This journal is©The Royal Society of Chemistry 2015 Chem. Commun.

Cite this:DOI: 10.1039/c5cc05577f

A novel preparation of core–shell electrodematerials via evaporation-induced self-assemblyof nanoparticles for advanced Li-ion batteries†

Zhiqiang Xie, Sarah Ellis, Wangwang Xu, Dara Dye, Jianqing Zhao* and Ying Wang*

We report, for the first time, a simple and novel synthesis of a Li-rich

layered-spinel core–shell heterostructure (L@S core–shell) via

evaporation-induced self-assembly (EISA) of Ni-doped Li4Mn5O12

nanoparticles (Li4Mn4.5Ni0.5O12) onto the surface of layered

Li[Li0.2Mn0.54Ni0.13Co0.13]O2 (LMNCO) without using any surfactant

during the coating process. The resultant L@S core–shell as a

cathode in lithium ion batteries demonstrates significantly improved

specific capacity, cycling performance and rate capability compared

to pristine LMNCO.

The main drawbacks of commercial LiCoO2 cathode materialssuch as limited delivery capacity, toxicity as well as high costhave hindered their application in plug-in hybrid electricvehicles (PHEV) or electric vehicles (EV).1,2 In this regard, Li-richlayered oxides have attracted extensive attention due to their highspecific capacity of B250 mA h g�1 when cycled over a broad voltagerange between 2.0 and 4.8 V versus Li/Li+ and other advantages suchas environmental benignity, safety and relatively low cost.3,4 AmongLi-rich layered oxides, Li[Li0.2Mn0.54Ni0.13Co0.13]O2, a solid solutionin a two component notation as 0.5Li2MnO3�0.5LiMn1/3Ni1/3Co1/3O2

(hereafter denoted as LMNCO), has attracted extensive attentiondue to its extremely high theoretical capacity of 321 mA h g�1,better cycling stability and rate capability than other Li-richanalogs. Unfortunately, these materials still suffer from unsatis-factory cycling stability and intrinsically poor rate capability.3–5

Moreover, it has been reported that Li-rich layered oxides sufferfrom surface vulnerability at high voltage and erosion fromelectrolytes.6–9 In order to address these challenges, many effortshave been devoted to improving the structural and surfacestabilities by using a simple surface modification strategy. Upto now, various metal oxides (Al2O3,10 CeO2

11 etc.), fluorides and

phosphates,12–14 as well as some other Li-ion conductingLiNiPO4,15,16 LiAlO2

17 and Li2ZrO318 have been applied to

stabilize the surface structure of Li-rich layered oxides andsuppress side-reactions between the electrode and electrolyte,thereby leading to improved cycling performance and thermalstability. However, such coating materials are either poorelectronic or ionic conductors and generally are not electro-chemically active, thereby leading to limited improvement inelectrochemical performance of Li-rich layered oxides.

Recently, lithium manganese oxide (LMO) based spinelcathodes have attracted intensive attention due to their highrate capability resulting from their efficient 3D Li+ diffusionchannels.19,20 Among them, spinel Li1+xMn2O4 has been studied asthe coating material to overcome the above-mentioned drawbacksof Li-rich layered oxide materials.21 In the design of a layered-spinelcore–shell heterostructure, the spinel coating with efficient 3DLi-ion transport channels was expected to stabilize the layered bulkupon high-voltage cycling and to rapidly transport Li ions betweenthe layered bulk and electrolyte, leading to improvements in bothcycling stability and rate capability of Li-rich layered oxide cathodes.However, preparation of core–shell heterostructures reported in theliterature required complex procedures and precise control ofreaction conditions such as pH and concentration of the solutions,which poses challenges for large-scale production for high-energyhigh-power LIBs.22 In addition, the spinel Li1+xMn2O4 has beenreported to have an unsatisfactory cycling stability due to Jahn–Teller distortion and manganese dissolution through a dispropor-tionation reaction.23,24

