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Synergism of Rare Earth Trihydrides and Graphite in Lithium Storage: Evidence of Hydrogen-Enhanced Lithiation Xinyao Zheng, Chengkai Yang, Xinghua Chang, Teng Wang, Meng Ye, Jing Lu, Henghui Zhou,* Jie Zheng,* and Xingguo Li* in MgH2, which shows a high theoretical capacity of 2038 mA h g−1 and gained much attention consequently.[3–5] Other hydrides such AlH3, TiH2, Mg2NiH4, Mg2CoH5, and Mg2FeH6 were also studied.[6,7] In addition to the high theoretical capacity, hydrides have the lowest charge/discharge hysteresis in all the conversion type anode materials as well as suitable lithiation potential, which make them highly promising as a new type of LIB anode materials.[3] The hydrides of rare earth (RE) elements have not been studied for lithium storage. RE can form both dihydrides (REH2) and trihydrides (REH3).[8] Assuming a conversion mechanism similar to that for MgH2, simple thermodynamic calculation suggests that only the H from the REH3–REH2 conversion is thermodynamically feasible for lithium storage, while the H in REH2 is too stable to react with Li+ to form LiH above the Li+/Li potential. In this case, the capacity would already be too low for any practical application even for the lightest RE element yttrium. However, the real situation is not that simple. In this work, we present an extensive study on the lithium storage in RE (RE = Y, La, and Gd) hydrides. The results suggest that REH2 is inactive for lithium storage, while REH3 shows a surprising synergetic lithium storage mechanism with graphite. We propose that the released H from REH3 can significantly enhance the Li+ binding to the graphene layer. The enhanced Li storage capacity is about three Li per H atom, which is very similar for RE = Y, La, and Gd. The H-enhanced lithiation model is confirmed by theoretical calculation, which suggests that the active H is negatively charged and thus can stabilize the extra Li+ binding to the graphene layer. The unexpected results provide new possibilities to design anode electrodes of LIBs. We start with the YH3–graphite composites (YH3/G-r, where r is the mass ratio of YH3/graphite). The samples are prepared by ball milling (BM) of YH3 powder and graphite under 0.4 MPa H2. The X-ray diffraction (XRD) pattern of YH3/G-0.5/1 (Figure S1, Supporting Information) contains diffraction peaks from both YH3 (JCPDS No. 12-0385) and graphite (JCPDS No. 65-6212), indicating that BM does not significantly change the crystal structure of the two components. The YH3 particles in the composite show irregular shape with average particle size about 200 nm, as suggested by the scanning electron microscope (SEM) image (Figure 1a). Energy dispersive spectrum (EDS) mapping suggests that the distribution

The lithium storage capacity of graphite can be significantly promoted by rare earth trihydrides (REH3, RE = Y, La, and Gd) through a synergetic mechanism. High reversible capacity of 720 mA h g−1 after 250 cycles is achieved in YH3–graphite nanocomposite, far exceeding the total contribution from the individual components and the effect of ball milling. Comparative study on LaH3–graphite and GdH3–graphite composites suggests that the enhancement factor is 3.1–3.4 Li per active H in REH3, almost independent of the RE metal, which is evident of a hydrogen-enhanced lithium storage mechanism. Theoretical calculation suggests that the active H from REH3 can enhance the Li+ binding to the graphene layer by introducing negatively charged sites, leading to energetically favorable lithiation up to a composition Li5C16H instead of LiC6 for conventional graphite anode. There is a continuous search for high-performance lithium storage materials to improve the energy/power density, safety, and life time of lithium-ion batteries (LIBs).[1] Graphite anode was a milestone for the wide commercialization of LIBs,[2] which remains the standard choice in the current commercial LIBs due to its excellent stability and low cost. However, limited by its low theoretical capacity (372 mA h g−1), graphite no longer meets the requirement for the next-generation high energy density LIBs. There have been tremendous research efforts on materials with higher lithium storage capacity. Recently, metal hydrides appeared as a very interesting alternative, which stores lithium through the conversion mechanism, i.e., forming LiH and the corresponding metal in the lithiated state. The Li storage in hydrides was first demonstrated

X. Zheng, C. Yang, X. Chang, T. Wang, Prof. H. Zhou, Prof. J. Zheng, Prof. X. Li Beijing National Laboratory for Molecular Science (BNLMS) College of Chemistry and Molecular Engineering Peking University Beijing 100871, P. R. China E-mail: [email protected]; [email protected]; [email protected] M. Ye, Prof. J. Lu School of Physics Peking University Beijing 100871, P. R. China The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.201704353.

