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An Ugent Call To Spent LIB Recycling - Whys and Wherefores For Graphite Recovery (Natarajan and Aravindan 2020)
An Ugent Call To Spent LIB Recycling - Whys and Wherefores For Graphite Recovery (Natarajan and Aravindan 2020)
Figure 1. a) Representation of the LixC6 structure illustrates the lithium accommodation sequences perpendicular to the basal plane. b) The natural
graphite resources around the world. Others include countries like the USA, Canada, Namibia, Pakistan, Russia, Sri Lanka, Ukraine, and Zimbabwe.[14]
charge carbons of both hard and soft carbon materials could the Nobel prize winner anode is impossible at present in the
exhibit better performance than the graphite; however, charge market, however the applications of graphite, especially the
density also needs to be considered when the condition arises EV market look to suffer in the future as a consequence of the
to store the lithium in the carbon bulk.[10,11] Hard carbons reveal increasing demand for this critical material graphite (Figure S1
better higher capacity as compared to the soft carbons, also not and Table S1, Supporting Information).
experiences the exfoliation problems like graphite. This kind
of hard carbon with d002 spacing of >0.372 nm established 1%
volume change upon lithiation (10% for graphite) and acquired 2. Present Status of LIB Recycling in Industries
outstanding reversibility. The number of studies explained the
reasons for “high specific charge” might be due to the accom- The evolution of LIBs on the various applications soon and
modation of additional lithium on the nanoscopic cavities of the demand for other raw materials are already well-predicted;
graphite. Also, Dahn et al.[12] explained the lithium could have however, graphite has not yet been noticed and underrated
been adsorbed on both sides of the single graphene layer sheets where countries are jump-started to sell electric vehicles (EV).
in terms of “falling cards,” and stated the lithium storage in the The main battery companies, like LG Chem, AESC, Samsung,
micropores. However, high specific charge carbons face severe Toshiba, and Panasonic, employed graphite in EV battery as
downsides such as high irreversible specific capacities, and anode material with various types of cathodes.[15] The content
lithium deposition pushes still the researchers toward finding of graphite in an electric hybrid car would be about 10 kg, and
the graphite-like carbon structures. Similarly, doping of heter- a full-EV requires about 50 kg,[16] while prediction reports the
oatoms on carbons as an insertion host for lithium results in number of 125 million EV would be in the world by 2030.[17]
high specific charges than graphite, nevertheless the interaction In brief, the cost of the anode graphite lies in between $8 and
between neighbor carbon and heteroatoms is still not clear apart 13 per kg in the market, highlights the material cost of around
from the discussion of the steric and electronic effects. The 10–15% in the typical commercial LIBs. Also, it should be noted
hydrogen-containing graphite also can display larger capacity; that ≈12–21 wt% content of graphite would be available in the
nonetheless, the overpotential during the de-lithiation hindered spent LIBs where 5–7% of lithium only present. At the same
the practical application. Besides carbonaceous anodes, interca- time, it should be noted that all kinds of graphite cannot be
lation type, zero-strain spinel Li4Ti5O12 is proposed and subse- employed, and only the large flake graphite gains significant
quently commercialized, but the lower capacity (≈175 mAh g–1) interest to be LIB anode in the market. Based on the forecast,
and higher working potential (≈1.55 V vs Li) has to be compro- the demand growth of graphite is estimated at 250 000 tons per
mised.[13] However, it eventually dilutes the net energy density year, in which about 72% will be employed in LIBs between
of the LIB. On the other hand, alloy type Si-nanostructures are 2016 and 2025.[18] Graphite mines only can produce 90–98%
worth investigating as a possible alternative. Still, issues like purity flake graphite, and though the purification methods are
huge volume variation (>300%), unstable SEI formation, and further requisite to upgrade 99.5% purity with spherical shape
poor cycling stability have to be addressed before the commer- to achieve a battery grade.[19] At the beginning of 2018, a new
cialization.[13] Therefore, finding a suitable material to substitute graphite mining project with a high-grade graphite deposit
300–600 °C to evaluate their performance as an anode mate- process would be helpful to convert the graphite into graphene
rial for LIBs. The resultant material at 600 °C exhibited a high or not in detail. The preparation of graphene oxide has been
charge capacity of ≈343 mAh g−1 with 98.7% capacity retention demonstrated in one step using the Hummer’s method with
after 50 cycles. In this approach, authors could not attain the already pre-swelled graphite which obtained during cycling.