To improve electrochemical properties of conventionalspinel Li1+xMn2O4, it is found in our recent work that Ni-dopedspinel Li4Mn5O12 (Li4Mn4.5Ni0.5O12) can be charged to around 5.0 Vand show remarkable high-voltage cycling stability at room tempera-ture.25 In addition, its 3D Li+ ion diffusion pathways ensure its excel-lent rate capability.26 Therefore, it can be expected to be a promisingcoating material to replace spinel Li1+xMn2O4. Herein, we report asimple and facile one-pot preparation of L@S core–shell structure(Li-rich layered-spinel core–shell heterostructure) via evaporation-induced self-assembly (EISA) of ultrafine Li4Mn4.5Ni0.5O12

Department of Mechanical & Industrial Engineering, Louisiana State University,

Baton Rouge, LA 70803, USA. E-mail: andrewxie1020@gmail.com, ywang@lsu.edu,

jzhao3@tigers.lsu.edu; Fax: +1-225-578-9162, +1-225-578-9162;

Tel: +1-225-578-8577, +1-225-329-3539

† Electronic supplementary information (ESI) available: Experimental details,SEM image of Ni-doped spinel Li4Mn4.5Ni0.5O12, CV curves of pristine LMNCOand spinel Li4Mn4.5Ni0.5O12. See DOI: 10.1039/c5cc05577f

Received 10th July 2015,Accepted 18th August 2015

DOI: 10.1039/c5cc05577f

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nanoparticles onto the surface of Li-rich layeredLi[Li0.2Mn0.54Ni0.13Co0.13]O2 (LMNCO) without using any surfactantduring the coating process. In this study, we also introduce a simpleroute to prepare ultrafine Li4Mn4.5Ni0.5O12 nanoparticles (5–20 nm)from the spinel Li4Mn4.5Ni0.5O12 bulk by the so-called sonofragmen-tation. Sonofragmentation is a well-known one-step process todirectly produce nanoparticles from large-grained powders.27,28 Ithas been reported that even intrinsically strong carbon nanotubescan be fragmented by sonication.29 As a result, the as-prepared L@Score–shell material demonstrates significantly improved specificcapacity, cycling performance and rate capability for applicationas a cathode in new-generation LIBs compared to pristine LMNCO.Due to the structural and functional versatility of nanoparticles, thesynthetic approach reported in this work can be generalized to othermaterials to form novel core–shell structures, for applications inLIBs or other fields.

Fig. 1 presents a schematic illustrating the facile synthesisprocedure of a L@S core–shell heterostructure via EISA,33 which isdifferent from the existing methods such as ‘‘dip and dry’’21 orco-precipitation.22 Briefly, simple top-down preparation of spinelLi4Mn4.5Ni0.5O12 nanoparticles is introduced by applying ultrasoni-cation to larger Li4Mn4.5Ni0.5O12 particles in ethanol for two hours.The large-sized Li4Mn4.5Ni0.5O12 particles are broken into smallernanoparticles due to the mechanical energy of ultrasonic wave.Afterwards, as described in the experimental part, the resultantsuspension of Li4Mn4.5Ni0.5O12 ultrafine nanoparticles in ethanol ismixed with the Li[Li0.2Mn0.54Ni0.13Co0.13]O2 suspension in ethanol,followed by continuously stirring at 80 1C until the solvent iscompletely evaporated. In this step, ultrafine nanoparticles ofLi4Mn4.5Ni0.5O12 tend to self-assembly on the surface of large-sizedLi[Li0.2Mn0.54Ni0.13Co0.13]O2 particles in order to drasticallyreduce the surface energy. Finally, after post-annealing at500 1C for 3 hours, a L@S core–shell heterostructure is successfullyobtained.

