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Electric potential-determined redox intermediates

Cite this: Green Chem., 2022, 24,
for effective recycling of spent lithium-ion
3723 batteries†
Yunhui Hua,‡a,b Zhenghe Xu,c Baojun Zhaob,d and Zuotai Zhang *a
Published on 30 March 2022. Downloaded on 10/16/2023 8:20:30 AM.

Recycling of spent lithium-ion batteries (LIBs) by hydrometallurgy faces a major problem of consuming
an excessive amount of acid and requiring different redox additives for effective metal leaching. Reducing
chemical consumption in the recycling process is highly desirable for the environmentally friendly and
sustainable development of renewable energy. In this study, an electrochemical approach for analyzing
electric potentials was developed to evaluate redox abilities. Based on the results, a salt leaching method
was proposed using water-soluble NH4Fe(SO4)2 as a redox intermediate for synergistic recovery of valu-
able metals from spent ternary lithium-ion batteries (NCM) and LiFePO4 batteries (LFP). More than 97% of
the Li, Mn, Co and Ni from the mixed cathode can be leached under mild conditions (50 °C, 30 min), with
PO43− being completely retained in residues. The first-step reaction between Fe3+ and LFP to release Fe2+
proceeded rapidly, whereas the following slower reaction between Fe2+ and NCM was the rate-control-
ling process. Thermodynamic analysis of leaching solutions was carried out systematically and shown to
Received 24th January 2022, be feasible for designing a precipitate recovery process for both LFP and NCM battery systems, with the
Accepted 29th March 2022
recovered products being used for regenerating new materials. The synergistic salt-leaching treatment of
DOI: 10.1039/d2gc00331g spent LFP and NCM batteries based on electrochemical principles helped achieve high efficiency and
rsc.li/greenchem high selectivity with a great benefit to preserving the environment.

1 Introduction performance to those of lead, Ni–Cd, and Ni–MH batteries.3,4

However, after their life span, large amounts of spent batteries
A global tendency toward sustainable development is leading are generated, with the associated environmental pollution in
to a rapid increase in applications of mobile equipment, the form of heavy metals and toxic organics.5,6 On the one
including electric vehicles (EVs) and other portable electronic hand, spent LIBs still have relatively high energy potential and
devices. According to statistics from international agencies, may be able to go through second life, which may extend their
the annual sales of EVs in 2021 still reached a growth of 98% lifetimes. The comprehensive use of spent LIBs can also
over 2020 despite the worldwide impact of the COVID-19 reduce the environmental pressure by providing flexibility and
pandemic.1,2 More countries are setting carbon-neutral pol- additional time to establish the required recycling facilities for
icies and more electric transportation modes are expected in sustainable development.7 Spent LIBs that finally reach the
the future. Electric transportation mostly utilizes lithium-ion end of their lifetime contain a high content of valuable metals
batteries (LIBs) as a power source because of their superior such as Co, Ni and Li, which can be an important resource for
sustainable production.8,9 Therefore, recycling of spent LIBs is
of great importance from both economic and environmental
a
School of Environmental Science and Engineering, Southern University of Science perspectives.
and Technology (SUSTech), Shenzhen 518055, China.
Most research on recycling of spent LIBs focuses on the
E-mail: [email protected]
b
School of Chemical Engineering, The University of Queensland, St Lucia 4072,
recovery of valuable metals from cathodes, including LiCoO2
Brisbane, Australia (LCO), LiNixCoyMnzO2 (NCM), LiNixCoyAlzO2 (NCA), LiMn2O4
c
Department of Materials Science and Engineering, Southern University of Science (LMO) and LiFePO4 (LFP).10 As for LCO, NCM, NCA and LMO,
and Technology (SUSTech), Shenzhen 518055, China these cathode materials are usually composed of high-valence,
d
Faculty of Materials, Metallurgy and Chemistry, Jiangxi University of Science and
transition metal oxides. The methods to recover these valuable
Technology, Ganzhou 341000, China
† Electronic supplementary information (ESI) available: Fig. S1–S12. See DOI:
transition metals are primarily pyrometallurgy and hydrome-
https://doi.org/10.1039/d2gc00331g tallurgy, while other methods including direct recycling are
‡ First author of the article. still in early stages of development.11 Pyrometallurgy uses a

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carbothermic reduction or salt-roasting method at high temp- extraction from both cathodes. It was revealed that the intro-
eratures to extract metals, which requires high energy con- duction of ferric ions into this synergistic treatment can effec-
sumption and generates greenhouse gases, toxic gases and tively extract valuable metals and completely precipitate phos-
other hazardous slags.12,13 The pyrometallurgical process phorus as ferric phosphate. The amount of ferric salt needed
therefore could impose a number of environmental risks for the process was close to theoretical calculations (stoichio-
including global warming and photochemical pollution.14 To metric amount), and there were no other impurities released
attain the energy-saving and carbon-neutral objective for throughout the process. A thermodynamic study on the leach-
future development, hydrometallurgy is becoming more prefer- ing solution is shown to be suitable for designing product
able.15 Hydrometallurgy uses inorganic acids (e.g., HCl16,17 recovery. The selective salt leaching by Fe3+ is a feasible
and H2SO4 18,19) or organic acids (e.g., acetic acid,20 citric approach for the green and efficient recycling of spent LIBs.
acid,21–23 and oxalic acid24,25) as leaching agents for metal
recovery. However, various kinds of spent battery cathodes
need to be separated first because they require different redox 2 Experimental
additives for metal recovery. For the spent NCM and LCO cath-
2.1 Electrochemical test of reaction potentials
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odes, for example, reductants (e.g., H2O2, NaHSO3, and

