content.
Conflicts of Interest: The authors declare no conflicts of interest.

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