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Core–shell nano-FeS2@N-doped graphene as an
Published on 16 November 2015. Downloaded by University of Newcastle on 14/12/2016 13:23:55.

advanced cathode material for rechargeable
Cite this: Chem. Commun., 2016,
52, 986 Li-ion batteries†
Received 25th September 2015,
Accepted 16th November 2015 Rui Tan,‡ Jinlong Yang,‡ Jiangtao Hu,‡ Kai Wang, Yan Zhao and Feng Pan*

DOI: 10.1039/c5cc08002a

www.rsc.org/chemcomm

We report the formation of core–shell nano-FeS2@N-doped graphene a controversial subject. FeS2, FeSx and S have been reported to
as a novel cathode material and its mechanism for use in rechargeable be the main products during the charge process,12,13 of which
Li-ion batteries. A benefit of the amount of FeS2 nano-crystals as the Li2Sx (2 r x r 8) may be formed during the charge–discharge
core for Li-ion storage with high capacity and using coated N-doped procedure and can dissolve in the electrolyte leading to unfavorable
graphene as the shell is that FeS2@N-graphene exhibits a remarkable side reactions with lithium metal. Owing to these reasons, the
1
specific energy (950 W h kg at 0.15 kW g 1) and higher specific power reported rechargeable cells that currently use FeS2 have low
1
(543 W h kg at 2.79 kW g 1) than commercial rechargeable LIB coulombic efficiency and degrade quickly. In order to improve
1
cathodes, as well as stable cycling performance (B600 W h kg at the performance of FeS2 cells, numerous approaches have been
0.75 kW g 1 after 400 cycles). tried, such as modifying the particle surface with conductive
materials to enhance the electronic conductivity,14,15 reducing
Rechargeable Li-ion cells play a pivotal role in energy storage and the size and changing shape of the pyrite FeS2 to shorten the
electronic devices. However because the energy density of commercial Li-ionic transfer length,16 utilizing all-solid-state electrolytes17
cathode materials (including LiCoO2, LiNi0.5Co0.2Mn0.3O2, LiMn2O4, and optimizing the polymer electrolyte18–20 to prevent unfavorable
LiFePO4, etc.) for Li-ion batteries is approaching an upper limit, shuttle effects of intermediate sulfur during operation. In previous
the next generation of cathodes need to be developed to satisfy studies, the cells with carbon-coated FeS2 have shown good
the increased demand for advanced Li-ion cells.1–4 performance and long-term stability at high current rate, indicating
Among the advanced electrode materials based on metal that low cost carbon-coated pyrite FeS2 is a promising candidate
sulfides,5–8 pyrite FeS2 is an interesting cathode material for a for commercial Li-ion batteries. For instance Yan Yu’s group21
new type of Li-ion battery which has lots of advantages such as developed a facile way to prepare FeS2@porous C-nanooctahedra,
high theoretical capacity, good thermal stability, abundance in which exhibit superior rate capability (at 5 C, 256 mA h g 1
nature, being environmentally benign and its safety. By reaction obtained) and stable cycling performance (at 0.5 C, 495 mA h g 1
with four Li-ions, pyrite FeS2 can provide 890 mA h g 1 (FeS2 + obtained after 50 cycles). Se-Hee Lee’s group22 used a polyacryloni-
4Li+ + 4e - Fe + 2Li2S), which is about 5 times the specific capacity trile (PAN) matrix to modify the FeS2 surface and to accommodate
of LiFePO4 (170 mA h g 1). Based on the advantage of its remarkably the volume expansion of FeS2 during the charge–discharge
high capacity for Li-ion storage, currently, pyrite FeS2 has been procedure. Due to the low conductivity of the PAN matrix, the
widely utilized in commercial primary batteries and shows remark- specific capacity of FeS2@PAN is still low. A composite of FeS2
able electrochemical performance.9 Recently, pyrite FeS2 has been microspheres@reduced graphene oxide was studied as a Li-ion
investigated as secondary Li-ion cell cathodes or anodes.10,11 cell anode by Chun-Sing Lee’s group, which showed high
However, the main problems associated with FeS2 being capacity and long life performance.11 They obtained 380 mA h g 1
applied in rechargeable Li-ion cells include the polysulfide at 10 C (8.9 A g 1) over 2000 cycles. In addition, doping of
dissolution in electrolyte, low conductivity and large volume heteroatoms (N, S, P, B, etc.) in the graphene shell23–25 can
expansion. The mechanism of performance of pyrite FeS2 is still improve its conductivity, which could be used to further
optimize the electrochemical performance of pyrite FeS2.