ascorbic acid26–28) are usually used to facilitate the reduction The reactants in this study include solid powders and aqueous
and release of the metals; but for spent LFP cathodes, solutions. Each gram of solid powder was mixed with 0.1 g
additional oxidants (e.g., H2O2 and Na2S2O8) are required to carbon black, 0.25 g ethyl cellulose, 19 ml ethanol and 1.5 ml
release Li for recovery.29,30 Moreover, excessive amounts of terpineol. The mixture was put in a beaker and stirred for 12 h,
leaching reagents are often needed to achieve high leaching and then kept still for another 12 h. The supernatant of the
efficiency because some components, such as H2O2 in the mixture was spin-coated on a conductive glass, followed by a
reagent, are unstable and easily decomposed by the catalytic thermal treatment at 200 °C for 2 hours. The aqueous solution
effect of the metal ions (e.g., Fe3+/Fe2+ (ref. 31 and 32)). It is was prepared by mixing the tested salt with sodium sulfate
desirable to investigate new processes to reduce the use of (Na2SO4) in water. The concentration of each tested reactant
reductant and oxidant additives to achieve green and highly was set at 0.1 M, with the Na2SO4 at 0.5 M to improve the
efficient recycling of spent LIBs.33 electro-conductivity.
To save energy and resources, some studies have proposed The electrochemical test was conducted with an electro-
“treating waste by waste”. For example, carbon black or alumi- chemical work station ( produced by Corretest, Wuhan, China).
num foil from spent LIBs have been taken as reductants for Coated conductive glass was used as the working electrode and
spent LCO or NCM cathodes.34,35 Spent Ni–MH batteries have a platinum foil electrode as the auxiliary electrode. A Hg(s)|
also been reported as reductants for LCO cathodes, and valu- Hg2SO4(aq.)| and Sat. K2SO4(aq.) electrode (reference potential:
able metals from both batteries can be effectively recovered.36 0.64 V vs. NHE) was used as the reference electrode. The elec-
LFP and NCM batteries have emerged as major battery types tric potential was obtained by measuring the open circuit
on the market and they are expected to occupy a greater potential of each system and then calculated according to
market share in the future.37 Some studies have attempted eqn (1):
to use sulfuric acid to recycle LFP, LCO and NCM E ¼ Em þ Ere ð1Þ
synergistically.38,39 It was reported that the intrinsic redox reac-
tion could limit the acid dosage and also reduce the addition where E is the system’s actual electric potential, Em is the
of reductants or oxidants. However, the kinetics and mecha- measured potential, and Ere is the reference potential. The test
nisms of the synergistic reactions remain unclear, and an was conducted when the system potential became stable, and
in-depth study is needed to achieve efficient production. each test lasted for 200 s.
Moreover, sulfuric acid as a leaching agent does not have
selectivity for every element. The phosphorus existing as PO43− 2.2 Process for metal leaching and recovery
(or H3PO4, H2PO4−, or HPO42−) in the leaching solution will The flow process for leaching and recovery of metals from
inevitably bring impurities into an NCM or LCO system, and spent cathode materials is given in Scheme 1. Spent NCM and
the iron from LFP may not be able to combine with PO43− LFP cathode powders were mixed with the selected salt in a
effectively for complete precipitation. Therefore, a selective glass flask. Water was added at a solid to liquid ratio of 50
leaching system is needed for the synergistic treatment of g L−1. The leaching reaction was conducted in a water bath
spent LFP and NCM batteries. under different conditions. After the reaction, the solution and
To achieve such selectivity, we proposed in this study a salt residue were separated in a centrifuge tube. In one treatment,
leaching method to recycle valuable metals from spent LFP the leaching residue was put into an H3PO4/NH4H2PO4 buffer
and LiNi0.6Co0.2Mn0.2O2 (NCM622) battery cathodes. The solution to regenerate FePO4·2H2O. The pH was adjusted
electrochemical measurements of electric potentials were con- according to theoretical calculations using Visual Minteq soft-
ducted to evaluate redox ability. Based on this electrochemical ware. After the reaction, the solid was heated at 600 °C under
study, the freely soluble ammonium ferric sulfate (NH4Fe an air atmosphere for 1 h to burn carbon and other
(SO4)2) was taken as an intermediate leaching agent for metal impurities.

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Scheme 1 Flow process for recycling of valuable components in NCM and LFP with Fe3+ as an intermediate.

