Journal of Power Sources 282 (2015) 429e436

Contents lists available at ScienceDirect

Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

Surface-modified concentration-gradient Ni-rich layered oxide

cathodes for high-energy lithium-ion batteries
Jin-Yun Liao, Arumugam Manthiram*
Materials Science and Engineering Program & Texas Materials Institute, The University of Texas at Austin, Austin, TX 78712, USA

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Concentration-gradient Ni-rich
layered oxides have been prepared
for lithium-ion batteries.

The material comprises a Ni-rich core
and a Mn-rich surface.

Concentration-gradient sample
shows superior electrochemical
performance.

A thin layer of Al2O3 is applied on
concentration-gradient sample for
further protection.

Al2O3 coated sample offers improved
cyclability, rate capability, and ther-
mal stability.

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

Article history: Concentration-gradient layered Li[Ni0.8Co0.2]0.7[Ni0.2Mn0.8]0.3O2 oxide with Ni-rich in the core and Mn-
Received 28 November 2014 rich in the surface region has been synthesized through a condition-controlled tank reactor reaction.
Received in revised form While the Ni-rich core facilitates high capacity, the Mn-rich surface enables good cyclability and thermal
30 January 2015
stability. The concentration-gradient sample exhibits a higher capacity of 204 mA h g1 at C/5 rate with
Accepted 13 February 2015
Available online 16 February 2015
superior cyclability and thermal stability compared to the constant-concentration LiNi0.62Co0.14Mn0.24O2
sample, which has the same net Ni, Co, and Mn contents as those present in the concentration-gradient
sample. The concentration-gradient sample was also coated with a thin layer of Al2O3 on the surface to
Keywords:
Lithium-ion batteries
stabilize the electrode/electrolyte interface and thereby further improve the electrochemical perfor-
Cathodes mance. Both the structural (gradient structure) and surface (Al2O3 coating) modifications help suppress
Layered oxides side reactions between electrode and electrolyte and reduce the decline in voltage during cycling. The
Nickel-rich oxides Al2O3-coated concentration-gradient sample exhibits improved long-term cyclability, rate capability, and
Concentration-gradient oxide thermal stability compared to the pristine uncoated sample.
Surface coating © 2015 Elsevier B.V. All rights reserved.

1. Introduction production of high-energy-density lithium-ion batteries (LIBs).

Since the development of the first LIB by Sony in 1991, extensive
The ever increasing demand for portable telecommunication research has been carried out over the 14 years to replace the
devices, laptops, and hybrid vehicles has given rise to the increased layered LiCoO2 cathode because of its limitations that include high
cost, low capacity, toxicity, and chemical instability at high poten-
tials [1e7]. In the past, LiNiO2 has been considered as an attractive
* Corresponding author. cathode material due to its higher discharge capacity and lower
E-mail address: [email protected] (A. Manthiram).

http://dx.doi.org/10.1016/j.jpowsour.2015.02.078
0378-7753/© 2015 Elsevier B.V. All rights reserved.
430 J.-Y. Liao, A. Manthiram / Journal of Power Sources 282 (2015) 429e436

