Waste Management 95 (2019) 192–200

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Waste Management
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Regeneration and characterization of LiNi0.8Co0.15Al0.05O2 cathode

material from spent power lithium-ion batteries
Yuehua Wang b, Liwen Ma a,b, Xiaoli Xi a,b, Zuoren Nie a,b, Yunhe Zhang c, Xiao Wen d, Zhe Lyu d
a
National Engineering Laboratory for Industrial Big-data Application Technology, Beijing University of Technology, Beijing 100124, China
b
College of Materials Science and Engineering, Key Laboratory of Advanced Functional Materials, Education Ministry of China, Beijing University of Technology, Beijing 100124, China
c
Jingmen GEM Co., Ltd., Jingmen 448000, China
d
Xiamen Tungsten Co., Ltd., Xiamen 361026, China

a r t i c l e i n f o a b s t r a c t

Article history: The use and scrap of lithium ion batteries, especially power lithium ion batteries in China, are increasing
Received 28 February 2019 every year. Regeneration of spent battery materials is not only important for environmental protection
Revised 29 May 2019 and resource saving, but also for the production of high value-added materials. In this research, spent
Accepted 6 June 2019
power lithium-ion battery cathode material LiNi1-xCoxO2 was acid-leached and a polymetallic leaching
solution containing Li, Ni, Co, Al and Cu was obtained. Cu was extracted from the leachate by using
CP-150 (2-hydroxy-5-nonyl salicylaldehyde oxime). The optimal conditions were found to be organic:
Keywords:
aqueous phase ratio (O/A) = 2:1, extraction agent concentration of 30%, and pH = 3. The precursor was
Spent power lithium-ion batteries
Recycling
prepared by coprecipitation of the leachate after Cu removal. Then, cathode material of lithium nickel
LiNi0.8Co0.15Al0.05O2 cobalt aluminate LiNi0.8Co0.15Al0.05O2 was synthesized under the optimal conditions of n (precursor): n
Electrochemical performance (lithium carbonate) = 1:1.1, calcination temperature of 800 °C for 15 h. The regenerated
LiNi0.8Co0.15Al0.05O2 product prepared under the optimized conditions was in a pure phase with a layered
structure and a smooth surface morphology. The first charge specific capacity was 248.7 mAh/g, and the
discharge specific capacity was 162 mAh/g. The interfacial impedance was 119 X. The 50th-cycle dis-
charge specific capacity was 149.1 mAh/g, and the capacity retention rate was high as 92%. Therefore,
the regenerated cathode material exhibited good performance.
Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction decommissioning is approaching. The recycling of spent power

Lithium-ion batteries are widely used for energy storage due to
their high capacity, high energy density and excellent cycle perfor-
mance, and can be applied to smartphones, notebook computers
and electric vehicles (Goodenough et al., 2013, Nam et al., 2006).
It is reported that the value of global Lithium-ion batteries market
is projected to reach $50 billion by 2020. The increase in the num-
ber of Lithium-ion batteries has also brought numerous spent
power lithium-ion battery materials and it is estimated that the
quantity of spent power lithium-ion battery materials only in
China will be 25 billion units weighing 500,000 metric tons by
2020. As spent power lithium-ion battery materials contain many
valuable metals and lead to environmental pollution, recycling
spent lithium-ion battery materials has been attracting extensive
attention (Yue et al., 2019). Therefore, with the surge in production
and sales of new energy vehicles, the peak of power battery
E-mail address: xixiaoli@bjut.edu.cn (X. Xi)
lithium-ion battery materials is essential.
There are many ways to recycle spent power lithium-ion bat-
tery materials, including pyrometallurgical (Fouad et al., 2007;
Träger et al., 2015) and hydrometallurgical processes (Huang
et al., 2016; Nayaka et al., 2016). Among them, the mechanical sep-
aration technology mainly uses crusher and vibrating sieve
machine for crushing and screening the spent battery materials
to obtain finely mixed electrode materials, which are then sub-
jected to other treatments to achieve the purpose of recycling
spent power lithium-ion battery materials (Bertuol et al., 2015).