In the other treatment, the solution was adjusted to a pH of vation energy were also determined based on leaching efficien-
over 3 and pumped with air to fully oxidize and precipitate the cies measured at different times and temperatures. Different
remaining Fe3+/Fe2+; it was then filtered with a 0.22 μm pore models including mass transfer in the liquid boundary layer,
size filter. After filtration, NaOH was added to adjust the pH chemical reaction on the surface and diffusion in the solid
for Mn, Co and Ni precipitation. The precipitation pH was also surface layer were used to fit the experimental results.
designed based on thermodynamic calculations. The precipi-
tates were separated and heated at 900 °C under an air atmo- 2.4 Characterization of materials and products
sphere for 1 h to obtain metal oxides, while Na2CO3 was added Materials and products at different stages were ground into a
into the supernatant to collect Li2CO3. The remaining alkaline powder and loaded on a silicon wafer and then characterized
solution can be used in gas control technology to absorb some by X-ray diffraction (XRD) using a Rigaku Smartlab XRD oper-
acidic greenhouse or hazardous gases, including CO2, SOx and ating at 45 kV and 200 mA. The scanning angle 2θ varied from
HCl to reduce their negative environmental impact. 10 to 80° at a scanning rate of 5° per minute.
The morphology and element distribution of products
2.3 Metal leaching efficiency analysis were analyzed using a scanning electron microscope (SEM)
To determine the composition of the spent NCM622 and LFP equipped with an energy-dispersive X-ray spectrometer (EDX)
cathodes, the cathode powder was digested with aqua regia and a Zeiss Merlin SEM. The scanning voltage for SEM and
(composed of hydrochloric acid and nitric acid with a volume EDX mapping was set at 15 kV.
ratio of 3 : 1) using digestion apparatus, and then diluted with Elements and their valences in the products were analyzed
deionized water. The metal concentrations in the leachate were by X-ray photoelectron spectroscopy (XPS) using a PHI 5000
analyzed by inductively coupled plasma mass spectrometry Versaprobe III XPS. MultiPak software was used to assist in the
(ICP-MS) using an Agilent Technologies 7700X ICP-MS. The identification of elements and their valences. The carbon
leaching efficiency was calculated using eqn (2): binding energy was set at 284.8 eV for standard calibration.
cV
x¼ ð2Þ
m
3 Results and discussion
where x is the leaching efficiency, c is the concentration of
different metal ions in the leachate, V is the volume of leach- 3.1 Design of the leaching system by reaction potentials
ing solution, and m is the initial mass content of the element The synergistic reaction involves two parts, including reducing
in the cathode powder. The reaction mechanisms and acti- high valence Mn, Co and Ni into corresponding Mn2+, Co2+

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and Ni2+,30,40 and oxidizing LiFePO4 into FePO4.41,42 NCM622 Table 1 Reaction potentials of related redox couples and their corres-
contains multiple transition metals with different valences. ponding pH
To understand the reduction reaction in the NCM622
Redox couple E (V) pH
cathode, the XPS analysis of its transition metals is given in
Fig. 1a–c. LiNi0.6Co0.2Mn0.2O2/Ni2+ 0.6419 7.08
LiNi0.6Co0.2Mn0.2O2/Co2+ 0.5833 7.22
The main peak at 642.18 eV is assigned to Mn(IV), and the
LiNi0.6Co0.2Mn0.2O2/Mn2+ 0.4094 7.17
small peak at 636.89 eV is an Auger peak of Mn.43–45 As for Co, FePO4/LiFePO4 0.1841 8.10
the main peak at 779.71 eV and the weaker peak at 781.7 eV Fe3+/Fe2+ 0.6077 2.30
Fe(OH)3/Fe2+ 0.4890 3.36
are assigned to Co(III) and Co(IV), respectively. The Ni in the
cathode mainly exists as Ni(II) (854.53 eV) and Ni(III) (856.30
eV).44–48 The satellite peak at 860.99eV is also assigned to
Ni(II).43,48 XPS peaks for Mn(III) in NCM111 or NCM523 are not
Table 1. The oxidation potential of LiFePO4 into FePO4 (eqn
detected.47–49 Based on the results from XPS analysis, tran-
(5)) was also determined.
sition metals in LiNi0.6Co0.2Mn0.2O2 can be expressed as NiO,
Published on 30 March 2022. Downloaded on 10/16/2023 8:20:30 AM.

NiO1.5, CoO1.5, CoO2, and MnO2. The reduction reaction invol- FePO4 þ Liþ þ e ¼ LiFePO4 ð5Þ
ving electron transfer in LiNi0.6Co0.2Mn0.2O2 expressed in eqn
(3) can also be separated and written as eqn (4) (MOx rep- It is noticed that the reaction conditions of the electro-
resents NiO, NiO1.5, CoO1.5, CoO2, and MnO2). chemical test ( pH and ion concentrations) were not the same
as the metal leaching conditions. Therefore, the potentials are
LiNi0:6 Co0:2 Mn0:2 O2 þ 4Hþ þ e ¼ converted into the actual pH and concentration by the Nernst
ð3Þ
Liþ þ 0:6Ni2þ þ 0:2Co2þ þ 0:2Mn2þ þ 2H2 O equation as given in eqn (6).

a ox þ ne ! b red
MOx þ 2xHþ þ ð2x  2Þe ¼ M2þ þ xH2 O ð4Þ
0:0591 ½cðox=cθ Þa
The measured reaction potentials of transition metal Eðox=redÞ ¼ Eθ ðox=redÞ þ lg ð6Þ
reductions in LiNi0.6Co0.2Mn0.2O2 are given in Fig. 1d and n ½cðred=cθ Þb

Fig. 1 XPS spectra of (a) Mn, (b) Co, and (c) Ni from the spent NCM622 cathode material; (d) reaction potentials of redox couples; and (e) calculated
reaction potentials of redox couples at different pH values according to the Nernst equation.

