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To meet the demanding requirements in plug-in hybrid electric vehicles (PHEVs) or electric vehicles (EVs), higher energy den-sity materials, such as the Li-rich, layered manganese-based oxides (LLOs) with the general formula xLi 2 MnO 3 ·(1-x)LiTMO 2 (TM = Mn, Ni, Co, etc.), are promising candidates as they possess higher revers-ible capacity (>250 mAh g −1 ), improved safety and much reduced cost. [ 4–9 ] Recent microscopic evidence reveals the inter-growth of rhombohedral LiTMO 2 ( R-3m ) and the monoclinic Li 2 MnO 3 -like layered structure ( C / 2m ) at the atomic scale in the oxide grains. [ 10 ] The Li 2 MnO 3 component serves as an electrochemically active phase for Li storage when cycled above 4.5 V versus Li/Li + . [ 8,11–14 ]

Nevertheless, these LLO materials undergo steady voltage/capacity decay

when cycled above 4.5 V, resulting in a substantial decrease of the cathode energy density. [ 15–18 ] The origin of voltage/capacity decay upon cycling stems from cation migration between TM layers and Li layers and subsequent phase transformation. [ 19,20 ] The cationic doping with other metallic cations (such as Mg, [ 21 ] Al, [ 22 ] Ti, [ 23 ] Sn, [ 24 ] Ru, [ 25 ] Y, [ 26 ] Zn, [ 27 ] etc.) and polyanion doping based on nonmetal elements, such as BO 4 5− , [ 28 ] SiO 4 4− , [ 29 ] PO 4 3- , [ 30 ] etc., have been employed to improve the cyclic dura-bility by weakening the TM–O covalency in the oxygen close-packed structure. In addition, surface coatings using metal oxides, [ 31–34 ] fl uorides and phosphates, [ 35–37 ] LiNiPO 4 and Li 3 VO 4 , [ 38–40 ] have been applied to protect the surface structure from side reactions with the electrolyte under high voltage and to restrain the layered-to-spinel transformation which occurs preferentially on the crystal surface and leads to capacity fading of LLO materials. However, the ionic dopants and coating mate-rials are mostly electrochemically inactive, so the improved cycling stability is achieved at the expense of reduced specifi c capacity/energy density of the cathode. Moreover, a conformal and continuous coating on the surface of oxide particles is rather diffi cult to obtain practically. Hence, advancing the struc-tural and cycling stability in both the bulk material and the surface structure through a simple way is highly desired for potential applications of LLO materials.

Herein, we develop a novel LLO material with a nanoscaled spinel-like surface layer through gradient doping of polyanions

Surface Structural Transition Induced by Gradient Polyanion-Doping in Li-Rich Layered Oxides: Implications for Enhanced Electrochemical Performance

Ying Zhao , Jiatu Liu , Shuangbao Wang , Ran Ji , Qingbing Xia , Zhengping Ding , Weifeng Wei , * Yong Liu , Peng Wang , * and Douglas G. Ivey

Lithium-rich layered oxides (LLOs) exhibit great potential as high-capacity cathode materials for lithium-ion batteries, but usually suffer from capacity/voltage fade during electrochemical cycling. Herein, a gradient polyanion-doping strategy is developed to initiate surface structural transition to form a spinel-like surface nanolayer and a polyanion-doped layered core material in LLOs simultaneously. This strategy integrates the advantages of both bulk doping and surface modifi cation as the oxygen close-packed structure of LLOs is stabilized by polyanion doping, and the LLO cathodes are protected from steady corrosion induced by electrolytes. A LLO material modifi ed with 5 at% phosphate (5%P@LLO) shows a high reversible discharge capacity of ≈300 mAh g −1 at 0.1 C, excellent cycling stability with a capacity retention of 95% after 100 cycles, and enhanced electrode kinetics. This gradient doping strategy can be further extended to other polyanion-doped LLO materials, such as borate and silicate polyanions.