The as-prepared spinel Li4Mn4.5Ni0.5O12 particles are char-acterized by both scanning electron microscopy (SEM) andtransmission electron microscopy (TEM). The SEM image ofLi4Mn4.5Ni0.5O12 particles before sonofragmentation in Fig. S1(ESI†) shows numerous highly-crystalline nanoparticles withsmooth surfaces. Fig. 2a and b display TEM and high-resolutionTEM (HRTEM) images of spinel Li4Mn4.5Ni0.5O12 powders beforeand after sonofragmentation, respectively. Fig. 2a reveals theaverage size of primary Li4Mn4.5Ni0.5O12 particles to be B500 nm.Interestingly, it is found in Fig. 2b and c that sonication can

effectively reduce the particle size of Li4Mn4.5Ni0.5O12 powdersto the nanoscale range (5–20 nm). The lattice fringes of eachnanoparticle in Fig. 2c are clearly observed. The zoom-in view oftwo regions in green rectangles in Fig. 2b is displayed in Fig. 2cand d. The lattice fringes of the Li4Mn4.5Ni0.5O12 surface coat-ing can be readily indexed to the (222), (400) and (220) planes,respectively, suggesting the efficient preparation of ultrafinemonocrystalline nanoparticles by using the sonication treat-ment. This approach demonstrates a promising way to producevarious inorganic nanoparticles and will find wide potentialapplications in many fields such as nano-scale electronic devices.

As revealed in the SEM image of pristine layered LMNCO inFig. 3a, the sample is composed of nanoparticles (B200 nm)with a smooth surface, indicating their highly crystalline nature.It is noted that the L@S core–shell sample looks very similar toLMNCO particles in SEM since the ultrathin coating cannot bedetected by SEM. Therefore, TEM is used to examine themorphology of the core–shell structure as shown in Fig. 3c and d.Crystal structures of the as-prepared pristine layered LMNCO,spinel Li4Mn4.5Ni0.5O12 and L@S core–shell samples are furtheridentified using powder X-ray diffraction (XRD) as shown in Fig. 3b.The main peaks for the Li4Mn4.5Ni0.5O12 sample can be readilyindexed to Li4Mn5O12 with the spinel phase of a face-centered

Fig. 1 Schematic illustration of a facile preparation of a L@S core–shellheterostructure.

Fig. 2 (a) TEM bright field images of spinel Li4Mn4.5Ni0.5O12 particlesbefore sonofragmentation, (b) HRTEM image of Li4Mn4.5Ni0.5O12 aftersonofragmentation, with (c) and (d) showing zoom-in view of two regionsin the green rectangles in (b).

Fig. 3 (a) SEM image of pristine layered LMNCO, (b) powder XRD patternsof spinel Li4Mn4.5Ni0.5O12, pristine layered LMNCO, L@S core–shell hetero-structured powders, (c) HRTEM images of the L@S core–shell sample and (d)zoom-in view of the surface of the L@S core–shell in the green rectangle in (c).

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cubic structure (ICDD: 46-0810). A secondary phase of monoclinicLi2MnO3 with C2/m symmetry (ICDD: 84-1634) is evidenced aswell, which might be ascribed to the decomposition of theLi4Mn5O12 spinel phase during post-heat treatment at 900 1C.25

The strong peaks for both pristine LMNCO and L@S core–shellheterostructure samples can be indexed to a layered a-NaFeO2

structural type with space group R3m symmetry and some weaksuperstructure reflections (marked as * in Fig. 3b) can be ascribedto monoclinic phase Li2MnO3. Compared to XRD patterns ofpristine LMNCO and spinel Li4Mn4.5Ni0.5O12, the XRD patternof the L@S core–shell heterostructure sample combines with thepatterns of both the layered structure and cubic spinel structurewith weak shoulder peaks assigned to the spinel coating as pointedby the arrows in Fig. 3b.

High-resolution TEM (HRTEM) is used to examine the L@Score–shell sample to further identify its surface structure. Asobserved in Fig. 3c, the bulk layered structure of pristine LMNCOis well-preserved in the L@S core–shell structure, displayinglattice fringes with an interplanar spacing of ca. 4.73 Å. It canalso be seen that a homogeneous outer layer is uniformly coatedon the surface of layerd LMNCO bulk. The enlarged view in Fig. 3dreveals a crystalline outer layer with lattice fringes showing aninterplanar spacing of ca. 1.38 Å, which do not belong to thelayered structure but are consistent with the (531) plane of thecubic spinel (Fd%3m), confirming that the outer layer is the spinelcoating. Therefore, it can be concluded that a novel L@S core–shell structure can be facilely synthesized via evaporation-inducedself-assembly of nanoparticles, which opens a new route forachieving various core–shell structures for different applications.