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In this study, reactions on NCM622 involved the partici- 3.2 Analysis of the leaching process
pation of H+; therefore, the redox reaction is affected by the
acidity of the system. The Nernst equation is expressed as eqn The NCM and LFP cathodes are both insoluble solid powders.
(7) (MOx = NiO, NiO1.5, CoO1.5, CoO2, and MnO2): Therefore, a water-soluble Fe(III) salt is needed to act as an
intermediate for an effective reaction. FeCl3 and Fe(NO3)3 were
0:0591 ½H þ 2x not suitable here because they have potential to generate
EðMOx =M2þ Þ ¼ Eθ ðMOx =M2þ Þ þ lg ð7Þ
2x  2 ½M2þ  hazardous Cl2 or NOx.16 Therefore, ferric sulfate including
Fe2(SO4)3 and NH4Fe(SO4)2 (which existed as NH4Fe
The oxidation of LiFePO4 into FePO4 does not involve the (SO4)2·12H2O) were selected for the metal leaching test. The
acidity or the concentration of the redox couple. Therefore, the comparison of the leaching effect between Fe2(SO4)3 and
potential remains unchanged under the test conditions. The NH4Fe(SO4)2 is given in Fig. S1.† The results reveal a better
variation of calculated reaction potentials with pH and the leaching performance of NH4Fe(SO4)2 than that of Fe2(SO4)3.
concentration of redox couples is given in Fig. 1e. In this The superior performance of NH4Fe(SO4)2·12H2O is attributed
study, the solid-to-liquid ratio (S/L) was set at 50 g L−1. to its higher dissolution rate and hence more Fe3+ released
Concentrations of metal elements in the solution ranged from
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into the solution in a shorter time. In contrast, the dissolution

0.1 to 1 M. However, as revealed in Fig. 1e, the concentration of Fe2(SO4)3 into water is a slow process, and thus the whole
differences do not have as much influence as pH on redox reaction rate is limited. The limit of slow dissolution of
reaction potentials. The acidity of the solution is the dominant Fe2(SO4)3 was confirmed by conducting an additional test by
factor for the redox reactions of NCM and LFP, and a lower pH using Fe2(SO4)3 solutions as the intermediate in the leaching
is preferable. NCM622 and LFP are both insoluble solids, and test. The results in Fig. S2† show a significantly improved
a water-soluble intermediate is needed for effective reaction. leaching efficiency by using Fe2(SO4)3 aqueous solutions as
To avoid introducing more elements into the system, the Fe3+ compared with the addition of Fe2(SO4)3 powders. In fact,
was assumed to be a good candidate of intermediates. leaching using Fe2(SO4)3 aqueous solutions could achieve
The ionic Fe3+ can only exist at low pH, whereas at pH similar (Li and Mn) or better (Co and Ni) efficiencies as com-
higher than 3, it will be transferred into Fe(OH)3 precipitates. pared with the case of using NH4Fe(SO4)2·12H2O in the
Redox potentials for an Fe3+/Fe2+ couple and an Fe(OH)3/Fe2+ powder as the intermediate. This finding suggests a great
couple are given in Fig. 1d and Table 1. The redox reactions benefit of using aqueous solutions rather than powder forms
are represented by eqn (8) and (9), with their corresponding of the intermediates, which will be further tested as an impor-
redox reaction potentials at different concentrations and pH tant parameter in the upcoming scale up tests and reported in
being calculated (eqn (10) and (11)) and shown in Fig. 1e. a separate communication. Furthermore, an overdose of
Fe2(SO4)3 to fully extract the transition metals from NCM622
Fe3þ þ e ¼ Fe2þ ð8Þ
inevitably leads to some extra Fe2+ in the liquid that needs to
be oxidized after leaching. Higher pH is desirable for oxidation
FeðOHÞ3 þ 3Hþ þ e ¼ Fe2þ þ 3H2 O ð9Þ and removal of Fe2+ (Fig. 1e) but it may also lead to the precipi-
tation of other transition metals. The ammonium present can
0:0591 ½Fe3þ  form a complex with Mn, Co and Ni, preventing them from
EðFe3þ =Fe2þ Þ ¼ Eθ ðFe3þ =Fe2þ Þ þ lg 2þ ð10Þ
1 ½Fe  precipitating at an early stage and providing more flexibility
for treating the remaining Fe2+. Therefore, NH4Fe(SO4)2·12H2O
EðFeðOHÞ3 =Fe2þ Þ ¼ was selected as a leaching intermediate in this study.
0:0591 ½Hþ 3 ð11Þ 3.2.1 Optimization of leaching conditions. The optimized
Eθ ðFeðOHÞ3 =Fe2þ Þ þ lg 2þ leaching conditions were determined by varying different
1 ½Fe 
leaching parameters. The internal variate included the mass
When Fe(III) exists as ionic Fe3+, the electric potential ratio between LFP and NCM622, and the amount of NH4Fe
remains unchanged with pH, but when Fe(III) exists as Fe (SO4)2·12H2O. The external variate included the reaction temp-
(OH)3, the potential decreases with increasing pH. On the one erature and time.
hand, the electric potential of Fe(III)/Fe2+ is always lower than The influence of the mass ratio between LFP and NCM622
those of Mn, Co, and Ni from NCM622, which indicates that is given in Fig. 2a and Fig. S3.† LFP and NCM622 theoretically
NCM622 can be reduced by Fe2+. On the other hand, it is pre- react at a molar ratio of 1 : 1. The mass ratio is therefore calcu-
dictable that at pH values higher than 5, Fe(OH)3 will no lated to be LFP/NCM622 = 1.63. Leaching results show that
longer be able to oxidize LiFePO4 into FePO4. According to LFP/NCM622 > 1.8 is suitable for high-efficiency metal extrac-
these analyses, Fe3+ should be an effective intermediate for the tion where over 97% valuable metals can be extracted from
synergistic treatment of NCM and LFP at low pH. Since Fe3+ both cathodes. For a higher mass ratio, the leaching efficiency
can already provide an acidic environment, additional acid of Li, Mn, Co, and Ni does not change markedly, but excessive
should not be needed for the metal extraction reaction. In con- Fe2+ will be generated, which needs additional oxidation by air
clusion, an electrochemical study is shown to be a convenient or another oxidant to separate it from other transition metals.
approach to design redox additives. Therefore, LFP/NCM622 = 1.8 is a suitable composition.