The heat treatment technology involves using high-temperature
heat treatment to mainly remove the organic binder (PVDF) and
electrolyte of the electrode material, and to explore its pyrolysis
behavior, which can reasonably and effectively recycle the battery
material (Zhong et al., 2019). The extraction and separation tech-
nology utilizes a suitable extraction agent to extract and separate
different metal elements under different conditions, thereby recov-
ering valuable metals from spent power lithium-ion battery mate-
rials (X. Chen et al., 2018; Torkaman et al., 2017). The chemical

https://doi.org/10.1016/j.wasman.2019.06.013
0956-053X/Ó 2019 Elsevier Ltd. All rights reserved.
 Y. Wang et al. / Waste Management 95 (2019) 192–200
precipitation technique utilizes a precipitant to react with certain
valuable metal elements to form a precipitate, which separates
and recovers different metal elements (Rabia et al., 2019; Yang
et al., 2017). The reduction leaching technique involves adding a
reducing agent to the leaching solution to improve the leaching
effect and accelerate the leaching process of the electrode material,
so that the recovery is more efficient (Vieceli et al., 2017). Among
all these methods, mechanical separation technology, heat treat-
ment technology and reduction leaching technology are mainly
used for the pre-treatment of the battery materials. Extraction sep-
aration technology and chemical precipitation technology are
mainly employed for the subsequent separation of metal elements
from battery materials. Besides metals recovery, some studies have
also focused on battery material regeneration and preparation. For
instance, the spent cathode material LiMn2O4 was used to regener-
ate the cathode material Li1.2[Mn0.56Ni0.16Co0.08]O2 by the method
of leaching and co-precipitation (Q. Meng et al., 2019). The mixed
spent cathode material was used to regenerate the Mn-rich cath-
ode material by the method of co-extraction and co-precipitation
(Yang et al., 2017). The spent cathode material was used to regen-
erate the cathode material LiNi0.5Co0.2Mn0.3O2 by the method of
two-step leaching and co-precipitation (P. Liu et al., 2018). The
spent cathode material LiNixCoyMn(1-x-y)O2 was used to regenerate
the cathode material LiNixCoyMn(1
x
y)O2 by the method of co-
precipitation and solid-state synthesis (Zheng et al., 2017).
LiMn1.977(Ce, Cu)0.023O4 was prepared by sol-gel method
(Taddesse and Belete, 2019). LiNi1/2Mn1/2O2 was prepared by
glycine nitrate pyrolysis method (Gopukumar et al., 2004).
LiNi0.5Mn0.5O2 was prepared by freeze drying method (Shlyakhtin
et al., 2004). Li[Ni0.5Mn0.5]O2 was prepared by co-precipitation
method (Lee et al., 2008). However, many of these studies are
not aimed at the regeneration of cathode materials of power
lithium-ion batteries.
Among cathode materials of power lithium-ion batteries, lay-
ered nickel-rich ternary oxides have been intensively investigated
due to their high specific capacities, elevated energy densities,
non-toxicity, and relatively low cost. LiNi0.8Co0.15Al0.05O2 is a
promising cathode material for power vehicles. Numerous reliable
synthetic routes have been developed until now to prepare
LiNi0.8Co0.15Al0.05O2 cathode powder, including solution combus-
tion pathway (Majumder et al., 2006), sol-gel synthesis (L. Li
et al., 2017), solid state sintering (X. Meng et al., 2019) and copre-
cipitation (Wu et al., 2015; Liu et al., 2011). Therefore, it is signif-
icant to consider the ternary cathode material LiNi0.8Co0.15Al0.05O2
as the object for regeneration of the spent cathode materials.