cost. However, LiNiO2 also has several disadvantages, such as dif- [Ni0.8Co0.2](OH)x was continuously reacted with a solution con-
ficulties to keep all nickel as Ni3þ and obtain a well-ordered ma- taining required amounts of NiSO4∙6H2O and MnSO4∙H2O (cationic
terial, poor cycling performance, and unsatisfactory thermal ratio of Ni:Mn ¼ 2:8). The co-precipitated precursor powders of
stability [8e11]. To overcome these difficulties, much effort has [Ni0.8Co0.2](OH)x, [Ni0.62Co0.14Mn0.24](OH)x and [Ni0.8C-
been focused on composition modifications, synthesis condition o0.2]0.7[Ni0.2Mn0.8]0.3(OH)x were filtered, washed with deionized
optimization, and surface modifications to improve the perfor- water, and dried at 100  C over night. Finally, these metal hydroxide
mance of LiNiO2. For example, the partial substitutions of Co, Mn, or precursors were thoroughly mixed with 3% excess LiOH∙H2O
other ions for Ni is one of the approaches that has been pursued to (Li:M ¼ 1.03:1) to compensate for any volatilization of Li during
lower the cost and improve the reversible capacity and structural synthesis and heated at 800  C for 15 h in air.
stability during cycling [5,12e14]. To produce the Al2O3 coating on the concentration-gradient
Particularly, the composition LiNi0.8Co0.2O2 has attracted much sample, 0.06 g of aluminum isopropoxide was dissolved in 20 mL
attention as 4 V cathode materials in the past years [15e17]. of ethanol and stirred at 50  C for half an hour. Then 2 g of the
However, the Li1-xNi0.8Co0.2O2 electrodes are structurally unstable prepared concentration-gradient oxide powder was slowly added
during thermal runaway reactions due to oxygen release from the and thoroughly mixed for another hour. The obtained mixture was
host structure. In addition, the released oxygen and the strong dried at 110  C overnight and then heated at 400  C for 5 h.
oxidizing power of Ni4þ ions can cause slow decomposition of the
liquid organic electrolyte and lead to safety problems [15,18e20].
2.2. Materials characterization
These issues make it difficult for conventional Ni-rich cathode
materials to be adopted in practical cells for large-scale applications
The phase-purity and crystal structure of the obtained materials
such as electric vehicles. Recently, Sun's group reported Ni-rich
were studied with X-ray diffraction (XRD, Phillip) with Cu Ka radi-
concentration-gradient cathode materials, where the concentra-
ation from 10 to 80 at a scan rate of 0.03 s1. Field emission
tion of Ni decreases and Mn increases gradually from the center
scanning electron microscopy (FE-SEM, Quanta 650), scanning
towards the surface to improve the cycle life and safety compared
to the constant-concentration nickel-rich oxides [21e23]. These
materials have shown superior performance and are promising.
Further improvements could be made by coating the surface of
such cathodes with an inert material to form an artificial protective
layer that serves as a substitute for the solid electrolyte interphase
(SEI) and also stabilizes the electrode/electrolyte interface [24e26].
As one of the excellent coating materials, Al2O3 has been employed
to coat the surface of both the anode and cathode materials for LIBs
[27e30].
We present here the synthesis, characterization, and electro-
chemical evaluation of the concentration-gradient Li[Ni0.8C-
o0.2]0.7[Ni0.2Mn0.8]0.3O2 cathodes in which the LiNi0.8Co0.2O2 core
and LiNi0.2Mn0.8O2 surface could facilitate, respectively, high ca-
pacity and cycle stability. The concentration-gradient sample is
then coated with Al2O3 via a chemical process to further improve
the electrochemical performance. The performances of the
concentration-gradient sample before and after coating with Al2O3
are compared with those of a constant-concentration sample that
has the same net Ni, Co, and Mn contents as in the concentration-
gradient sample.

2. Experimental

2.1. Materials synthesis

The constant-concentration [Ni0.8Co0.2](OH)x and [Ni0.62C-

o0.14Mn0.24](OH)x were synthesized by a one-step co-precipitation
process. The appropriate amounts of NiSO4∙6H2O, CoSO4∙7H2O,
and MnSO4∙H2O dissolved in deionized water were used as the
starting solutions for [Ni0.8Co0.2](OH)x (cationic ratio of
Ni:Co ¼ 8:2) and [Ni0.62Co0.14Mn0.24](OH)x (cationic ratio of
Ni:Co:Mn ¼ 0.62:0.14:0.24), respectively. The solution was then
pumped continuously into a stirred tank reactor under nitrogen
atmosphere. At the same time, 2.0 M aqueous NaOH and desired
amount of ammonium hydroxide solution were pumped into the
reactor. The mole ratio of metal ions to ammonia was 2:1, and the
pH was controlled to be at 11 with aqueous NaOH. The concen-
tration of the solution, pH, temperature, and stirring speed of the
solution in the tank reactor were carefully controlled for repro-
ducibility. The concentrations of metal ions and ammonia solutions
were 2 mol L1 and 0.5 mol L1, respectively. For the concentration- Fig. 1. (a) XRD patterns of CC, CG. and CG-Al2O3 samples and (b) Rietvelt refinement
gradient [Ni0.8Co0.2]0.7[Ni0.2Mn0.8]0.3(OH)x synthesis, the resulting results of the XRD data of the CG-Al2O3 sample.
 J.-Y. Liao, A. Manthiram / Journal of Power Sources 282 (2015) 429e436 431