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Fig. 2 (a) Leaching efficiency of metals at different LFP/NCM622 mass ratios (g g−1) with NH4Fe(SO4)2·12H2O/mixed cathode powder = 3 : 1 (g g−1)
at 50 °C for 30 min; (b) leaching efficiencies of metals with different amounts of NH4Fe(SO4)2·12H2O with LFP/NCM622 = 1.8 (g g−1) at 50 °C for
30 min; and (c–f ) leaching efficiencies of metals at different temperatures and times with LFP/NCM622 = 1.8 (g g−1) and NH4Fe(SO4)2·12H2O/mixed
cathode powder = 3 : 1 (g g−1).

The amount of NH4Fe(SO4)2·12H2O added is also important According to the electrochemical study discussed earlier, such
for full metal extraction. According to the reaction function, it a pH range is assumed to be suitable for the redox reaction
is theoretically predicted that 2.56 g of NH4Fe(SO4)2·12H2O is between LiNi0.6Co0.2Mn0.2O2 and LiFePO4 with the assistance
needed for complete metal extraction from 1 g of the mixed of the intermediate Fe3+. The leaching efficiency of phosphate
powders. It is revealed in Fig. 2b that at least 3 g of NH4Fe is given in Fig. S4 and S5.† PO43− is not extracted in all tests,
(SO4)2·12H2O is needed to fully extract the metals. Excessive which is different from the leaching with a strong inorganic
Fe3+ introduced into the solution does not have any more posi- acid. With the addition of Fe3+ into the system, the phosphate
tive influence on leaching efficiency or other process beha- remains as residue. Previous studies also showed that PO43−
viors. Therefore, 3 g of NH4Fe(SO4)2·12H2O to treat 1 g of remains as a FePO4 solid in such a pH range.50,51 The high-
mixed powder (LFP/NCM622 = 1.8) is proposed to be the opti- efficiency selective leaching demonstrates that the proposed
mized internal condition. Under the optimized internal con- electrochemical test and calculation method are applicable
ditions, the system pH is found to be 0.91 at the beginning for treating mixed spent LIB cathodes with different redox
and 2.88 after the reaction is completed (as colored in Fig. 1e). properties.