This paper focuses on the recycling and regeneration of cathode
material LiNi0.8Co0.15Al0.05O2 from spent power lithium-ion battery
material LiNixCo1-xO2. Extraction, coprecipitation and calcination
were employed and the optimal process conditions were deter-
mined. XRD, SEM, and XPS analyses were carried out on the
obtained LiNi0.8Co0.15Al0.05O2 to determine the phase structure,
surface morphology and valence states of elements. Finally, the
electrochemical properties of the LiNi0.8Co0.15Al0.05O2 material pre-
pared under different synthetic conditions were studied.
2. Experimental
2.1. Recycling of cathode materials
The spent battery cathode material was alkali-dissolved from
the aluminum foil with sodium hydroxide solution, decomposed
at a high temperature of 700 °C and then acid leached with a
2 mol/L H2SO4 solution and 10% H2O2 (by volume) at 90 °C for
2 h. The obtained leaching solution contained Ni 25.2 g/L, Co
4.9 g/L, Al 0.68 g/L, and Cu 0.21 g/L. The copper ion impurity in acid
193
leaching solution was removed by copper extractant CP-150. The
effects of the following conditions on the extraction rate were
studied to determine the optimum set of conditions: the ratio of
organic phase to aqueous phase (O/A) (1:0.5, 1:1, 1:2, 1:3), pH
(1.5, 2, 2.5, 3, 3.5) and extractant concentrations (15%, 20%, 25%
30%, 35%). Appropriate amounts of nickel sulfate, cobalt sulfate
and aluminum sulfate were added into the raffinate to prepare
2 mol/L mixed salt solution with n(Ni):n(Co):n(Al) ratio of
80:15:5. Sodium hydroxide solution (6 mol/L) was thoroughly
mixed with 28% volume fraction of concentrated ammonia to
obtain mixed alkali solution. The pH of the mixed salt solution
was adjusted to 8.5 using the mixed alkali solution at 50 °C for
10 min, and then the pH was maintained at 10.7 at 50 °C for
1.5 h to obtain the precipitate. The precipitate was dried at 60 °C
for 12 h and ground into fine powder. This precursor powder was
thoroughly mixed with lithium salt and then calcined in a muffle
furnace to obtain the regenerated cathode material. The following
set of conditions were varied and the effects on regeneration were
studied: different lithium sources (LiOH, Li2CO3), different addition
amounts of lithium carbonate (n (precursor):n (lithium carbonate)
= 1:1.05, 1:1.1, 1:1.15), different calcination temperatures (750 °C,
800 °C, 850 °C), and different calcination times (10 h, 15 h, 20 h).
When the single-factor experiments were carried out, the follow-
ing conditions were fixed: Li2CO3, n (precursor): n (lithium carbon-
ate) = 1:1.1, 800 °C, and 15 h. The entire process is depicted in
Fig. 1.
2.2. Characterization
The concentrations of various metal ions in the solutions were
determined by ICP-AES (Optima 7000DV, PerkinElmer, USA). The
pH values of the aqueous solutions were measured with a pH
meter (S220-Bio, Mettler Toledo, Switzerland). The structures of
the cathode materials were investigated by XRD (XRD-7000,
Rigaku, Japan). The morphology of the cathode material was
observed by SEM (JSM-5600LV, JEOL, Japan, conditions: operating
voltage 20 kV, amplification factor 100,000 times). The decomposi-
tion and synthesis process of the cathode material were analyzed
by DTA-TG (Labsys evo, France, conditions: 0–1000 °C, 10 °C/
min). The structure of the cathode material was analyzed by IR
(Nicolet-6700, Nicolet, USA, conditions: scan range 400–
4000 cm
1, resolution 4 cm
1). The valence state of elements in
the cathode material was analyzed by XPS (Sigma Probe X-ray,
THERMO VG, UK).
2.3. Electrochemical tests
Electrochemical tests were carried out by assembling a button
battery with the regenerated battery material as the cathode mate-
rial. Polar plate preparation: The cathode material and carbon
black were mixed uniformly in a mortar. Then, polyvinylidene flu-
oride was added, and the ratio of the three materials was 8:1:1.