School of Advanced Materials, Peking University, Peking University Shenzhen Herein, for the first time we report a facile and novel method
Graduate School, Shenzhen 518055, China. E-mail: panfeng@pkusz.edu.cn;
to prepare pyrite nano-FeS2 wrapped in an N-graphene framework
Tel: +86-755-26033200
† Electronic supplementary information (ESI) available: Experimental procedures,
(core–shell nano-FeS2@N-graphene). The nano-size FeS2 has a short
theoretical details, figures and tables. See DOI: 10.1039/c5cc08002a Li-ionic diffusion distance, the N-graphene shell has optimized
‡ These authors contributed equally to this work. electronic conductivity to enhance structure stability, and the

986 | Chem. Commun., 2016, 52, 986--989 This journal is © The Royal Society of Chemistry 2016

3 eV means that carbon atoms within carbon layers particles which share a boundary at the N-graphene layer. 2016. (285. corresponding to carbon atoms in five different applications.8–401. In our previous work. The preparation scheme and basic characterisation of the as synthesized core–shell FeS2@N-graphene are shown in Fig. 2d).5 A g 1 after 400 cycles.).27–30 electrode materials with micron dimensions can take advantage of The high resolution C1s banding energy can be fitted to four high volumetric specific energies and facile processability for practical components. 2c and Fig. S4b.55. When cooled down and exposed to air. the TEM image of FeS2@N-graphene particles. greigite. In order to obtain more detailed observations of temperature).2 g cm 3.4 mA h g 1 (543 W h kg 1) at 5 A g 1 at room temperature. the prime FeS2 (red) particle. The peaks at low stable at high temperature (decomposition at B300 1C). graphene layers were observed in Fig. The high Meanwhile the thermal stability measured by thermogravimetric resolution N1s XPS spectrum of FeS2@N-graphene can be fitted to analysis (TG) seen in Fig. 2a. (c) EDX image (inserted SEM image and table show the element distribution and content of the sample respectively. core–shell g-Fe2O3@N-graphene (SEM and TEM images seen in the Fig. nano-sized FeS2 has a short Li-ionic diffusion distance while the N-graphene frameworks with optimized electronic conductivity can supply more contact area to reduce resistance. and Raman spectroscopy (Fig.. binding energy 398. and then carbon layers were attached to energy of N1s in FeS2@N-graphene sample. (d) binding by reduction with glucose. S4a. 400. 2 (a) SEM image of FeS2 particles (red) and carbon regions (blue). Csp3 50–100 nm in size. 1a briefly illustrates the synthesis process. 1 and 2. chemical environments (Fig. S3 (ESI†).49 eV). 1 (a) Brief illustration of the fabrication of FeS2@N-graphene (RT: room the particles. 2a. As shown in Fig.23. As a result pyrite FeS2 cells. Commun. This means that charge transfer channels are created around Fig. Downloaded by University of Newcastle on 14/12/2016 13:23:55. Nitrogen (pink) is combined previously reported work. element mapping at 2700 cm 1 confirmed the graphene layer structure. shell materials were characterised by HRTEM (Fig.7 mA h g 1 at 0. Additionally. a = 5. (c) high-resolution the N-graphene frameworks connected to single prime FeS2. core–shell g-Fe2O3@N-graphene formed. The XRD pattern (Fig.2 and 401. ESI†). View Article Online Communication ChemComm N-graphene framework between the nanoparticles possesses more fast charge transfer channels to reduce the resistance. Fig.2 eV).2 eV correspond to pyridinic N The inserted SEM image in Fig. XPS was carried out (Fig. S2.26 when Prussian blue precursors were calcined Fig. nano-Fe and FexC were produced (b) XRD patterns. have superior electrochemical performance with a high reversible capacity of 484. S5 (ESI†) shows that FeS2@N-graphene is three main peaks (at 398. under an argon atmosphere. A large number of comparable to commercial LiFePO4. 