Fig. 4a and b compares initial three charge/discharge curvesof pristine LMNCO and L@S core–shell heterostructured cath-odes when cycled between 2.0 and 4.99 V vs. Li/Li+ at 25 mA g�1

(B0.1C). It is found that the L@S core–shell heterostructuredcathode is capable of providing a discharge capacity ofB272 mA h g�1 after three cycles, which is higher than thatof pristine LMNCO that delivers a discharge capacity ofB248 mA h g�1. Compared to the discharge plot of pristineLMNCO, two newly-formed plateaus at around 4.7 and 2.7 V areobserved for the L@S core–shell heterostructured sample, whichis associated with the coating of spinel Li4Mn4.5Ni0.5O12.25,26

Therefore, lithium ions can be intercalated into the spinel coat-ing at around 4.7 and 2.7 V (marked by arrows) during thedischarge process, thereby leading to higher discharge capacitiesof the L@S core–shell structure.

In order to compare the cycling stability of L@S core–shell andpristine LMNCO cathodes, both samples are cycled at 0.1 and 0.5C inthe wide high-voltage range between 2.0 and 4.99 V vs. Li/Li+,respectively, as shown in Fig. 4c and d. As observed in Fig. 4c, pristineLMNCO delivers a maximal capacity of B258 mA h g�1 and main-tains B233 mA h g�1 after 60 cycles at 0.1C. In contrast, the L@Score–shell cathode delivers a maximal capacity ofB286 mA h g�1 andretains 273 mA h g�1 after 60 cycles exhibiting a higher capacityretention of 95.4% than that of the pristine LMNCO (90.3%). Fig. 4dcompares cycling performances of the two samples at a higherrate of 0.5C. In this test, the L@S core–shell delivers a maximalcapacity of B183 mA h g�1 and retains B153 mA h g�1 after

100 cycles, which is much higher than that of pristine LMNCOgiving B125 mA h g�1 after 100 cycles. The improvement incycling performance and specific capacity herein can beascribed to the stabilizing effect of the thin spinel phase coating,which not only helps to reduce the erosion from electrolytes athigh voltage but also restrain the bulk LMNCO active-mass lossduring long cycling.

Fig. 4e summarizes rate performances of pristine LMNCO andL@S cathodes at various charge/discharge rates, namely 0.1C, 0.2C,0.5C, 1C, 2C and 5C at 2.0–4.99 V vs. Li/Li+. It is found that pristineLMNCO shows a poor rate capability, with almost no dischargecapacity at 5C though with a good recovery to B225 mA h g�1 whencycled back to 0.1C. On the contrary, the L@S core–shell sampledelivers initial discharge capacities of 126 mA h g�1, 97 mA h g�1

and 37 mA h g�1 at 1C, 2C and 5C, respectively; when cycled back to0.1C from 5C, its discharge capacity reaches as high as 269 mA h g�1,demonstrating an outstanding electrochemical reversibility. Suchenhanced rate performance results from the following factors. First,the spinel coating with excellent structural stability can effectivelystabilize the surface structure of the LMNCO core, thereby reducingthe erosion from the electrolyte and the bulk active-mass loss.Second, the spinel coating facilitates fast Li ion diffusion from theelectrolyte to the layered LMNCO core. In addition, due to structuralcompatibility between the layered LMNCO and spinel phase coating,L@S is expected to have high structural stability. It is also noted that

Fig. 4 Initial three charge/discharge curves of (a) pristine layered LMNCO,(b) L@S core–shell heterostructured cathodes when cycled between 2.0and 4.99 V vs. Li/Li+ at a specific current of 25 mA g�1 (0.1C). (c) and (d)Cycling performances of pristine LMNCO and L@S core–shell cathodes at0.1 and 0.5C, respectively. (e) Rate performances of pristine LMNCO andL@S core–shell cathodes at various charge/discharge rates. (f) Cyclicvoltammograms of L@S core–shell cathodes in the first three cycles at ascan rate of 0.1 mV s�1 in the voltage range of 2.0–4.99 V vs. Li/Li+.