DOI: 10.1002/adfm.201600576

Y. Zhao, J.-T. Liu, R. Ji, Q.-B. Xia, Z.-P. Ding,Prof. W.-F. Wei, Prof. Y. Liu State Key Laboratory of Powder Metallurgy Central South University Changsha , Hunan 410083 , P. R. China E-mail: weifengwei@csu.edu.cn Dr. S.-B. Wang, Prof. P. Wang National Laboratory of Solid State Microstructures College of Engineering and Applied Sciences and Collaborative Innovation Center of Advanced Microstructures Nanjing University Nanjing 210093 , P. R. China E-mail: wangpeng@nju.edu.cn Prof. D. G. Ivey Department of Chemical and Materials Engineering University of Alberta Edmonton , Alberta T6G 1H9 , Canada

1. Introduction

Currently, the rechargeable lithium ion battery (LIB) is one of the most important chemical energy storage technologies. Lay-ered transition metal oxides, with the general formula LiTMO 2 (TM = Ni, Co, Ni/Mn/Co), are the most widely used positive elec-trode materials in commercialized LIBs due to their high oper-ating voltage and high specifi c capacity of 140–180 mAh g −1 . [ 1–3 ]

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such as PO 4 3− , as shown in Scheme 1 . The concentration gra-dient driven diffusion of PO 4 3− polyanions triggers surface structural transition to form a nanoscaled spinel-like surface layer and a polyanion-doped layered core material in a single process. The off-stoichiometric, spinel-like surface structure, characteristic of enrichment of Ni and P (depletion of Mn), can serve to protect the LLO material from steady corrosion induced by organic electrolytes and facilitate Li + and electron transport. In addition, a moderate amount of polyanions is doped into the LLO bulk material, which can effectively stabilize the oxygen close-packed structure and enhance the electrochemical stability of the LLO cathode materials. Similar surface structural changes are found in other polyanion-doped LLO materials, such as BO 4 5− , SiO 4 4− , etc. Detailed microscopic and spectroscopic anal-yses are performed to get a better understanding of the struc-tural properties behind the enhanced battery performance.

2. Results and Discussion

The average structural information for the materials with and without PO 4 3− doping was characterized using powder X-ray

diffraction (XRD) ( Figure 1 ). All the XRD patterns, normalized on the basis of the intensity of (003) refl ection, can be indexed to a layered α-NaFeO 2 -type structure (space group of 3R m) and a Li 2 MnO 3 -like structure (space group of 2/C m). The enlarged graphs of the (003) and (104) refl ections (Figure 1 b) suggest that the PO 4 3− doping leads to a substantial increase in (003) and (104) d -spacings relative to pristine material. To obtain quantitative crystallographic information, Rietveld refi nement of the XRD data was conducted and the results are shown in Figure S1 and Tables S1 and S2 of the Supporting Information. The calculated lattice parameters are tabulated in Table 1 . It is apparent, in the PO 4 3− -doped materials, that both lattice param-eters a and c increase steadily as the doping level is raised. [ 30 ] As shown in Figure 1 c, additional XRD peaks in the 2-theta range of 20–22° are considered as superlattice refl ections of the Li 2 MnO 3 -like phase. As the PO 4 3− doping level reaches 5 at% or higher, sharper and stronger (020) peaks are observed when compared with the pristine material (Figure 1 c). This phenomenon indicates that the magnitude of Li and TM cation ordering within the TM layers becomes prominent as more PO 4 3− polyanions are incorporated. This can be ascribed to the PO 4 3− polyanions, with higher electronegativity, that alter the

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Scheme 1. Schematic illustration of surface structural transition induced by gradient polyanion-doping in LLO materials.

Figure 1. Structural information for as-prepared LLOs with and without PO 4 3− doping. a) Powder XRD patterns of pristine and PO 4 3− -doped samples. b) Enlarged regions for the (003) and (104) refl ections taken from the corresponding powder XRD patterns in (a). c) Enlarged region of XRD patterns showing details of the superlattice refl ection peaks.