52. Hereafter. demonstrating that the carbon shell has a high degree shell FeS2@N-graphene particles by sealing g-Fe2O3@N-graphene of graphitization. ESI†): Csp2 (284. and instrumental errors.24 N-doped graphene can further improve with FeS2 (blue and green). 42-1340. ESI†) tapped density of the obtained FeS2@N-graphene is B1.1 mA h g 1 (613. Considering the low nitrogen content the conductivity and electrochemical performance of pyrite FeS2. is closely wrapped by the N-doped graphene framework (blue). the cells with core–shell nano-FeS2@N-graphene cathode have excellent long-term stability and high specific Published on 16 November 2015.2. LiTFSI/DOL/DME/LiNO3. The peak at high binding energy nano-FeS2@N-graphene composite aggregates as micron sized 400. 2c shows that the core–shell and pyrrolic N respectively. C–O (286.2 eV) and CQO (289.7 W h kg 1) at 0. impurities inevitably occur in small amounts. FexC to generate a shell structure.419 Å) without any other unwanted impurities like marcasite. 1b) and This journal is © The Royal Society of Chemistry 2016 Chem. space group Pa3% . The percentage of ESI†) was used as an important intermediate template to form core– Csp2 is 68.3 eV).4 eV). surface states of FeS2 were investigated by TEM (Fig. pyrrhotite or sulfur. which is correlated to the amount of prime FeS2 nano-crystals in the core–shell measured by TEM in Fig. 986--989 | 987 . S4c.2 and 400.49 W h kg 1 and a fast rechargeable performance of 281. energy. But because of utilizing glass tubes in the synthesis process. Based on is shown in Fig. In this structure. 2b) with well-defined diffraction peaks shows nano-FeS2 with a cubic structure (JCPDF card no. In order to understand in more detail the graphene and sulfur in a small tube and heating (see Fig. S4a (ESI†) and the 2D peak To prove that the shell is N-doped graphene. The shell. S1.5 A g 1 corresponding to a specific capacity of 713. ESI†). The average particle size is approximately 50 nm as measured by XRD and calculated according to the Scherrer formula. Li-ion are substituted by nitrogen atoms in form of graphic N. (b) TEM image of FeS2@N-graphene particles. which is higher than commercial rechargeable Li-ion batteries and also more stable than that of most other reported FeS2 batteries. containing 401.

forming a Li–N–S–O passivating layer coating upon the lithium anodes. the iron is oxidized to provide electrons to react with Li2S to cycle curve in Fig. to the superior electrochemical performances of core–shell nano- FeS2@N-graphene for Li-ion battery use. S8). 3c and d). performances are shown in Fig. cycle number shown at 0. the B3 nm N-graphene shells are tightly attached to FeS2. the structure stability enhancement by the N-graphene shell and the fast charge transfer paths around the N-graphene frameworks lead Published on 16 November 2015. S9 (ESI†).5 A g 1. 0. Downloaded by University of Newcastle on 14/12/2016 13:23:55. View Article Online ChemComm Communication HRTEM (Fig.61 V) were seen. S10 (ESI†).2 mV s 1. Next to the N-graphene frameworks. the redox reaction voltages are stage of Li+ extraction. 0. in the initial As the cycle number increases. State 3) able.20 In this work. further indicating 988 | Chem.32 Besides shrinking the FeS2 particle to shorten the Li+ diffusion distance. the SEM images of lithium anode surfaces after discharging shown in Fig. which directly affects the transfer ability of Li ions. S6 and S7 (ESI†).2 mV s 1). predicted that if the size of the FeS2 particles becomes smaller and from which Fe can form a conductive framework to promote the the electronic conductivity of FeS2 particles gets better. when combined with the advantages of short Li-ionic distance in the nano-size FeS2. LiNO3 plays a very essential role in alleviating parasitic reactions between Li metal and already present sulfur species to optimize cycling the performance of FeS2 based Li-ion batteries.48 and 1.3 M LiNO3 in DOL/DME at a typical charge–discharge curves).9 mA h g 1 per (State 1 to 2. 