Fig. 2. SEM images of the (a) CC, (c) CG, and (e) CG-Al2O3 samples. (b) EDS line-scanning profile of Mn content relative to the Ni content in the CC particle. (d) EDS line-scanning
profile of the Mn content relative to the Ni content in the CG particle. (f) EDS spectra of the Al2O3-coated CG particle.

transmission electron microscopy (STEM, S-5500), and transmission fabricated with a mixture consisting of the synthesized layered
electron microscopy (TEM, JEOL 2010F) were used to examine the oxide powder (80 wt.%), carbon black (10 wt.%), and polyvinylidene
morphologies, crystalline structures, and elemental distributions of fluoride (PVDF) (10 wt.%) in Nmethyl-2-pyrrolidone (NMP). The
the samples. The total average chemical compositions in the syn- slurry was spread onto an aluminum foil and dried in a vacuum
thesized samples were analyzed with a Varian 715-ES inductively oven at 110  C. The discharge-charge cycling was performed be-
coupled plasma-atomic emission spectrometer (ICP-AES). tween 4.5 and 2.7 V (vs. Li/Liþ) at room temperature at different C-
rates of C/5 to 5C with an Arbin Instruments cycler
(1C ¼ 180 mA g1). Cyclic voltammetry (CV) testing was performed
2.3. Electrochemical evaluation between 4.5 and 2.7 V (vs. Li/Liþ) with a scan rate of 0.1 mV s1
(VoltaLab PGZ 402, Radiometer Analytical).
The electrochemical characterizations were performed with
2032-type coin cells assembled in an Ar-filled glove box with the
synthesized cathode materials, Li metal anode, 1 M LiPF6 in 2.4. Thermal properties
ethylene carbonate (EC)/dimethyl carbonate (DMC) (1/1 by vol-
ume) electrolyte, and polypropylene separators. The cathode was The thermal stability of the samples was analyzed with
432 J.-Y. Liao, A. Manthiram / Journal of Power Sources 282 (2015) 429e436

Fig. 3. TEM and HRTEM images of (a) CC, (b) CG, and (c,d) CG-Al2O3 samples.

differential scanning calorimeter (DSC). For the DSC experiments, cause any significant changes in the layered oxide.
the assembled cells were charged to 4.3 V and disassembled in an The SEM images of the samples shown in Fig. 2 and Fig. S2
Ar-filled glove box, followed by removing the wet cathode and indicate spherical morphology and the maintenance of the parti-
sealing it into a stainless steel crucible with a perforated lid and a cle size of the hydroxides after the high-temperature treatment
gold foil seal. The DSC data were then collected with a Netzch STA with lithium hydroxide. Fig. 2b and d show the energy dispersive
449 thermal analysis system at a heating rate of 10  C min1 up to spectroscopic (EDS) line scan results of, respectively, the CC and CG
400  C and nitrogen purge gas. particles. The relative elemental Mn/Ni intensity ratio across the CG
sample particle increases from the center to the surface, while that
3. Results and discussion of the CC sample particle almost remains constant from the center
to the surface. This indicates the formation of a Mn-rich phase
The XRD patterns of the synthesized concentration-gradient Li along the surface and Ni-rich phase along the center in the CG
[Ni0.8Co0.2]0.7[Ni0.2Mn0.8]0.3O2 (hereafter designated as CG) and the sample. The Al2O3-coating layer can hardly be seen in the SEM
constant-concentration LiNi0.62Co0.14Mn0.24O2 (hereafter desig- image shown in Fig. 2e due to the rather small thickness. However,
nated as CC) samples are presented in Fig. 1, and the patterns of the the existence of Al2O3 in the coated sample can be evidenced by the
corresponding hydroxide precursors are given in Fig. S1. All of the EDS data illustrated in Fig. 2f. The carbon content seen is due to the
observed peaks of the synthesized oxides in Fig. 1 could be indexed carbon tape used during SEM characterization.
on the basis of the hexagonal a-NaFeO2 structure with R-3m space Fig. 3 shows the TEM and high-resolution TEM (HRTEM) images
group as seen in Fig. 1. Although the CG sample was synthesized by of the three synthesized samples. Both the CC and CG samples in
a two-step synthesis with two different hydroxide compositions at Fig. 3a and b display a bare and clean surface and an apparent
the interior and exterior, cationic diffusion could occur during the layered structure with an interplanar spacing of ca. 0.47 nm cor-
high-temperature firing, so we presume a smooth variation in responding to the (003) plane. In order to determine the thickness
cationic compositions from the interior to the exterior without any of the Al2O3 layer, the Al2O3-coated CG particle was observed by
abrupt changes at the interface between the two compositions. The TEM as well. The TEM micrograph in Fig. 3c shows that the size and
Al2O3-coated CG sample (hereafter designated as CG-Al2O3) also morphology of the layered oxide particles are maintained during
displays a pattern similar to the uncoated samples without any the Al2O3 coating process. The high magnification TEM image of the
extra peaks due to the smaller amount and/or the poor crystallinity outer edge of the particle (Fig. 3d) indicates an Al2O3 coating
of Al2O3. Both the coated and uncoated CG samples show similar thickness of around 10 nm.
lattice parameters of, respectively, a ¼ 2.875 and c ¼ 14.234 and The electrochemical performances of the as-prepared CC, CG,
a ¼ 2.874 and c ¼ 14.230, indicating that the Al2O3-coating did not and CG-Al2O3 cathodes were evaluated in half cells with a metallic
 J.-Y. Liao, A. Manthiram / Journal of Power Sources 282 (2015) 429e436 433