original capacity of the graphite because of the presence of The symmetric supercapacitor using this resultant rGO dis-
residual, which made negative electrochemical effect during played 312 F g−1. In contrast, the rGO produced from pristine
the performance. Rothermel et al.[37] have investigated the suit- one exhibited 99 F g−1, proves that battery cycling eases the
ability of spent LIBs graphite as an anode for the LIBs before preparation of GO and saves the time period. As well, high
and after electrolyte extraction. Also, the hydrometallurgical production of 33–36% of graphene attained compared to the
method without separation steps has been reported by Wang graphene obtained from pristine one via shear-mixing due to
and his co-workers[38] elucidate the recovered graphite could be the lattice expansion during the battery cycling that broken the
reached a comparable capacity of 377 mAh g–1 at 0.1 C. Wang graphite bonding layers to get higher exfoliation efficiency. Fur-
et al.[39] reclaimed the graphite with simple water treatment ther, H2SO4 treatment enabled the productivity up to 83.7% via
regains 345 mAh g−1 after 100 cycles where residual Li present further swelling the graphite. For the practical applications, the
in the graphite layers react with water separated the SEI layer mechanical properties of the graphene composite have been
by producing H2 gas. Recently, Subramanyan et al.[40] reported made with epoxy that displayed good mechanical properties.
the possibility of using the mechanically separated graphitic Other than above applications, graphite has been efficiently
anode toward the fabrication of ≈1.4 V class Li-ion cells with reused for dye removal and polymer-graphite film prepara-
LiCrTiO4 cathode by utilizing the Ti4+/3+ couple. Aravindan tion using the recovered separator and graphite from spent
et al.[28] proposed the possibility of reusing the graphite as an LIBs.[44,45]
anode material with pre-lithiation/treatment for LIB and Li-ion It is important to note that the possible impurities may pre-
capacitor (LIC) application by pairing the olivine LiFePO4 and sent in the spent graphite during regeneration are residual
activated carbon (AC) as the cathodes, respectively. Thus con- cathode materials along with elemental Cu, Fe, Al, etc. Gen-
structed LIB delivered energy of 313 Wh kg–1, and LIC provides erally, oxidative lixiviation can be performed to eliminate the
≈112 Wh kg–1 with decent cycling profiles. Recently, our group elemental impurities, whereas high-valence impurities such
has fabricated a high-energy LIC using recovered graphite from as Co and Mn can be removed via the reductive lixiviation
spent LIBs as an anode and AC as the cathode (Figure 3).[27] process. Recently, researchers demonstrated the removal of
After simple heat treatment and pre-lithiation, the constructed contaminants from the spent graphite by sulfuric acid at low
LIC delivered a maximum energy density of 185.54 Wh kg–1 and temperature where all high-valence metals transformed into
the temperature performance results in pieces of evidence that low-valence sulfates and regenerated the graphite in its original
the spent LIB graphite can be reutilized for commercialization structure at a higher temperature. The regenerated graphite
if recycled in a proper technique by researchers/industries. also exhibited an initial charge capacity of 349 mAh g−1, and it
From the results mentioned above, it is evident that the recov- claimed no wastewater generation in this process encourages
ered graphite is not only valuable for LIB as an anode, also for us to find more routes to purify the graphite efficiently.[25] Also,
the utilization of anode for high energy LIC in the pre-lithiated it is noteworthy to include the reuse of graphite, if the structure
state with AC as a counter electrode.[27,28] gets distorted as a result of the several charge–discharge cycles.