4 (a) Rate performances of cells at 0. (d) Discharge energy peaks (at approximately 1.2 to 4 in Fig. Li2FeS2 starts to supply Li ions and phase structure vs.22 V are attributed to the decomposition of LiNO331 (providing a large irreversible capacity). at B1.5 A g 1. S nano-particles are always generated in general cases and have low dissolution ability in electrolytes. the reversible reaction mechanism sible redox to proceed with fast kinetics.5 A g 1. Additionally. With the number of and phase transformation were illustrated in Fig. 3c and d with the extracted Li ions increased.5. 2. 3c and d). 1. For the first cycle. (b) long cycling performance from 2nd to 400th cycle at 0. The reduction peaks with the theoretical discharge specific energy of commercial cathode materials. 52. 3c and d). reflecting good reversibility of nano-FeS2@ the interface between the Fe nano-particle and Li2S (State 1 in N-graphene. in Fig. wrapped in conductive frameworks have shorter Li+ diffusion Combining with the CV analysis and XRD patterns at different distances and more electron transfer channels. and the reduction reversible reaction of Li2S. 3 (a) Cyclic voltammetry curves (from 1st to 4th cycle at 0. (c and d) schematic two other kinds of electrolytes were investigated and the cycling diagram for reaction mechanism.1. iron can react with Li2S to form Li2FeS2 at nearly unchanged. Fig. It can be transforms to Li2FeS2 (State 2) and then to Fe and Li2S (State 1). then further to form FeSy. The typical cycling curves in Fig.05. electrochemical performance during the electrons to form Li2 xFeS2 (State 2 to 3. (c) Discharge energy density of FeS2@N-graphene particles scanning rate of 0. A mechanism of LiNO3 doping was proposed where LiNO3 can be directly reduced by lithium to LixNOy and oxidized by sulfur species to LixSOy. In this case. 3c and d) until all the iron and Li2S transform into Li2FeS2 the capacity of the cells decays very slowly with B0. 986--989 This journal is © The Royal Society of Chemistry 2016 .1 in Fig. the Li ions and electrons are easier to extract from Li2 xFeS2 due to the shorter Li-ionic diffusion distance and better electronic conductiv- ity. which correspond to the voltage platform at the 1st tically. nano-FeS2@N-graphene cells with (b) cycling curves from 2nd to 100th cycle at 0.22 V) and two oxidation density of FeS2@N-graphene particles vs. 1c). FeSy ( y r 2. The Li-ion storage performance of as-synthesis nano-FeS2@ N-graphene were studied by cyclic voltammetry (CV) and its electrochemical properties were studied using two-electrode coin cells.48 and 1. Commun. 5 A g 1 (inset is the N-graphene with 1 M LiTFSI and 0.5 A g 1 along reduction peaks (1. The advantage of the shell structure with excellent electronic conductivity is that it can both improve the conductivity of the FeS2 surface as well as enhance the structural stability due to volume change in the charge–discharge process. 2016. Therefore the shutter reaction due to Li2Sx (2 r x r 8) and generation of S nano-particles may be avoided because S2 prefers to form (S2)2 to combine with Fe3+ (from State 3. This allows rever- charge/discharge state (Fig. e.. During the charging procedure.g. Fig. two wide reduction compared to other commercial Li-ion cell cathode materials. During the intermediate structure of Li2 xFeS2 is unstable and change- the discharging procedure (Fig. theore- of nano-FeS2.89 and 2. smaller particles cycle from the 2nd to the 400th cycle at 0. it can be observed that the surface of the Li anode is not smooth with dark species formed on the lithium. Note that charge–discharge process with different ‘‘State’’ (State 1–4). Therefore. 3a shows the first four CV curves of nano-FeS2@ Fig. 3c and d). 3b and 4b show that Fig. form Li2FeS2. Actually.