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the L@S core–shell cathode needs more charge–discharge cycles toreach its maximum capacity at 0.1C than the pristine LMNCOcathode. The reason for this difference can be attributed to therelatively uniform spinel Li4Mn4.5Ni0.5O12 coating at the outer surfaceof the LMNCO core, which leads to the gradual electrochemicalactivation of the Li2MnO3 component in the LMNCO core during theinitial several cycles. As a result, the L@S core–shell compositecathode needs more electrochemical cycles to reach its maximumcapacity in comparison with the pristine LMNCO.

Cyclic voltammetric (CV) measurements are then carried out tofurther explore the electrochemical characteristics of the core, shell,and core–shell materials. Fig. S2 (ESI†) presents the first CV threecycles of pristine LMNCO and spinel Li4Mn4.5Ni0.5O12, respectively,at a scan rate of 0.1 mV s�1 in the voltage range of 2.0–4.99 V. As forthe CV curve of pristine LMNCO (Fig. S2a, ESI†), the first pair ofredox peaks at 4.16/3.63 V in the first electrochemical cycle corre-sponds to the redox reactions of Ni2+/Ni4+ followed by Co3+/Co4+,while Mn still remains as tetravalent in the LiMn1/3Ni1/3Co1/3O2

structure.30,31 The anodic peak at 4.67 V is associated with decom-position of Li2MnO3 to Li2O and Li-active MnO2, the unavoidabledecomposition of the electrolyte and formation of a solid electrolyteinterphase (SEI) at such a high potential above 4.5 V.32 Such anelectrochemical activation process of Li2MnO3 would result in highcapacity of LMNCO via simultaneously losing oxygen irreversibly asLi2O and MnO2. Therefore, the cathodic peak at B3.0 V becomesapparent after charging to 4.99 V and can be attributed to the redoxreaction of Mn3+/Mn4+ that may take place in the electrochemicalreaction after the Li2MnO3 component is electrochemically activated.It is also found that the anodic peak at 4.67 V in the first CV curvedisappears in subsequent CV cycles. Fig. S2b (ESI†) displays a typicalCV curve of spinel Li4Mn4.5Ni0.5O12. It is clearly observed that the2nd and 3rd curves of spinel Li4Mn4.5Ni0.5O12 are almost identical,indicating outstanding electrochemical reversibility and structuralstability during cycling over a wide voltage range between 2.0 and4.99 V vs. Li/Li+, which is expected to be a promising surface coatingfor pristine LMNCO. In the CV curves of LMNCO coated with spinelLi4Mn4.5Ni0.5O12 (L@S core–shell) as shown in Fig. 4f, it is found thatthe L@S core–shell cathode shows a slightly better electrochemicalreversibility than pristine LMNCO. The redox peaks at 4.16/3.63 Vare associated with oxidation of the Co3+/Co4+ redox only from theLMNCO core and the Ni2+/Ni4+ redox from both the LMNCO coreand the spinel Li4Mn4.5Ni0.5O12 shell. Interestingly, the above redoxpeaks for the L@S core–shell show higher corresponding currentdensity than that of pristine LMNCO, probably attributed to the thinspinel coating that reduces the erosion from electrolytes andtransition-metal ion dissolution. It is also noted that some peaks(pointed by arrows in the Fig. 4f) and another extra peak at 4.88 V canbe ascribed to the spinel phase coating, confirming the L@S core–shellheterostructure, which is consistent with the XRD and TEM results.

In conclusion, we report a simple and novel synthesis of a L@Score–shell structured electrode material via facile evaporation-inducedself-assembly (EISA) of ultrafine crystalline Li4Mn4.5Ni0.5O12 nano-particles on the surface of Li-rich layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2

particles. This L@S core–shell cathode material demonstrates signifi-cantly improved specific capacity, cycling performance and ratecapability compared to pristine Li-rich layered cathodes. Due to

structural and functional versatility of nanoparticles, our study pro-vides new insights into the preparation of various core–shell struc-tures via EISA of nanoparticles for applications in LIBs or otherenergy-related fields.

This work was supported by the Research EnhancementAward (REA) and the Research Awards Program (RAP) spon-sored by LaSPACE.

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