Liang et al.[29] performed the calcination at different tem- This type of damaged structure certainly can be employed as an
peratures to evaluate the spent LIBs graphite as an anode for electrode for the reversible Na-storage process with carbonate-
Na and K-ion batteries. The optimized electrodes exhibited based electrolytes owing more number of defects in their lay-
a good specific capacity of 162 and 320 mAh g–1, respectively, ered structure.[46] In the case of more mechanical damage in the
for Na and K-ion battery applications (Figure 3i–n). Further, graphite structure, it can be easily milled and renewed as a hard
the recovered graphite can be transformed into graphene for carbon that can intercalate both Li and Na-ions reversibly.[47,48]
multifarious applications like gas storage,[41] supercapacitor Undoubtedly, the hard carbon is one of the promising anodes
electrodes,[42] etc.[22] One of the interesting approaches is the for Na-ion batteries and high power anode for Li-ion capacitors;
re-synthesis of reduced graphene oxide (rGO) from the recov- thus, the transformation of damaged graphite to hard carbon
ered graphite and outer metallic cases of spent LIBs. In this paving a route to prepare this kind of commercialized carbo-
study, the recovered aluminium and metallic cases were used naceous materials from the spent LIBs.[49] Additionally, the for-
as a reducing agent in the presence of HCl to synthesis rGO mation of metal composites (e.g., Si-graphite) is commendable
separately for supercapacitor application, offered high cycling using the damaged graphite toward the goal of developing next-
stability of 20 000 cycles indicates that the recovered graphite generation anode for high energy Li-ion power packs.[50]
can be reused for the preparation of graphene derivatives.[42]
The resultant material has shown promising results toward
H2 and CO2 storage applications.[41] The above positive results 4. Conclusion and Future Requirement of Graphite
shed light on the opportunity of developing the reuse of spent
Electrode Recycling
LIBs graphite in the existing as well as in the emerging energy
storage applications (Figure 2). Li and his co-workers[43] pro- As discussed earlier, industries/research has focused on the
posed a new strategy to prepare graphene oxide and graphene recovery/reuse of spent LIB cathodes to compensate for the
from spent LIBs. They have analyzed the influence of cycling future raw materials demand for the futuristic needs, and
on the graphite and answered the battery charge/discharge none of the LIB recycling industries so far have targeted the
Figure 3. a,b) Surface morphological features of recovered graphite, c) High resolution-transmission electron microscope (HR-TEM) images with
lattice fringes. Inset: TEM picture, d) selected area electron diffraction pattern; Electrochemical performance of graphitic carbon (GC) between 0.005
and 1.5 V versus Li at a current density of 100 mA g–1. Reproduced with permission.[27] Copyright 2020, Royal Society of Chemistry. e) Typical charge–
discharge curves for the first three cycles. Inset: the differential capacity profile. f) Plot of capacity versus cycle number; Electrochemical performance
of AC/pre-lithiated GC based LIC between 2 and 4.3 V at various current densities. g) Typical galvanostatic charge–discharge curves, and h) cycling
profiles of LIC at a current density of 1 A g–1. Reproduced with permission.[28] Copyright 2019, John Wiley and Sons. Galvanostatic charge–discharge
curves of the initial five cycles at a low current density of 0.05 A g–1, rate capability at various current densities, and cycling performance of recovered
graphite heat-treated at 1300 °C. i–k) Na-ion half-cells with 1 m NaCF3SO3 in diethylene glycol dimethyl ether electrolyte, and l–n) K-ion half-cells with
0.8 m KPF6 in ethylene carbonate: diethyl carbonate (1: 1 in volume) electrolyte. For the tests of cycling performance at (k) 2 A g–1, and (n) 0.2 A g–1
in Na-ion battery and K-ion battery, respectively, both cells are firstly stabilized at 0.05 and 0.1 A g–1. Reproduced with permission.[29] Copyright 2019,
Royal Society of Chemistry.
recovery/reuse of graphite using the existing technologies. Few the bulk scale process. The issues associated with the current
industries have been involved in the graphite reduction process graphite recycling/reuse process from spent LIBs are as follows:
of metals along with cathode materials, or it will be burned
during the pyrometallurgical process that cannot be acceptable 1. LIB recycling is considered one of the complex operations
in which demand is growing at an increasing rate and also a due to the usage of a large variety of cathode combinations
lot of opportunities behind to be reused in the various applica- by the industry. Hence, the “second-life” has been prosed as a
tions. However, few research groups are emerging on the reuse short-term solution, since the spent LIB can retain 70–80% of
of graphite for energy storage applications, which has shown initial capacity and function for several years in low-end
promising results that may help to attain in the industrial scale. applications like residential and commercial spaces, grid
Though some concerns need to be solved before executing storage, power backups, etc.[51]
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