L. 5590. Zhang. and Shenzhen Science Published on 16 November 2015. Lee. X. Lingyun. Notes and references ponding to the specific energy of 637. Adv. Y. Weichert and J. Mater. J. X. 2013. L.1 W h kg 1 (in Fig. Weiling. 120. Yersak. Jing. 5 A g 1 18 T. Zhu. 25 N. 22 S. H. S. In summary. Wang. Qiao and J. C. G. Even compared to the reported pyrite 19 E. J. FeS2/electrolyte interface to reduce the resistance. whose specific energy retention is up 27 Y. S. Pan. Xie. M. H. P.5.. electroactive FeS2 cathode species. H. 5 T. 2015. F. FeS2@N-graphene has a higher energy density of 26 J. Ed. 3. Jianchun. Lin. Mater. Shenzhen). S. Tang and C. cathode material for the next generation of Li-ion batteries.5. 2015. ACS Nano. Wu. Note that these Energy Mater. Adv. 5 A g 1 respectively. J. 3. Nano Lett. 81. Dubey and stable cycle specific energy. Am. Rct changes little. 7689. 2012. Hu. 630. 114.-B. D. 4b).. S. Zhu and Y. Fu. Stoldt and S. H. Zheng. Guo. Li and H. Li. Yue. Guidotti. 2010. 445. J. Zu and Y. Soc. Amine and F. Soc. 4c 15 L. shell nano-FeS2@N-graphene. 177. Le Mehaute and A. M. X. Wen. which can be 1 X. J. A.-D. Liu. Interfaces. Hence FeS2@N-graphene is a very promising 0. C. Kim.3 V). 15874. Power Sources.21 the specific energy of core–shell FeS2@N-graphene of 2014. 51. Chung.-S. 2015. 4c).2–1. 798. M. Wei.-M. W. Xiaoshu. Chem..5 to 12. J. 2011. 2112. Jianchun. This journal is © The Royal Society of Chemistry 2016 Chem. 7386. Gullapalli. Yu and X. 986--989 | 989 . X. E. A. Dugast. J. Commun. 3206. 2. 1300961. 7855. Macpherson. 5.1. Yu. 4. Phys. To further clarify reasons behind the good performance of core– Funct. V. as well as a stable very good with 768. Qing. indicating that uniform and continuous N-graphene carbon frame. Oh. C. Rosamaria. Y. 159. to B80%. 2015. L. R. 2003. Trevey. W.. 701 W h kg 1 after 100 cycles. Y. S.. M. J. D. Yafei. 29 S. Wang. Han. Wan. J. K. Yang. we compared 1989. L. Zhao. C. Wei. A. Tadé and S. Son. Piper. V. LiMn2O4. View Article Online Communication ChemComm that the ether-based electrolyte with LiNO3 plays a pivotal role in N-doped graphene as the shell is that core–shell FeS2@N-graphene promoting the electrochemical stability. Power Sources. 2012.-H.15 It is generally believed that the electrical conductivity 7 D. Zhu. Xiaosi. Zhen. S.5Co0. Jiang. Zhang. Y.-J. Piper. 475 mA h g 1 at 0. Palacin.-L.05. which are much higher than other commercial S. Yuan. B. Zhang. P.5 A g 1. J. H. Son. 3. 391 and 285 mA h g 1 at 0. Ren. van Aken. S. ZDSY20130331145131323. Y. H. A. 5. S. The benefit of the amount of nanosize FeS2 32 C.. Y.1 A g 1) The nano-FeS2@N-graphene for Li-ion cells exhibits good rate and higher specific power (543 W h kg 1 at 2. S. LiFePO4. to have very high specific energy at different currents (1275. 115. J. He and Y. S. of Rct from the 1st to the 5th cycle are changed from 10. 2010. C. 484. N.14. Ding. J. A. Kang. 713. 26. S. 30 Y.7 mA h g 1) after 400 cycles at 0. J. Q. Su. H. 2014. 25. 6337. J. Yichen. Wang and F. 2015. 2013. 119. Zhaolong and nano-crystals as the core for Li-ion storage and using coated C. LiNi0. L. Liu. F. Hu. After long-term 10 S. and d. Tian. Bourgeois. Le Cras. as shown in Fig. of Rct in this work can be attributed to the N-graphene frame. 543. S. LiFePO4 (B450 W h kg 1 at 0. Jia and S. carried out to give curves for the 1st. Cheng.. Ji. J. T. Downloaded by University of Newcastle on 14/12/2016 13:23:55. Electrochem.. What is more. 4350.-H. Xiaosi and B. Y. H.05. FeS2@C. S. shown in Fig. Z. Li-ion cells with core–shell FeS2@N-graphene still have very high capacity (401.3O2. Z. Solid State Ionics. 6. Bhat. J. Kim. Masset and R. 241.5 A g 1). O. Y. Liu. T. long-term stability is one of the key challenge for FeS2 batteries. H. Compared to the reported LiCoO2 P.. Cao. K. 348. Chem. Power Sources..