Fig. 4. First five CV cycle curves of the (a) CC, (b) CG, and (c) CG-Al2O3 electrodes at a
scan rate of 0.1 mV s1 between 2.7 and 4.5 V. Fig. 5. Chare-discharge curves between 2.7 and 4.5 V of the (a) CC, (b) CG, and (c) CG-
Al2O3 electrodes at room temperature.
434 J.-Y. Liao, A. Manthiram / Journal of Power Sources 282 (2015) 429e436

Fig. 6. Comparison of the cycling performances (C/5) of the three cathodes (a) at room
temperature and (b) at 55  C.
Fig. 7. (a) Rate performances at various current densities from C/5 to 5C
(1C ¼ 180 mA g1) of the CC, CG, and CG-Al2O3 electrodes and (b) electrochemical
lithium anode. Fig. 4aec show the cyclic voltammogram (CV) plots impedance spectra (Nyquist plots) of the CG, and CG-Al2O3 electrodes at the fully
of the first five cycles for all the three electrodes at a sweep rate of charged states after 10 chargeedischarge cycles.

0.1 mV s1 within a potential window of 2.7e4.5 V (vs. Li/Liþ). As

can be seen, all the three samples undergo similar Liþ-ion extrac-
suppresses the side reactions further and thereby decreases the
tion/insertion. The initial anodic peaks at about 4.2 V correspond to
voltage decline further. Thus, the data demonstrate that the
the oxidation process of Ni2þ/Co3þ to higher oxidation states. The
structural and surface modifications suppress side reactions of the
potential differences among the redox peaks of CC, CG, and CG-
cathode surface with the electrolyte and thereby improve lithium
Al2O3 at the fifth cycle are, respectively, 188, 157, and 150 mV,
diffusion through the surface and enhance the electrochemical
indicating a slightly reduced polarization of the electrode from CC
performance.
to CG to CG-Al2O3 samples [31,32]. These CV results are consistent
Fig. 6a shows the discharge capacity retention at C/5 of the CC,
with the increasing electrochemical performances of the samples
CG, and CG-Al2O3 samples. Although the CC sample retains only
from CC to CG to CG-Al2O3 shown below.
62.6% of its initial discharge capacity value after 100 cycles (fading
To investigate the structural stability of the cathodes, char-
from 206 mA h g1 to 129 mA h g1), the CG sample shows much
geedischarge profiles at C/5 rate at different stages of cycling, i.e.,
higher capacity retention of around 80% (fading from 204 mA h g1
1st, 2nd, 10th, 20th, and 50th cycles, are shown in Fig. 5aec and
to 163 mA h g1). The rapid capacity fade of the CC sample is due to
Fig. S3. The polarization loss and decline in voltage during cycling
the direct exposure of a high content of nickel ions on the surface to
decreases from the CC sample to the CG sample, and then to the CG-
the electrolyte at high potentials and the consequent chemical
Al2O3 sample. In the CG sample, the high Mn content (or low Ni
decomposition of both the surface of the electrode and the elec-
content) on the surface compared to that in the CC sample, sup-
trolyte. In the case of CG-Al2O3 sample, the first discharge capacity
presses the side reactions with the electrolyte and thereby de-
value of 195 mA h g1 increases slightly in the beginning four cy-
creases the insulating SEI layer formation and voltage decline
cles, which could be ascribed to the improvement in lithium-ion
during cycling. In the CG-Al2O3 sample, the Al2O3 coating
diffusion through the Al2O3 coating as the electrode is cycled.
 J.-Y. Liao, A. Manthiram / Journal of Power Sources 282 (2015) 429e436 435