Then, N-methylpyrrolidone was added and the mixture was
ground into a thick paste. The material was coated on an aluminum
foil and placed in a forced air oven at 70 °C to dry. After that, it was
processed into a tablet by a tablet press. A microtome was used to
cut the tablet into small pieces of 8 mm in diameter, which were
bagged and stored for later use. Battery assembly: the negative
electrode was a metal piece, the diaphragm was an imported
polypropylene microporous membrane, the electrolyte was
1.0 mol L
1 LiPF6, the solvent was EC + DMC + DEC (volume ratio
1:1:1), and the button batteries were installed under Etelux inert
gas. The battery assembly sequence was: first the negative shell,
spring piece, and gasket were placed. Next, the cathode material
was placed and the electrolyte was added. Then, the diaphragm
was placed and the electrolyte was added. Finally, the lithium
194 Y. Wang et al. / Waste Management 95 (2019) 192–200

Fig. 1. Flow chart of the regeneration process.

sheet and the cathode shell were placed. Electrochemical impe-
dance spectroscopy (EIS) was also performed on the Autolab elec-
trochemical workstation with the frequency range from 100 kHz to
0.01 Hz. Galvanostatic cycling tests were carried out on the LAND
CT2001A battery tester with the voltage between 2.5 and 4.3 V
(versus Li+/Li) at the current density of 0.5 C (1 C = 278 mA g
1).
3. Results and discussion
3.1. Impurity removal
Fig. 2 shows the copper ion removal curves in terms of phase
ratio (extractant agent concentration 30%, pH = 1.5), pH (extractant
agent concentration 30%, phase ratio 2:1), and extractant agent
concentration (pH = 1.5, phase ratio 2:1).
The extraction rate of copper decreased from 97.6% to 29.5% as
the phase ratio varied from 1:0.5 to 1:4, as shown in Fig. 2a. More-
over, when the O/A ratio was 1:0.5, the extraction rates of lithium,
nickel, cobalt and aluminum ions were 13%, 8.3%, 10.2% and 11.7%,
respectively. Therefore, the O/A ratio of 1:0.5 was appropriate for
the maximum copper impurity removal.
The extraction rate of copper decreased from 100% to 95.2%
and then increased again to 100% when the pH was varied from
1.5 to 3.5, as shown in Fig. 2b. However, when the pH was 3,
the extraction rates of lithium, nickel, cobalt and aluminum ions
were 4.3%, 6.7%, 10.2%, and 8.82%, respectively. Therefore, the pH
value of 3 was appropriate for the best effect of copper impurity
removal.
The extraction rate of copper increased from 71.4% to 100% and
then decreased to 76.19% as the extraction agent concentration
was varied from 15% to 35%, as shown in Fig. 2c. However, when
the extraction agent concentration was 30%, the extraction rates
of lithium, nickel, cobalt and aluminum ions were 13%, 8.3%,
10.2%, and 11.7%, respectively. Therefore, the extraction agent con-
centration of 30% was appropriate for the best effect of copper
impurity removal.
In summary, the optimal experimental conditions for copper
extraction were determined as: O/A phase ratio of 2:1, extraction
agent concentration of 30%, and pH of 3.
3.2. SEM and XRD analyses of precursor
The precursor was obtained by coprecipitation of the acid leach-
ing solution after removal of copper. Fig. 3a presents the SEM
image of precursor, which shows agglomerated morphology with
partial polyhedral shape. As cathode material, morphology of the
precursor changed from agglomerated to polyhedron at high tem-
perature, promoting formation of polyhedral morphology of the
cathode material. Fig. 3b shows the XRD pattern of the precursor.
Diffraction peaks appeared at two-theta values of 19.18, 32.94,
38.44, 51.94, 58.87, 62.45, 70.18 and 72.69, which were slightly
offset from the characteristic diffraction peaks of pure Ni(OH)2
(PDF#01-1047) and no impurity peaks were present. These data
suggested the successful replacement of Ni atoms by Co and Al
atoms in the crystal lattice of Ni(OH)2 crystal, forming solid solu-
tion of nickel cobalt aluminium hydroxide (Liu et al., 2011).