-U. 1. 7945.2Mn0. Int. Chem. Adv. 2015. Guo. Mater. F. J. S. Mahmood. 2013N080). 2. 15. Xu. Duan. Sun. which is then able to return to candidate as a next generation advanced Li-ion cathode. 31 S. (B504 W h kg 1). Xue. 2 Y. Xiao. The reversible specific capacity is also commercial rechargeable LIB cathodes. 229. X. influences Rct immensely. 2014. Yang. 136. Mater. Kang.-S. 2015. etc. C. C.2Mn0. Oh and S.-B. cycling. X. (B390 W h kg 1 7. Fig. Angew. Xiao. Zhihui and B. 6787. further 21 J. 17 V. Cabana. 50. Mater. 395. Jin. S. Y. Z. C. 2014. Mater. Zhang. Z.. S. 4a. 323. Caban-Acevedo. Xiang. S. 7. 2015.1. specific power-specific energy of core–shell nano-FeS2@N-graphene 13 A. W. Z. 639. L. H. Yichen. Li. Mater. Adv. 4. Therefore. Pan. corres. Sun. L. D. 2015.3O2 (B530 W h kg 1 at 0. Xia. Lin. Lee. 5th and 400th cycle in the 4 Z.. C. W. Manthiram. Xing. 2013. Wei and FeS2@N-graphene was prepared as a novel cathode material for L. Flamary. Yang. 2008. D. C. W. Power Sources. Mater. 4b). meaning that the shell structure of 11 H. for solving the problems associated with the 5. H. Le. works being able to provide fast charge transfer channels at the 9 J. Electrochem. The coulombic efficiency of any cycle is very close to 100%. 5463. prime FeS2 particles. K. H. J. Wu. A. Gu. Chem.. X. Chem. S. nano-FeS2@N-graphene is very stable. The JCYJ20140903101633318).2 O. Maier and Y.. 137. 24 Z. Gowda. H.5 A g 1) and LiMn2O4. 22. LiNi0. Wen. C. Srivastava. 15. S. ACS Nano. 6025.5 A g 1 (Fig. 52. Suh. W. M. Compared to low conductive The research was financially supported by National Project for PAN matrix encapsulation. Strauss. Lee. 1. Zheng. Nano Lett. Liu. 28 W. EV Batteries (20121110. Soc. J. 73. Evans. Z. X. materials. Yu. Nano Res. 0. J. 2016. 0. Appl. Kang. Chem. Adv. Yu. W. L.79 kW g 1) than capability as shown in Fig. K. Commun. Lee. 2015. Hence. Guangdong ble capacity due to the continuous conductive paths formed by the Innovation Team Project (No..4 O. Maier. Chem. D. Mai. Zhao. Lin. OptimumNano. K. B. The significant advantage of nano-FeS2@N-graphene is 16 L. X. D. attributed to the stable shell structure. Y. Cho. 2012. S11 (ESI†). M. 14 D. Wang. A. 2015.22 FeS2@N-graphene has a high reversi. Xiaoshu. 9. Peng. 595. Energy Mater. Y. H. S. Z. The values K. Liu. Ajayan. 51. Wang. Zhang. cycling performance. Z. results are much lower than those reported with FeS2@C 6 P. Kim. this work is higher especially at high current rate area. Z. 1436. Chem. Z. and then until the 400th cycle to about 61. A. Hu.-B. B.5Co0. 217.. a novel core–shell nano. Larcher and M. M. L. 1983. Hu. ACS Appl. and Technology Research (Grant No. J. A. exhibits a remarkable specific energy (950 W h kg 1 at 0. Guo. A920. Xu. N-graphene frameworks among the FeS2 particles. 172–173. the FeS2@N-graphene is a potential Li-ion Catal. Commun. S. Kim. 2011. T. J.5 A g 1). 11751. H. 359. 26. to other commercial Li-ion battery cathodes. Qiu and J. L. Reddy. Y. Ang.-S. Oh and respectively). Y. Jones. 20 A. at 0. Kim. Pecquenard and F. Monconduit. for evaluating the practical value. M. 12 F. 4d shows that the FeS2@N-graphene has 23 A. Zhuo.. J. Feng and X. W. Hou. 950.-H. ACS Nano. M. Furthermore. 21. Duan. the AC-impedance measurement was 3 C. S. Liwei. Changhong. Tu. Liu. Ling. Nanoscale.. J. L. such as LiCoO2. the big improvement of values 8 D. R. Xu. Li. 2011. 11508. Rev. Dahn and C. Li-ion cell cathodes (Fig. R.. Liu. Girard and S. H. D. J. 2014. Hongwei. works can provide more continuous conductive paths between any Y. E170. Electrochem. Pelé. 6278. 10307. J. Zhang. J. 3. 364 W h kg 1 at 0. 0. discharged state (1. Yersak. Li-ion batteries. Cui. ACS Nano. J. Adv. 2011.