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The external reaction conditions including temperature and fore be divided into two steps of solid–liquid reactions. In the
time were also investigated, and the results are given in first step, the Fe3+ added is reduced by LiFePO4 to produce
Fig. 2c–f. Higher temperatures and longer reaction times were Fe2+ as expressed in eqn (8). In the second step, the Fe2+ pro-
shown to improve the leaching efficiencies. With increasing duced reduced LiNi0.6Co0.2Mn0.2O2 to Mn2+, Co2+ and Ni2+
temperatures, the leaching time for full extraction is reduced (eqn (12)). The H+ came from the hydrolyzation of Fe3+ as
gradually. According to the experimental results, 50 °C and expressed in eqn (13). With the consumption of H+ in the
30 min are regarded as suitable conditions. During the leach- second step, more Fe(OH)3 was generated. The overall reaction
ing process, Li is extracted from both LiNi0.6Co0.2Mn0.2O2 and between LFP and NCM622 with Fe3+ as an intermediate can be
LiFePO4, featuring a faster leaching rate than transition expressed as eqn (14).
metals. At 30 °C, for example, over 50% of Li is already
released into the solution within 5 min. Mn, Co and Ni are LiNi0:6 Co0:2 Mn0:2 O2 þ Fe2þ þ 4Hþ ¼
ð12Þ
known to be uniformly distributed in the cathode structure. Liþ þ 0:6Ni2þ þ 0:2Co2þ þ 0:2Mn2þ þ Fe3þ þ 2H2 O
Therefore, even though they have different redox potentials,
they eventually have similar leaching characteristics and are Fe3þ þ 3H2 O $ FeðOHÞ3 þ 3Hþ ð13Þ
simultaneously released into the solution.
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4
In summary, the optimal leaching conditions are LiNi0:6 Co0:2 Mn0:2 O2 þ LiFePO4 þ Fe3þ þ 2H2 O ¼
3
determined to be LFP/NCM622 = 1.8 (g g−1) and
2Liþ þ 0:6Ni2þ þ 0:2Co2þ þ 0:2Mn2þ þ ð14Þ
LiNi0.6Co0.2Mn0.2O2/mixing cathode = 3 (g g−1) at 50 °C and
4
30 min. Under these conditions, valuable metals from both FePO4 þ FeðOHÞ3
3
LFP and NCM622 cathodes can be effectively extracted, while
the Fe2+ and Fe3+ that need further treatment are minimized. The reaction kinetics was studied in terms of various solid–
A comparison of cathode material leaching from NCM and liquid reaction models. In general, the solid–liquid reaction is
LFP is given in Table 2. In most studies, inorganic acids or controlled by the following three factors: mass transfer in the
organic acids are used as leaching agents to extract metals liquid boundary layer (eqn (15)), chemical reaction on the
from the cathode. Additional reductants for LCO and NCM, or surface (eqn (16)) and diffusion in the solid surface layer (eqn
oxidants for LFP, are also necessary to improve the leaching (17)).53,55
efficiency. Compared with the results from previous studies,
x ¼ k1 t ð15Þ
the leaching process developed in this study does not require
the addition of an acid. Moreover, the intrinsic redox reaction
1  ð1  xÞ1=3 ¼ k2 t ð16Þ
between LiNi0.6Co0.2Mn0.2O2 and LiFePO4 also reduces the
additional reductant or oxidant to a large extent. Synergistic 1  3ð1  xÞ2=3 þ 2ð1  xÞ ¼ k3 t ð17Þ
leaching is a feasible method for treating mixed cathodes from
spent LIBs. where x refers to leaching efficiency during the reaction time t
3.2.2 Reaction kinetics and mechanism. In order to clearly (min), and k1, k2 and k3 are the reaction rate constants (min−1).
understand the reaction mechanism, a comparison of results The activation energy of the leaching process is calculated
using NH4Fe(SO4)2 to leach LFP and NCM622 individually or based on the Arrhenius equation described in eqn (18):
synergistically is given in Fig. S6.† It can be noticed that  
Ea 1
NH4Fe(SO4)2 is able to fully react with LFP and release Li+, ln k ¼  þ ln A ð18Þ
R T
while it has limited leachability for NCM. With the addition of
LFP, metals from NCM were able to be reduced and leached where k represents the reaction rate constant (min−1), A is
out. With the addition of 1,10-phenanthroline in the NH4Fe the pre-exponential factor, T represents the temperature of the
(SO4)2 – LFP group, the red color of the liquid reveals the gene- reaction (K), Ea is the activation energy of the reaction (J mol−1),
ration of Fe2+ (Fig. S7†). The whole reaction process can there- and R is the universal gas constant (8.314 J mol−1 K−1).

Table 2 Leaching results of metals from cathodes by different leaching agents

Cathode Leaching agent Conditions Efficiency Ref.

−1
NCM, LFP 0.3 M NH4Fe(SO4)2 50 g L , 50 °C, 30 min 97.8% Li, 98.3% Mn, 98.9% Co, 99.0% Ni This study
NCM, LFP 0.25 M H2SO4 32 g L−1, 80 °C, 4 h >96% Li, Mn, Co, Ni 38
LCO, LFP 0.5 M H2SO4 30 g L−1, 20 min 99% Li, Fe, P, 92.4% Co 39
LCO, LMO, NCM, LFP 4 M H2SO4, 30% H2O2 70–80 °C, 2–3 h Li, Mn, Co, Ni dissolved, LFP partly dissolved 51
LCO 2 M H2SO4, 6% H2O2 100 g L−1, 60 °C, 1 h 97% Li, 98% Co 19
LCO 1.25 M citric acid, 1% H2O2 20 g L−1, 90 °C, 30 min 100% Li, >90%Co 21
NCM 2.5 M H2SO4, 0.8 M NH4Cl 100 g L−1, 80 °C, 1 h 99.11% Li, 97.34% Mn, 97.55% Co, 97.49% Ni 52
NCM 3 M formic acid, 6% H2O2 50 g L−1, 60 °C, 2 h 98.22% Li, 99.95% Mn, 99.96% Co, 99.96% Ni 53
LFP 0.3 M H2SO4, H2O2/Li = 2.07, 60 °C, 2 h 96.85% Li 29
H2SO4/Li = 0.57
LFP 0.8 M acetic acid, 6% H2O2 120 g L−1, 50 °C, 30 min 95.05% Li 54