3.3. DTA-TG analyses of precursor and lithium carbonate
Fig. 4a depicts the DTA-TG curve of mixture of precursor and
lithium carbonate. Three distinct endothermic peaks were seen
in DTA curve over the entire temperature range. As the tempera-
ture increased, the first obvious endothermic peak appeared at
about 100 °C, and the corresponding TG curve decreased rapidly.
This step was associated with volatilization of adsorbed water
molecules in the mixture and decomposition of crystal water.
The second obvious endothermic peak appeared between 200
and 400 °C, and the TG curve decreased rapidly. At this time,
decomposition of the precursor Ni0.8Co0.15Al0.05(OH)2 occurred
according to the following reaction:
D
Ni0:8 Co0:15 Al0:05 ðOHÞ2 !ðNi0:8 Co0:15 Al0:05 ÞO þ H2 O ð8Þ
The third obvious endothermic peak appeared between 600 °C
and 800 °C, corresponding to the melting and decomposition of
Li2CO3. The declining rate of the TG curve gradually increased,
and the weight loss rate was smaller than the theoretical value
due to complete decomposition of Li2CO3. As Ni2+ and Co2+ were
initially oxidized by oxygen from air into Ni3+ and Co3+, the follow-
ing chemical reaction (9) occurred in this temperature range:
 Y. Wang et al. / Waste Management 95 (2019) 192–200 195

Fig. 2. Copper ion removal curves: (a) phase ratio, (b) pH and (c) extraction agent concentration.

Fig. 3. SEM image (a) and XRD pattern (b) of the precursor.

D Sunose (KAS) method. KAS method is the most commonly used

ðNi0:8 Co0:15 Al0:05 ÞO þ O2 ! ðNi0:8 Co0:15 Al0:05 Þ2 Ox ð9Þ
type of multiple scanning rate method (Song et al., 2008). The basic
As temperature continued rising, the DTA curve decreased non-isothermal kinetic relationship in thermal analysis can be
rapidly between 750 °C and 880 °C but the TG curve decreased expressed by Eqs. (1) and (2):
slowly. This temperature range could be interpreted as the diffu-
sion process of ions to form crystallized hexagonal layered struc- da=dt ¼ kf ðaÞ; ð1Þ
ture. Above 880 °C, the TG curve declined rapidly and the weight
started to decrease again. At this temperature, lithium was volati- f ðaÞ ¼ ð1
aÞn ; ð2Þ
lized and crystal structure of the material started to be destroyed The Arrhenius formula is expressed by Eq. (3):
(Zhang et al., 2012). Therefore, the synthesis temperature of the
material should not exceed 880 °C. k ¼ Aexpð
E=RTÞ ð3Þ
Eq. (1) is the differential equation used for solving dynamic
3.4. Kinetics of decomposition reaction of precursor and lithium problems and Eq. (2) represents the dynamic equation for non-
carbonate isothermal conditions. After a series of transformations by Kis-
singer process, Eq. (4) was obtained:
Thermal decomposition reaction kinetics of the precursor and
lithium carbonate were further studied by Kissinger-Akahira- ðEdT=dtÞ=RT 2 ¼ Anð1
aÞn
1 expð
E=RTÞ ð4Þ
196 Y. Wang et al. / Waste Management 95 (2019) 192–200
Fig. 4. DTA-TG profile (a), DSC curve of the precursor at different heating rates (b) and the fitted line using the Kissinger method (c) of precursor and lithium carbonate.
where a is the reaction conversion rate, A is the pre-factor, T is the
thermodynamic temperature, E is the reaction activation energy, R
is the ideal gas constant (R = 8.314 J mol/K), and n is the reaction
order.