be attributed to the consumption of electrolyte and deposition of

thick SEI film on the cathode surface during the chargeedischarge
process, leading to its fast capacity degradation and poor rate
capability.
The thermal stability and safety of cathode materials are critical
in considering them for practical cells. Accordingly, a differential
scanning calorimetry (DSC) study was performed on all three
cathodes after charging the cells to 4.3 V in the presence of 1 M
LiPF6/EC-DMC electrolyte. As shown in Fig. 8, no heat flow was
detected with DSC within the temperature range from 100  C to
150  C for all three samples. For the CC electrode, the onset tem-
perature of the exothermic reaction occurred at around 278  C,
with a peak at 286  C. The CG electrode, on the other hand, shows a
higher onset temperature (283  C) and slightly reduced heat gen-
eration compared to the CC electrode, which could be due to the
high Mn content in surface. The onset temperature of 283  C is very
close to the temperatures reported for the concentration-gradient
samples Li[Ni0.64Co0.18Mn0.18]O2 (270  C) and Li[Ni0.72Co0.18Mn0.10]
O2 (280  C) [21,33]. The slightly higher temperature of 283  C for
our sample may be ascribed to the lower Ni content of 0.62 and
higher Mn content of 0.24. For a comparison, as shown in Fig. S4,
Fig. 8. Differential scanning calorimetry traces showing the heat flow from the reac-
tion of the electrolyte with the CC, CG, and CG-Al2O3 electrodes charged to 4.3 V. the lower onset temperature of the Mn-free and high-nickel con-
tent LiNi0.8Co0.2O2 electrode indicates a very unstable cathode
material because of the easier oxygen release from the host struc-
More importantly, after being activated during the first several ture [34]. Interestingly, the CG-Al2O3 electrode shows the highest
cycles, the discharge capacity remains much more stable than the onset temperature and peak temperatures of, respectively, 295  C
other two uncoated electrodes. The discharge capacity decreases and 301  C. Also, the CG-Al2O3 electrode shows the lowest heat
from 197 mA h g1 in the 4th cycle to 175 mA h g1 in the 100th generation, which is consistent with the previous findings with
cycle. other Al2O3 coated sample [35].
To further assess the cyclability of the CG-Al2O3 electrode, an
aggressive test profile was selected where the cells were charged 4. Conclusions
up to 4.5 V and cycled at 55  C (Fig. 6b). All three electrodes show a
high initial discharge capacity of over 205 mA h g1. However, the A concentration-gradient cathode with a Ni-rich interior and a
CC electrode retains only 51% of its initial capacity after 50 cycles, Mn-rich surface has been synthesized and evaluated as a cathode in
while the CG and CG-Al2O3 samples retain, respectively, 81% and lithium-ion cells. It exhibits a high reversible capacity of
89% under the same cycling conditions. The high capacity retention 204 mA h g1with good cycling and thermal properties due to the
of the CG-Al2O3 electrode at high temperatures demonstrates the suppressed surface reaction with the electrolyte. Furthermore,