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local electronic structure of the layered oxides. [ 30 ] Moreover, at a concentration of 7 at% PO 4 3− , an impurity phase of Li 3 PO 4 appears (Figure 1 a), which is consistent with observations in a previous report. [ 30 ]

The electrochemical behavior of the materials with and without PO 4 3− doping was evaluated using galvanostatic

charge–discharge testing. Figure 2 a compares the initial charge–discharge curves of the pristine and PO 4 3− -doped LLO materials at a current density of 0.1 C (25 mA g −1 ) from 2.0 to 4.8 V at room temperature. With PO 4 3− content increasing from 1 to 5 at%, the charge plateaus below 4.4 V shift to lower voltages, whereas the discharge plateaus shift to higher voltages (arrows 1 and 3 in Figure 2 a). The pristine material delivers an initial charge capacity of 382 mAh g −1 and the charge capacities gradually decrease to 328 mAh g −1 for the 7% P@LLO mate-rial (arrow 2 in Figure 2 a), while the pristine material delivers an initial discharge capacity of 276 mAh g −1 . Hence, the ini-tial Coulombic effi ciency of the pristine material is only 72%, whereas the 5% P@LLO material exhibits a discharge capacity of ≈300 mAh g −1 and a Coulombic effi ciency of 86% for the fi rst cycle; both values are much higher than those for pris-tine (Table S3, Supporting Information). A further increase PO 4 3− polyanion concentration, however, leads to lower specifi c

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Table 1. Refi ned crystallographic parameters for as-prepared LLOs with and without PO 4 3− doping.

Materials a [Å] c [Å] c / a ratio Refi nement parameters

Pristine 2.84015 14.11242 4.9689 Rwp: 5.65

1%P@LLO 2.84146 14.12464 4.9709 Rwp: 10.38

3%P@LLO 2.84434 14.12748 4.9668 Rwp: 4.61

5%P@LLO 2.84595 14.12772 4.9641 Rwp: 6.96

7%P@LLO 2.84789 14.13188 4.9622 Rwp: 5.92

Figure 2. Electrochemical performance of as-prepared LLOs with and without PO 4 3− doping tested between 2.0 and 4.8 V (vs Li + /Li). a) Initial charge–discharge profi les tested at a rate of 0.1 C. b) Cycling performance of as-prepared LLOs with and without PO 4 3− doping. c,d) Galvanic discharge profi les (3rd, 25th, 50th, and 100th cycles) of the pristine and 5% P@LLO materials at a rate of 1 C. e,f) Charge–discharge profi les of the pristine and 5% P@LLO materials at various C rates.

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capacity, probably due to the formation of the Li 3 PO 4 impurity phase. The results indicate that incorporation of a reasonably high amount of PO 4 3− polyanions may facilitate Li + diffusion and markedly reduce the irreversible removal of Li 2 O from the Li 2 MnO 3 component during the charge process.

The cycling performance of the materials with and without PO 4 3− doping is shown in Figure 2 b. The specifi c capacity of the pristine material degrades substantially when cycled at 1 C (Figure 2 b) and the corresponding discharge profi les experience noticeable voltage decay with increased cycling (Figure 2 c). In contrast, the PO 4 3− -doped materials exhibit excellent cycling performance after 100 cycles at 1 C (Figure 2 b) and voltage decay is effectively suppressed (Figure 2 d). In par-ticular, the 5% P@LLO material demonstrates excellent cycling stability with a capacity retention rate of 95% after 100 cycles at 1 C and maintains a stable capacity of 270 mAh g −1 as the rate is changed back to 0.1 C rate (Figure 2 b and Table S4, Sup-porting Information). Furthermore, the rate performance of PO 4 3− -doped materials is notably enhanced in contrast with the pristine material (Figure S2, Supporting Information). The 5% P@LLO material shows high rate performance with 252 mAh g −1 at 0.2 C, 194 mAh g −1 at 1 C, 165 mA h g −1 at 2 C, 135 mAh g −1 at 4 C, and 121 mAh g −1 at 6 C. The pris-tine material, on the other hand, delivers a discharge capacity of 197 mAh g −1 at 0.2 C, 83 mAh g −1 at 1 C, 57 mA h g −1 at 2 C, 31 mAh g −1 at 4 C, and 17 mAh g −1 at 6 C (Figure 2 e,f).