Kissinger method is related to the peak temperature. Assuming
that maximum reaction rate of thermal decomposition occurred at
peak position of the DSC curve, the corresponding temperature is T
and conversion rate is a. Then, n(1
a)n
1 will be independent of b
(heating rate) according to Kissinger method, and its value will be
approximately 1. Thus, Eq. (5) can be obtained from Eq. (4):
Eb=RT 2 ¼ Aexpð
E=RTÞ; ð5Þ
The logarithm of Eq. (5) on both sides will yield Eq. (6):
lnðb=T 2 Þ ¼ lnAR=E
E=RT i ; i ¼ 1; 2; 3; 4; ð6Þ
Eq. (6) represents the Kissinger formula. Using DSC curve
recorded at different heating rates, the peak temperature T values
were obtained and the results are compiled in Table 1. The plot of
ln(b/T2)
1/T yielded a straight line, and Ek was obtained from the
slope and Ak from the intercept.
Fig. 4b presents the DSC curves of the precursor at different
heating rates, and Table 1 shows the corresponding peak tempera-
tures. Fig. 4c shows the fitted line using the Kissinger method for
precursor and lithium carbonate. The straight line obtained by Kis-
singer method showed good fitting with R2 of 95.691%, which indi-
cates that the thermal decomposition of the precursor was in
accordance with kinetic model of KAS.
Table 1
Peak temperatures of the DSC curves of the precursor at different heating rates.
Heating rate /(Kmin
1) 3 5
Peak temperature /K 608.791 618.929
The activation energy Ek of the exothermic peak was calculated
as 24 kJ/mol, indicating that the precursor was relatively easy to
decompose.
3.5. Characterization of regenerated cathode material
LiNi0.8Co0.15Al0.05O2
3.5.1. SEM analysis
Figs. S1–S3 in the supporting information file show the SEM
images of regenerated LiNi0.8Co0.15Al0.05O2 powder. It can be seen
from the images that the powder morphology was a polyhedral
shape. Moreover, the particle size increased first and then
decreased with the increase in amount of lithium carbonate and
calcination time. With the increase in temperature, the particle
size increased gradually. The increasing trend was not obvious
when the temperature was 800 °C and 850 °C. When lithium car-
bonate content was low, calcination temperature was too low or
calcination time was insufficient, the particles could not fully
develop. Therefore, the particle size was smaller. On the other
hand, when the lithium carbonate content was high, calcination
temperature was too high or calcination time was too long, then
the development of particles was limited, the surface morphology
of particles was affected, and the structure was destroyed. There-
fore, the content of lithium carbonate, calcination temperature
and calcination time had important effects on the morphology of
the material.
10 15 20
623.223 627.613 634.122
 Y. Wang et al. / Waste Management 95 (2019) 192–200
3.5.2. XRD analysis
As Ni2+ in high-nickel materials is difficult to completely con-
vert into Ni3+ during synthesis, Ni2+ remaining in LiNi0.8Co0.15-
Al0.05O2 could easily replace Ni3+, inducing lower cationic electric
charge. To maintain the electric charge balance, part of Ni2+ would
occupy the position of Li+, and thus, cation mixing between Ni2+
and Li+ would easily occur. The cation mixing would deteriorate
the thermal stability of the material and induces large initial irre-
versible capacity. In order to inhibit cationic mixing and improve
the positive valence ions of materials, increasing the ratio of
lithium was proposed as a suitable method. Therefore, the effects
of lithium source, lithium content, calcination temperature and
calcination time on the structure of LiNi0.8Co0.15Al0.05O2 were stud-
ied. The results are presented in Fig. 5 and Table S1 in supporting
information file.
The (0 0 3) XRD peak is associated with hexagonal structure,
while the (1 0 4) peak reflects the sum of both hexagonal and cubic
structures. Thus, the ratio of intensities of (0 0 3) to (1 0 4) peaks
corresponds to the mixing status of lithium ions and nickel ions,
with theoretical value above 1.20. The ratio of the spent battery
cathode material for this study is far below 1.2, only 0.59, which
can reflect that the order of the structure has been damaged and
must be recycled, as shown in Fig. S5. Smaller ratios between the
sum of (0 0 6) and (0 1 2) peak intensity with (1 0 1) peak intensity
would mean layered structure with higher degree of order. The
separation between (0 1 8) and (1 1 0) peaks could also provide
information regarding the electrochemical performances. The c/a
value of the material structure is positively related to the layered
structure stability of the material. At c/a > 4.899, the crystal struc-
ture stability of the material should be good, and larger ratios
reflect better structural stability of the material (Zhang et al.,
2018; Li et al., 2015).