criticality of the cathode surface in contact with the electrolyte with surface-coating of the concentration-gradient sample with Al2O3
Ni-rich cathodes to obtain high performance. provides further improvement in cycle life, rate capability, and
Fig. 7a compares the rate capability of the CC, CG, and CG-Al2O3 thermal stability. The Al2O3-coated sample retained ~89% of the
samples from C/5 to 5C and then back to C/5 rate. Clearly, the rate capacity after 100 cycles at a C/5 rate. The results demonstrate the
capability increases from the CC to CG, and to CG-Al2O3 sample. The importance of having optimum surface compositions and struc-
superior rate capability of CG and CG-Al2O3 electrodes were further tures to enhance the commercial viability of the Ni-rich layered
analyzed by electrochemical impedance spectroscopy (EIS). The oxide cathodes for the next-generation of lithium-ion batteries.
Nyquist plots of the CG and CG-Al2O3 electrodes after the 10th cycle
shown in Fig. 7b exhibit a semicircle at the high-medium frequency Acknowledgment
region and an inclined line at the low frequency region, which
correspond, respectively, to interfacial resistance and Liþ-ion This work was supported by the Assistant Secretary for Energy
diffusion resistance inside the cathode particle. The impedance Efficiency and Renewable Energy, Office of Vehicle Technologies of
spectra were fitted with the equivalent circuit, shown as an inset in the U.S. Department of Energy under Contract No. DE-EE0006447.
Fig. 7b, where Rs represents the bulk electrolyte ionic resistance, The authors thank Dr. Yubao Zhao for assistance with TEM mea-
and Ri is associated with the interfacial resistance between the surements and Dr. Wang Hay Kan for assistance with XRD refine-
active material and electrolyte, which includes the charge-transfer ment work.
resistance (Rct) and any passivation surface film resistance (Rp). The
W (Warburg impedance) as reflected by the declined line at low Appendix A. Supplementary data
frequency corresponds to the Liþ ion diffusion resistance in the bulk
phase of the active material. The fitted result reveals the Rs values to Supplementary data related to this article can be found at http://
be 8.6 and 6.1 U for the CG sample and CG-Al2O3 sample, while the dx.doi.org/10.1016/j.jpowsour.2015.02.078.
Ri values are 75.5 and 51.3 U for CG sample and the CG-Al2O3
sample, respectively. This result suggests that the CG-Al2O3 elec- References
trode has relatively lower kinetic barrier for Liþ-ion insertion/
extraction, thus enabling a fast faradic reaction and the enhanced [1] Y.M. Wu, Z.H. Wen, J.H. Li, Adv. Mater. 23 (2011) 1126e1129.
high-rate performance of the CG-Al2O3 electrode compared to the [2] A.V. Murugan, T. Muraliganth, A. Manthiram, J. Phys. Chem. C 112 (2008)
14665e14671.
uncoated electrode (Fig. 7a). The uncoated CG electrode shows [3] A. Manthiram, K. Chemelewski, E.S. Lee, Energy Environ. Sci. 7 (2014)
higher electrolyte resistance and interfacial resistance, which can 1339e1350.
436 J.-Y. Liao, A. Manthiram / Journal of Power Sources 282 (2015) 429e436