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The fitting of the data to these leaching reaction models and of components, and overgrowth of the solid electrolyte
the corresponding fitting parameters are given in Fig. 3a–d, interphase.13,59,60 Most of the metals are preserved in the
while others are given in Fig. S8 and S9.† battery cell. The recovered metals are proposed to generate
According to the fitting results, the leaching of transition new materials after separation and proper treatment. In this
metals Mn, Co and Ni is mainly controlled by the surface study, the leaching system includes components from both
chemical reactions. At a relatively low leaching temperature of LFPs and NCMs. The study aimed at separating various com-
30 °C and 40 °C, the reaction is also influenced by mass trans- ponents into the Fe–P system and Ni–Co–Mn system as in the
fer. Lower leaching temperatures led to slow precipitation of form of original batteries. In the current case, the precursors
FePO4 and Fe(OH)3 with the precipitates being dispersed in FePO4, NiCoMn oxides and Li2CO3 were proposed to be syn-
solution to increase the viscosity of the system. The increasing thesized. To obtain pure products, thermodynamic calcu-
leaching temperature increases the thermal energy and hence lations on solution systems were conducted to assist in deter-
weakens interactions among the molecules in solution, which mining the experimental conditions.
decreases the system viscosity. At the same time, increasing 3.3.1 Recovery and characterization of FePO4. The residue
the leaching temperature also increases the rate of FePO4 and obtained after leaching is mainly composed of FePO4 and Fe
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Fe(OH)3 precipitation. Under these conditions, the influence (OH)3. The excessive amount of Fe(III) from Fe(OH)3 needs to
of mass transfer becomes weaker. In this study, it was found be balanced by additional phosphorus to obtain FePO4. Fe3+ is
that surface diffusion does not have a noticeable impact on known as a ternary weak base that can hydrolyze to become
transition metal leaching. Finally, the fitting of activation different hydroxides and ions. H3PO4 is a ternary moderate
energy given in Fig. S10† shows an increase in apparent acti- acid that can exist in multiple forms with different numbers of
vation energies of 47.47, 53.21, 55.39 and 58.03 kJ mol−1 for H+ being deprotonized. The acidity of the system is expected to
Li, Ni, Co and Mn, respectively. be the dominant factor for ion concentrations and solid-phase
The leaching rate of Li is higher than those of transition species. To determine proper conditions, thermodynamic cal-
metals and kinetic analysis reveals that the reaction of Li is culations on related species were systematically conducted
influenced by both surface chemical reaction and diffusion. using Visual Minteq software as described in the Experimental
However, at 30 °C, the leaching result of Li does not fit well section, and the results are given in Fig. 4a.
with any of the models. In the first minute, a large amount Extra water-soluble H3PO4 and NH4H2PO4 were added to
(more than 30%) of Li was leached out rapidly into the solu- adjust pH and to balance Fe. Species with concentrations
tion. After 2 minutes of leaching, Li exhibited a similar leach- below 10−6 M in the calculated range were considered negli-
ing trend to other transition metals. The analysis of the reac- gible in the solution. At pH below 1, there are still considerable
tion mechanisms is given in Fig. 3e. Li comes from both amounts of different Fe(III) ion species including Fe3+ and
LiFePO4 and LiNi0.6Co0.2Mn0.2O2. LiFePO4 has an olivine FeH2PO42+ in solution. The solid phase is simply FePO4, in
crystal structure and Li stays in octahedral voids. With a small equilibrium with the corresponding soluble species. At low
ion radius, Li+ is easy to transfer without changing the struc- pH, the ionization of H+ from H3PO4 is known to be impeded,
ture of LiFePO4. which limits the combination of Fe3+ and PO43−. All Fe(III) ion
Similar to the working mechanism of LFP, the oxidation of species decrease in concentration with increasing pH. Fe(III) is
LiFePO4 by Fe3+ simply involves the electron transfer and predicted to be completely precipitated out at pH above 2.
release of Li+, while the whole olivine structure of LiFePO4 is However, when the pH exceeds 4.5, the FePO4 precipitates are
not destroyed during the reaction.54,56 The reaction is simple converted into Fe(OH)3. Therefore, in this study, the leaching
and can proceed at a fast rate, which explains the high leach- residue was washed with an H3PO4–NH4H2PO4 solution at pH
ing efficiency of Li in the first few minutes. The redox reaction 2–3. The product after washing is verified to be ferric phos-
between Fe2+ and LiNi0.6Co0.2Mn0.2O2 on the other hand is phate hydrate (FePO4·2H2O) with two kinds of crystal struc-
more complicated. The LCO and NCM cathodes have layered tures (Fig. S11†). To clarify the component and eliminate the
structures formed by Mn, Co, Ni and oxygen. Li exists as inter- possible impurities, the product was calcined under an air
laid ions in the voids between the layers. During the redox atmosphere at 600 °C. As given in Fig. 4b, the anhydrous
reaction, electron transfer occurs between Fe2+ from the solu- FePO4 is obtained after the calcination. The SEM image and
tion and Mn, Co and Ni from the cathode. The H+ generated EDX mapping in Fig. 4c–e show that P and Fe distribute uni-
by Fe3+ hydrolysis needs to break chemical bonds in the layer formly in the product. Other metal elements (Ni, Co or Mn)
structure to take away the oxygen. Mn, Co and Ni can only be from NCM cathodes are not detected in the recovered FePO4.
released after the structure is destroyed.57,58 Therefore, com- The results suggest that such a method is feasible for FePO4
pared with the oxidation of LiFePO4, the reduction of recovery and the product can be used to produce a second LFP
LiNi0.6Co0.2Mn0.2O2 has a slower reaction rate and becomes cathode material.
the controlling process of the whole reaction. 3.3.2 Recovery and characterization of NiCoMn oxides. The
transition metals Mn, Co, and Ni are leached into the solution
3.3 Product recovery and analysis and the precipitation is a good method for their recovery. In a
The degradation of LIBs is usually caused by a number of pro- alkaline environment, these transition metals are known to
cesses, including structural failure, aging and decomposition form precipitates completely.50 As mentioned, the introduction

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Fig. 3 (a) Fitting results of (a) Li, (b) Mn, (c) Co and (d) Ni, according to a surface chemical reaction model, and (e) reaction mechanisms of synergis-
tic metal extraction from NCM and LFP using Fe3+ as an intermediate.