Fig. 5. XRD patterns of cathode material under different conditions: (a) different lithium sources, (b) different ratios of precursors to lithium carbonate, (c) different
calcination temperatures and (d) different calcination times.
197
In summary, the optimum conditions were found to be: lithium
carbonate as lithium source, precursor to lithium carbonate ratio of
1:1.1, temperature of 800 °C and calcination time of 15 h.
3.5.3. IR analysis
Fig. S6 in the supporting information file shows the IR spectrum
of regenerated LiNi0.8Co0.15Al0.05O2 obtained under different condi-
tions. The types of bonds in the regenerated cathode material may
be classified into three types, OAH bond, MAO bond (M = Ni, Co,
Al), and C@O double bond. It can be seen from the figure that there
was a strong peak at 500–1000 cm
1 corresponding to the MAO
bond in MOx (M = Ni, Co, Al). This result indicated that an oxide
of nickel, cobalt or aluminum was formed. Two peaks were
observed at 1000–2000 cm
1, corresponding to C@O in CO2
3 . The
peak intensity of C@O double bond was the lowest at the condi-
tions of 800 C, 1:1.1 and 15 h, which indicated that there was less
lithium carbonate residue in this regenerated material, and that
the synthesis reaction proceeded to completion. There was a weak
absorption peak at 3500–4000 cm
1, corresponding to OAH bond
in the material, which indicates that the material contained a small
amount of adsorbed water (Liu et al., 2013).
3.5.4. XPS analysis
Ni2+ has larger radius than Ni3+. High content of Ni2+ in the cath-
ode material of LiNi0.8Co0.15Al0.05O2 during charge and discharge
processes would induce oxidation of Ni2+ to Ni3+ with smaller
radius, causing collapse of the hexagonal layered structure. Hence,
lithium ion insertion and extraction would be hindered, resulting
in poor electrochemical performances. Therefore, it is desirable to
have more Ni3+ initially in the cathode material (L. Li et al., 2017;
X. Li et al., 2017; Zhao et al., 2018). It can be concluded from
Fig. 6 and Table S2 in supporting information file that the highest
198 Y. Wang et al. / Waste Management 95 (2019) 192–200
Fig. 6. XPS spectra and corresponding fitting curves of Ni 2p (a): 750 °C, 15 h, and 1:1.1. (b) 800 °C, 15 h, and 1:1.1. (c) 850 °C, 15 h, and 1:1.1.
Ni3+ and lowest Ni2+ contents in the material were achieved under
the following calcination conditions: 800 °C, 15 h and n (precur-
sor):n (lithium carbonate) = 1:1.1.
3.6. Electrochemical tests
3.6.1. First charge and discharge tests
Fig. S1 and Table S3 in supporting information file show the first
charge and discharge test results of LiNi0.8Co0.15Al0.05O2 as cathode
material prepared under different conditions. Comparison of the
specific capacities of the first charge and discharge indicated that
relatively high charge and discharge platform was obtained under
the conditions of 800 °C, 15 h and n (precursor):n (lithium carbon-
ate) = 1:1.1. These data agreed well with the results of XRD and
SEM analyses of LiNi0.8Co0.15Al0.05O2 cathode material.
3.6.2. Electrochemical impedance spectroscopy (EIS) tests
Electrochemical impedance spectroscopy (EIS) tests were per-
formed on LiNi0.8Co0.15Al0.05O2 obtained at temperatures of
750 °C, 800 °C and 850 °C after 20 cycles. The results are shown
in Fig. 7a. The impedance spectrum consisted of two parts, a
high-frequency semicircle and a low-frequency linear line. The
high-frequency semicircle represents the interface impedance or
membrane impedance, while the low-frequency linear line repre-
sents lithium ion diffusion impedance (W.M. Liu et al., 2018; T.