To elucidate the origin of the comprehensive improvements in the electrode kinetics, the fi rst cycle irreversible capacity and long-term cycling stability observed in the PO 4 3− -doped materials, structural changes to both the bulk and electrode

surface need to be characterized. The XRD analysis above does not provide direct evidence of local structure and coordinate chemical information, so the surface structures were exam-ined using electron microscopies (scanning electron micros-copy (SEM), high-resolution transmission electron microscopy (HRTEM), and aberration-corrected scanning transmission electron microscopy (STEM)) and X-ray photoelectron spec-troscopy (XPS). The SEM images of the materials with and without PO 4 3− doping, as shown in Figure 3 a,c and Figure S3 of the Supporting Information, reveal that all materials consist of well-crystallized particles with very similar dimensions and morphologies. Figure 3 b shows a typical HRTEM image and FFT (fast Fourier transformed) diffraction patterns taken from the core (region 1) and the surface part (region 2) of pristine material. Well-defi ned lattice fringes with an average spacing of 0.475 nm and similar FFT patterns along the [010] hexag-onal zone axis confi rm that the whole pristine particle shows a high degree of crystallinity and well faceted surfaces. For the PO 4 3− -doped materials, in addition to a well-defi ned layered structure in the core part, there exists a surface layer (≈2 nm thick) along certain crystallographic facets (Figure 3 d). For the FFT patterns along [010] hexagonal zone axis of the core parts, another set of diffuse streak patterns is evident in the FFT images taken from the surface regions in the doped materials, shown as red circles in the FFT pattern (Figure 3 d). These dif-fuse streak patterns arise from the surface layer and are indexed to a spinel-like phase ( 3Fd m) along the [01-1] zone axis.

To analyze the surface structure at the atomic scale, high angle annular dark fi eld-scanning transmission electron microscopy (HAADF-STEM) images were obtained. Figure 4 a

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Figure 3. SEM images of a) pristine and c) 5% P@LLO material. HRTEM images and FFT patterns of b) pristine and d) 5% P@LLO material.

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shows a representative atomic resolution STEM image of a pristine particle along the [010] zone axis projection, where alternative stacking of Li slabs and TM slabs along the [003] direction is clearly observed. As the PO 4 3− -doped particles are viewed along the same [010] zone axis projection (Figure 4 b), the presence of a spinel-like structure on selected surface facets of the particles is confi rmed. The orientation relationship between the layered bulk and the spinel surface is described as: (003) L �(1-11) S and [010] L �[01-1] S . Interestingly, Figure 4 b shows that preferential exposure of {111} crystallographic planes exists on these surface layers, which are recognized as stable facets for the spinel structure. [ 41 ] It is worth noting that TM atoms (especially Ni) substitute for some of the lithium atom columns in the spinel lat-tice and the extra HAADF imaging contrast are due to the presence of antisite defects (line profi le of Li slabs in Figure 4 b). Atomic resolution X-ray energy-dispersive spectros-copy (XEDS) line scans across the surface confi rm that there is segregation of Ni at the expense of Mn (Figure S4, Supporting Infor-mation). The structural and spectroscopic analyses confi rm the idea that gradient poly-anion-doping leads to a surface structural transition in the PO 4 3− -doped LLO materials. More fascinating, similar surface structural changes were also revealed in BO 4 5− - and SiO 4 4− -doped LLO materials ( Figure 5 ).

XPS surface analysis and depth profi ling were employed to provide further evidence

for the presence of the off-stoichiometric, spinel-like surface layer induced by gradient polyanion-doping. Figure 6 a–c com-pares typical XPS spectra for Ni 2p, Co 2p, and Mn 2p for the pristine and PO 4 3− -doped materials before etching. Incorpora-tion of phosphate leads to slight shifts to higher binding ener-gies for the Mn/Co cations, suggesting that the average valence of Mn/Co cations increases in order to balance the negatively charged PO 4 3− . [ 30 ] For the PO 4 3− -doped material, the P 2p peak is detected at 133.7 eV (Figure S5, Supporting Information), corresponding to the presence of phosphate polyanions. [ 42 ] To confi rm that gradient polyanion-doping occurs in the mate-rial surface, XPS depth profi les were collected (Figure 6 d–f).