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Fig. 4 (a) Calculated ion concentrations and solid phase compositions of Fe(III)-PO43− at different pH values; (b) XRD pattern and (c) SEM image of
synthesized FePO4 after 600 °C calcination; EDX mapping images of (d) P and (e) Fe from synthesized FePO4 after 600 °C calcination.

of NH4+ into the solution by NH4Fe(SO4)2 may also lead to the of pH on the recovery of the transition metal precipitate. With
formation of the ammonium complex in the alkaline environ- increasing basicity, Ni(OH)2 is first precipitated and fully
ment. In some previous studies, ammonium leaching has also recovered, followed by Co(OH)2 and Mn(OH)2. This finding
been applied as a metal leaching method.61,62 Therefore, indicates that the pH should be higher than 11.5 to fully pre-
thermodynamic calculations were also performed to investi- cipitate the transition metals. To fully recover the transition
gate suitable precipitating conditions and the results are given metals as hydroxides, the system pH of 12–13 is considered
in Fig. 5a and b. According to Fig. 5a, the concentration of suitable.
Mn2+, Co2+, and Ni2+ decreases with increasing pH. When the After filtration and separation, the remaining alkaline solu-
pH is lower than 10 (a weakly alkaline environment), some of tion needs to be neutralized to reduce its potential negative
the Mn, Co and Ni will combine with NH3 to form soluble impact on the environment. It can be used to absorb acidic
complexes Mn(NH3)n2+, Co(NH3)n2+, and Ni(NH3)n2+. Based on greenhouse gases or industrial off gas including CO2, SOx and
the results of solution chemistry calculations, the concen- HCl which may bear implications of carbon neutralization or
tration of Ni(NH3)n2+ increases on increasing the pH to 9.5. reduction in emissions of other toxicities into the environ-
Then its concentration decreases with further increase in the ment. Normally, the acidic off gas from industrial production
basicity of the solution. A similar trend is found for Mn, but requires neutralization by an additional alkali (e.g., CaO and
the highest concentration is obtained around pH 8.5. As for NaOH). During such treatment with the remaining solution,
Co, its ammonium complex concentration decreases gradually ammonium and sodium salts can be obtained, with the water
with increasing basicity of the solution. At pH > 12, all forms being reused in the process and air pollution reduced. The
of the ammonium complex were precipitated or transferred recovered transition metal hydroxides were dried and calcined
into other kinds of ion complexes. Therefore, the precipitation at 900 °C for full decomposition to obtain metal oxides. Fig. 5c
pH should not be lower than 12. shows the solids of NiO and MnCo2O4 crystal structures after
Mn, Co and Ni can also combine with OH− to form the calcination, indicating the presence of transition metals
complex ions in a strongly alkaline environment. from the NCM cathode. The XPS analysis of the calcined metal
Concentrations of Mn(OH)n2−n, Co(OH)n2−n and Ni(OH)n2−n oxides is given in Fig. S12.† The valences of transition metals
follow a similar trend where they first decrease and then in the recovered solids were found to be the same as that in
increase with increasing pH. Fig. 5b also shows the influence the raw material, which provides the possibility of regeneration

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Fig. 5 (a) Calculated ion concentrations of Mn(II), Co(II), and Ni(II) at different pH values. (b) Precipitation rate of Mn(OH)2, Co(OH)2, and Ni(OH)2 at
different pH values. (c) XRD pattern and (d) SEM image of the synthesized MnCoNi oxide after 900 °C calcination. EDX mapping image of (e) Mn, (f )
Co, and (g) Ni from the synthesized MnCoNi oxide after 900 °C calcination.

of new materials. The SEM and EDX mapping images of the In short, the salt leaching by Fe3+ selected from the electric
calcined mixed oxides are given in Fig. 5d–g, showing the cal- potential measurements can achieve synergistic treatment of
cined products as fine particles with little agglomeration. Ni, spent NCMs and LFPs. Li, Mn, Co and Ni can all be fully
Co and Mn have a nearly uniform distribution. Other extracted while FePO4 is completely separated and preserved in
elements, such as Fe or P from LFPs, are not detected. The residues. Therefore, it is anticipated that this salt leaching
analysis of the product indicates that not only is the selective method will be effective for treating mixed spent battery cath-
leaching method by Fe3+ suitable for the effective recovery of odes with high efficiency and selectivity. Moreover, the product
transition metals from NCM, but also the recovered product recovery is designed based on thermodynamic calculations
can be used to regenerate new materials with proper precipi- and the experimental results are consistent with the predic-
tation and calcination. tions. Therefore, it can be concluded that a theoretical study is

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feasible for designing reaction conditions for a solution JCYJ20200109141227141). We are also grateful to the
system and such a method is expected to have a wide applica- Guangdong Province Universities and Colleges Pearl River
bility in designing metal solution reactions. Scholar Funded Scheme 2018.

4 Conclusions Notes and references

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