Chen et al., 2018; X. Chen et al., 2018). As shown in Fig. 7a, the
interface impedance values were 171 X, 119 X and 137 X for the
materials obtained at 750 °C, 800 °C and 850 °C, respectively. The
results show that the interface impedance of regenerated cathode
material was the smallest when the temperature was 800 °C.
Fig. 7a shows that the slope of the low frequency linear line was
the largest when the temperature was 800 °C. Thus, the lithium
ion diffusion impedance of the regenerated cathode material pre-
pared at 800 °C was smaller than that of the Li+ cathode material
prepared at other temperatures.
3.6.3. Electrochemical testing under optimal conditions
Charge and discharge experiments were performed on LiNi0.8-
Co0.15Al0.05O2 obtained under the optimized conditions at the cur-
rent density of 0.5 C. The results are shown in Fig. 7b and c. The
first charge specific capacity was 248.7 mAh/g, and the first dis-
charge specific capacity was 162 mAh/g. The discharge specific
capacity remained at 149.1 mAh/g after 50 cycles with capacity
retention rate of 92%.
Fig. 7d depicts the dQ/dV curve, which showed only one distinct
redox couple of oxidation peak and reduction peak in the voltage
range of 2.5–4.5 V. This indicates that the material did not change
from hexagonal to monoclinic structure and exhibited better inter-
calation and deintercalation reversibility (Xia et al., 2009). As the
cycle number increased, the oxidation peak shifted to the positive
direction while the reduction peak did not change significantly.
This may be caused by polarization phenomenon with increasing
cycle numbers. The polarization increased the electrical resistance,
and weakened the reversibility of intercalation and deintercalation
of lithium ions.
4. Conclusions
The optimal experimental conditions for copper extraction from
spent battery material were determined to be: O/A phase ratio of
2:1, extraction agent concentration of 30%, and pH value of 3.
The prepared precursor exhibited successful replacement of Ni
atoms by Co and Al atoms in the crystal lattice of Ni(OH)2 crystal,
 Y. Wang et al. / Waste Management 95 (2019) 192–200
Fig. 7. (a) Alternating current impedance analysis. (b) Charge and discharge curves. (c) Cycle number-specific capacity curve. (d) dQ/dV curve analysis.
forming solid solution of nickel cobalt aluminium hydroxide.
According to the results of DTA-TG, SEM, XRD, IR, and XPS analyses,
the regenerated LiNi0.8Co0.15Al0.05O2 cathode material with highest
content of Ni3+, most stable layered structure and highest crys-
tallinity was obtained when the material was prepared under the
following conditions: 800 °C, 15 h and n(precursor):n(lithium car-
bonate) = 1:1.1. The activation energy Ek of precursor decomposi-
tion was calculated as 24 kJ/mol. The EIS results showed that the
Li+ diffusion impedance of the regenerated LiNi0.8Co0.15Al0.05O2
obtained at 800 °C was smaller than that of material prepared at
other temperatures. For the regenerated LiNi0.8Co0.15Al0.05O2
obtained under the optimal conditions, the first charge specific
capacity was 248.7 mAh/g, the first discharge specific capacity
was 162 mAh/g, the discharge specific capacity after 50 cycles
was maintained at 149.1 mAh/g with capacity retention rate of
92%, and the regenerated cathode material had better intercalation
and deintercalation reversibility. Therefore, this study has demon-
strated the successful regeneration of cathode material from spent
battery material, which could be useful for industrial applications
in the future.
Acknowledgement
This work was supported by National Natural Science Founda-
tion of China (51621003), the Construction Project for National
Engineering Laboratory for Industrial Big-data Application Tech-
nology (312000522303) and Green Manufacturing Project of Min-
istry of Industry and Information Technology.
Appendix A. Supplementary material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.wasman.2019.06.013.
199
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