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Figure 4. Comparison of HAADF-STEM images, corresponding line profi les and crystallographic model of as-prepared LLOs with and without PO 4 3− doping. a) Pristine material along [010] zone axis. b) 5% P@LLO material with spinel surface and the layered bulk along [01–1] and [010] zone axes, respectively.

Figure 5. Atomic resolution HAADF-STEM images of as-prepared LLOs doped with a) 5% SiO 4 4− and b) 5% BO 4 5− polyanions (spinel surface and the layered bulk in [011] and [010] zone axes, respectively).

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Depletion of Mn is associated with the enrichment of Ni and P and is evidence of doping in the surface region (as marked by the dotted box) for the PO 4 3− -doped samples (Figure 6 d–f and Table S5, Supporting Information). The results suggest that IV P cations tend to occupy the tetrahedral interstitial sites formed by three planes of MO 6 octahedra and one plane of a LiO 6 octahedron in the layered bulk material because of their small ionic radii of 0.34 Å (Figure S6a, Supporting Informa-tion). [ 43 ] PO 4 3− -doping can effectively restrain the migration of TM cations and alleviate the fi rst cycle irreversible capacity and capacity/voltage decay during electrochemical cycling. With the assistance of PO 4 3− polyanions, a signifi cant amount of Ni cations occupy the octahedral sites in the Li layer of the layered structure preferentially and induce the formation of nanoscaled spinel-like surface structure (Figure S6b,c, Supporting Informa-tion). Since this surface layer is associated with Mn depletion (Figure 6 ), attack by hydrofl uoric acid (HF) and Mn dissolution can be effectively suppressed, [ 44,45 ] leading to more stable inter-faces in contact with the electrolyte. Moreover, the nanoscale electrochemically active spinel-like surface layer, characteristic of high electronic and Li + conductivities, facilitates Li + and elec-tron transport on the electrode surface, which accounts for the reduced overall polarization and improved rate capability in the PO 4 3− -doped LLO materials.

To confi rm the improvement of gradient PO 4 3− polyanion-doping, XRD and HAADF-STEM analyses were carried out on the cycled materials with and without PO 4 3− polyanion-doping ( Figure 7 ). The XRD patterns show that the PO 4 3− -doped mate-rial possesses improved structural integrity compared with the pristine material during electrochemical cycling (Figure 7 a). For the pristine oxide after 110 cycles (Figure 7 b), the Z-contrast decreases signifi cantly and local spinel/amorphous domains are

formed in coexistence with the layered structure, indicating infe-rior structural stability. By contrast, the layered structure in the PO 4 3− -doped material is retained after the same amount of elec-trochemical cycling. Cation mixing or layered-spinel phase trans-formation occurs primarily on the surface regions (Figure 7 c).

3. Conclusion

In summary, a lithium-rich layered cathode with a nanoscale spinel-like surface layer was prepared through gradient doping of PO 4 3− polyanions. The spinel-like surface nanolayer, char-acterized by Mn depletion, protects the cathode material from attack by hydrofl uoric acid (HF) and Mn dissolution, and facili-tates Li + and electron transport. In addition, a moderate amount of polyanions was doped into the bulk material, effectively sta-bilizing the oxygen close-packed structure and enhancing the electrochemical stability of the LLO cathode materials. Similar surface structural changes were found in other polyanion-doped LLO materials such as BO 4 5− , SiO 4 4− , etc. We anticipate that this gradient polyanion-doping strategy should shed light on the design and development of a wide range of other layered cathode materials.

4. Experimental Section Materials Synthesis : Li 1.17 Mn 0.5 Ni 0.17 Co 0.16 (PO 4 ) x O 2-4x (X = 0, 0.01, 0.03,

0.05, 0.07) was prepared using a coprecipitation method, as described previously. [ 46 ] A 1 M mixed solution of MnSO 4 ·H 2 O, NiSO 4 ·6H 2 O, and CoSO 4 ·7H 2 O (Mn:Ni:Co molar ratio of 3:1:1) and a 2 M NaOH aqueous solution with an appropriate amount of NH 3 ·H 2 O were separately pumped into a continuously stirred reactor under N 2 atmosphere

Figure 6. Chemical information for as-prepared LLOs with and without PO 4 3− doping. a–c) XPS spectra for Mn 2p, Co 2p, and Ni 2p for pristine and borate-doped samples. d) XPS spectra for P 2p at various depths in the PO 4 3− -doped sample. e,f) Compositional variation for the TMs and P as a func-tion of etched depth. The dotted box shows the depletion of Mn (enrichment of Ni and P) in the surface region of the PO 4 3− -doped sample.