[4] S. Venkatraman, A. Manthiram, Chem. Mater. 15 (2003) 5003e5009. J. Power Sources 217 (2012) 128e134.
[5] M.J. Lee, S. Lee, P. Oh, Y. Kim, J. Cho, Nano Lett. 14 (2014) 993e999. [20] S.A. Song, S.B. Park, J. Han, Jpn. J. Appl. Phys. 51 (2012) 31102.
[6] D.L. Li, M. Tian, R. Xie, Q. Li, X.Y. Fan, L. Gou, P. Zhao, S.L. Ma, Y.X. Shi, [21] Y.K. Sun, S.T. Myung, B.C. Park, J. Prakash, I. Belharouak, K. Amine, Nat. Mater.
H.T.H. Yong, Nanoscale 6 (2014) 3302e3308. 8 (2009) 320e324.
[7] L. Tao, G. Rousse, J.N. Chotard, L. Dupont, S. Bruyere, D. Hanzel, G. Mali, [22] Y.K. Sun, S.T. Myung, M.H. Kim, J. Prakash, K. Amine, J. Am. Chem. Soc. 127
R. Dominko, S. Levasseur, C. Masquelier, J. Mater. Chem. A 2 (2014) (2005) 13411e13418.
2060e2070. [23] Y.K. Sun, Z.H. Chen, H.J. Noh, D.J. Lee, H.G. Jung, Y. Ren, S. Wang, C.S. Yoon,
[8] D. Aurbach, M.D. Levi, E. Levi, B. Markovsky, G. Salitra, H. Teller, U. Heider, S.T. Myung, K. Amine, Nat. Mater. 11 (2012) 942e947.
V. Hilarius, Proceedings of the Symposium on Batteries for Portable Applica- [24] Y. Cho, J. Cho, J. Electrochem. Soc. 157 (2010) A625eA629.
tions and Electric Vehicles, vol. 97, 1997, pp. 941e952. [25] J.G. Li, Q. Zhang, C. Liu, X.M. He, Ionics 15 (2009) 493e496.
[9] M.Y. Song, H.U. Kim, H.R. Park, Ceram. Int. 40 (2014) 4219e4224. [26] Y.M. Chung, K.S. Ryu, B Korean Chem. Soc. 30 (2009) 1733e1737.
[10] X.H. Xiong, Z.X. Wang, G.C. Yan, H.J. Guo, X.H. Li, J. Power Sources 245 (2014) [27] X.M. He, W. Pu, F.H. Zhao, J.R. Ying, C.Y. Jiang, C.R. Wan, S.C. Zhang, Key Eng.
183e193. Mat. 336e338 (2007) 517e520.
[11] R. Kostecki, F. McLarnon, Electrochem. Solid St. 5 (2002) A164eA166. [28] S. Huang, J.P. Tu, X.M. Jian, Y. Lu, S.J. Shi, X.Y. Zhao, T.Q. Wang, X.L. Wang,
[12] S.H. Guo, H.J. Yu, P. Liu, X.Z. Liu, D. Li, M.W. Chen, M. Ishida, H.S. Zhou, J. Mater. C.D. Gu, J. Power Sources 245 (2014) 698e705.
Chem. A 2 (2014) 4422e4428. [29] S.C. Jung, Y.K. Han, J. Phys. Chem. Lett. 4 (2013) 2681e2685.
[13] F. Wu, N. Li, Y.F. Su, H.F. Shou, L.Y. Bao, W. Yang, L.J. Zhang, R. An, S. Chen, Adv. [30] E.M. Lotfabad, P. Kalisvaart, A. Kohandehghan, K. Cui, M. Kupsta, B. Farbod,
Mater. 25 (2013) 3722e3726. D. Mitlin, J. Mater. Chem. A 2 (2014) 2504e2516.
[14] M. Gu, I. Belharouak, J.M. Zheng, H.M. Wu, J. Xiao, A. Genc, K. Amine, [31] J.Y. Liao, X. Xiao, D. Higgins, D. Lee, F. Hassan, Z. Chen, Electrochim. Acta 108
S. Thevuthasan, D.R. Baer, J.G. Zhang, N.D. Browning, J. Liu, C.M. Wang, Acs (2013) 104e111.
Nano 7 (2013) 760e767. [32] L.J. Liu, Z.X. Wang, H. Li, L.Q. Chen, X.J. Huang, Solid State Ionics 152 (2002)
[15] J.R. Ying, C.R. Wan, C.Y. Jiang, J. Power Sources 102 (2001) 162e166. 341e346.
[16] K.C. Mahesh, G.S. Suresh, A.J. Bhattacharyya, T.V. Venkatesha, J. Electrochem. [33] Y.K. Sun, D.H. Kim, C.S. Yoon, S.T. Myung, J. Prakash, K. Amine, Adv. Funct.
Soc. 159 (2012) A571eA578. Mater. 20 (2010) 485e491.
[17] S.H. Wu, C.W. Yang, J. Power Sources 146 (2005) 270e274. [34] H. Arai, S. Okada, Y. Sakurai, J. Yamaki, Solid State Ionics 109 (1998) 295e302.
[18] G.T.K. Fey, P. Muralidharan, C.Z. Lu, Y.D. Cho, Solid State Ionics 176 (2005) [35] S. Oh, J.K. Lee, D. Byun, W.I. Cho, B.W. Cho, J. Power Sources 132 (2004)
2759e2767. 249e255.
[19] W.S. Yoon, K.W. Nam, D. Jang, K.Y. Chung, J. Hanson, J.M. Chen, X.Q. Yang,