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at 60 °C. During the coprecipitation process, the pH value was kept at 11. The coprecipitated product was fi ltered, washed with distilled water, and dried in a vacuum oven at 110 °C for 12 h. The obtained precursor was thoroughly mixed with a stoichiometric amount of NH 4 H 2 PO 4 and LiOH·H 2 O (8% rich), calcined at 500 °C for 5 h and then heated to 850 °C for 15 h in air.

Materials Characterization : The chemical composition of the as-prepared Li 1.17 Mn 0.5 Ni 0.17 Co 0.16 (PO 4 ) x O 2-4x materials was deter mined using inductively coupled plasma-atomic emission spectros copy (ICP-AES). The crystallographic structure of the Li 1.17 Mn 0.5 Ni 0.17 Co 0.16 (PO 4 ) x O 2-4x materials were characterized by powder XRD (Rigaku D/Max-2500 Diffractometer with Cu Ka radiation, λ = 1.54056 Å) and selected area electron diffraction (SAED) with a JEOL JEM-2100F fi eld-emission transmission electron microscope (FE-TEM). The morphology was evaluated using a Nova Nano SEM230 fi eld emission scanning electron microscope (FE-SEM). A FEI Titan3 G2 60–300 TEM equipped with a double aberration-corrector for both the probe-forming and imaging lenses was used to perform ABF/HAADF imaging. Chemical state and composition analysis were carried out by XPS using an ESCALAB 250Xi X-ray photoelectron spectrometer. Etching with Ar + ions was used to obtain depth profi les of Mn, Ni, Co, and P. The etching rate was estimated as 5.4 nm min −1 . All XPS spectra were calibrated using the C 1s line at 284.8 eV. Curve fi tting and background subtraction were accomplished using Thermo Advantage Version 5.52 software.

Electrochemical Characterization : The synthesized materials were mixed with acetylene black and polyvinylidene fl uoride in a weight ratio

of 8:1:1 in N-methyl-2-pyrrolidone to form a slurry. Subsequently, the slurry was coated onto Al foil and then dried at 110 °C for 12 h in a vacuum oven to obtain the as-prepared cathodes. The electrochemical testing was conducted with CR2025 coin-type half-cells assembled in an Ar-fi lled glove box. The half-cells consisted of an as-prepared cathode, a Li metal anode, a Celgard 2500 separator and 1 M LiPF 6 in EC-DMC (weight ratio 1:1) electrolyte solution. The cells were cycled on a battery testing system (LANHE CT2001A, Wuhan LAND Electronics Co., P. R. China) between 2.0 and 4.8 V.

Supporting Information Supporting Information is available from the Wiley Online Library or from the author.

Acknowledgements Y.Z. and J.-T.L. contributed equally to this work. This work was supported by the Recruitment Program of Global Youth Experts, the National Natural Science Foundation of China ( 51304248 and 11474147 ), the Program for New Century Excellent Talents in University ( NCET-11-0525 ), the Doctoral Fund of Ministry of Education of China ( 20130162110002 ), the Program for Shenghua Overseas Talents from

Figure 7. Comparison of structural information for the pristine and PO 4 3− -doped materials after 110 cycles. a) XRD patterns. b) HAADF-STEM image for the cycled pristine material. c) HAADF-STEM image for the cycled PO 4 3− -doped material.

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Central South University, and the State Key Laboratory of Powder Metallurgy at Central South University. The authors would like to thank Mingquan Xu and Qin Guo for helpful discussion.

Received: February 1, 2016 Revised: March 9, 2016

Published online: May 9, 2016

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