DOI: 10.1002/adma.201704353

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Figure 1. a) An SEM image and element distribution by EDS of YH3/G-0.5/1. b) TEM images of YH3/G-0.5/1. c) Potential profiles of YH3/G-0.5/1 and YH2/G-0.5/1, respectively, during the first discharge/charge process at 50 mA g−1. d,e) XRD patterns of YH3/G-0.5/1 and YH2/G-0.5/1 at different lithiation/delithiation stages indicated by the corresponding numbers in panel (c).

of Y and C in the composite is very homogeneous (Figure 1a). The transmission electron microscope (TEM) image suggests that the aggregated YH3 particles around 200 nm are composed of smaller particles of ≈20 nm in diameter (Figure 1b). In the high-resolution TEM image, lattice fringes with 0.34 nm interspace that are intersected at 60° can be identified, which matches well with the (200) and (020) planes of hexagonal YH3. Curved graphene layers in graphite can also be observed (Figure 1b). Figure 1c shows the potential profiles of YH3/G = 0.5/1 and YH2/G = 0.5/1 samples during the galvanostatic discharge/ charge process. As to YH3/G = 0.5/1, the lithiation and delithiation capacities of the first cycle are 1430 and 800 mA h g−1, respectively. The loss of initial Coulombic efficiency (ICE) is mainly due to the irreversible Li+ consumption during the formation solid electrolyte interface layer. Ball-milled graphite samples often exhibit low ICE due to the high specific surface area[9–11] and high density of defects caused by BM.[12] The whole process is indicated by the plateau at 1.0 V in the first lithiation step. The characteristic lithiation plateau becomes very inclined and resembles to that of amorphous carbon materials,[13,14] which is attributed to the BM-induced disorder. The products at different lithiation/delithiation stages are analyzed by XRD (Figure 1d). After lithiation to 0.3 V, diffraction peaks corresponding to YH2 (JCPDS NO. 12-0388) appear together with the weakening of the YH3 peaks, indicating that YH3 is converted to YH2 during the lithiation process. The fully

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lithiated sample is composed of YH2 and graphite. There is neither appreciable shift of the (002) peak of graphite nor formation of lithium carbide. During the delithiation process, part of the YH2 phase is converted back to YH3. The same reversible YH2–YH3 conversion induced by lithiation/delithiation can still be clearly identified after 100 cycles at higher current density of 500 mA h g−1 (Figure S2, Supporting Information), as suggested by XRD pattern (Figure S4, Supporting Information). The XRD analysis clearly demonstrates that only one of the three H atoms in YH3 is active for lithium storage through the YH3–YH2 conversion. This can be further confirmed by the XRD study on the lithiation/delithiation process of the YH2/G composite (Figure 1e). The YH2 peak at 29.8° and 34.5° persists in the XRD patterns of the as-prepared, fully lithiated, and fully delithiated samples, indicating that YH2 is inactive for lithium storage. The stable capacity of the YH2/G-0.5/1 sample is only around 400 mA h g−1, with much shorter discharge/charge plateau at low potential. As will be shown later, this lithium storage behavior is characteristic of ball-milled graphite. An intriguing paradox here is the fact that only 1/3 of the H in YH3 is active for lithium storage, while the measured capacity for the YH3/G-0.5/1 sample reaches 800 mA h g−1. In addition, the high capacity is very stable. After 250 cycles at low current density of 50 mA g−1, a very stable capacity of 720 mA h g−1 is obtained (Figure 2a). Unfortunately, the capacity rapidly decreases as the current density increases. At

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Figure 2. a) Cycling performance of YH3/G-0.5/1 at 50 mA g−1. b) Cycling performance of YH3/G-0.5/1 at various current densities. The current density (in mA g−1) is indicated by corresponding number. c) Cycling performance of the YH3/G samples with different compositions at 50 mA g−1. The YH3/ graphite mass ratio is indicated by the numbers. d) The stable capacity versus the mass ratio of YH3/graphite. The capacity after 50 cycles is used as the stable capacity. Each data point is the average value from several repeated measurements. e) CV curves (the second cycle) of YH3/G-0.5/1 and YH2/G-0.5/1 with potential scan rate of 0.1 mV s−1.

2500 mA g−1, the capacity is only 170 mA h g−1. Interestingly, when the current density is switched back to 50 mA g−1, the high capacity of 720 mA h g−1 is almost immediately restored, as shown in Figure 2b. The above observation suggests that there is a high capacity but kinetically slow lithium storage process in the YH3/G composite. The YH3/G-0.5/1 electrode remains intact with little cracks or particle aggregation after 100 cycles (Figure S3, Supporting Information), which is in agreement with the good cyclic stability as shown in Figure 2a. Another important observation is that the reversible capacity strongly depends on the YH3/G ratio. As shown in Figure 2c, all the samples exhibit very stable cyclic stability after 60 cycles. The potential profiles of YH3/G samples with various mass ratio share very similar general features, while the capacity

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is different (Figure S5, Supporting Information). Figure 2d summarizes the correlation between the mass ratio of YH3/G and the stable capacity. The highest capacity is 720 mA h g−1, obtained with YH3/G mass ratio of 0.5/1. The capacity decreases when the ratio varies away from the optimal value. The capacities for YH3/G-0.05/1 and YH3/G-1/1 samples are only 444 and 366 mA h g−1, respectively. The extraordinarily high capacity of the YH3/G sample cannot be explained by the conventional conversion reactionbased lithium storage mechanism.[15,16] Particularly, the strong composition dependence implies that the YH3 may enhance the lithium storage capacity of graphite. To elucidate the role of YH3, it is illustrative to compare the cyclic voltammetry (CV) curves of the pure YH3, YH3/G, and YH2/G samples. Figure 2e

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shows the CV curves of these samples in the second cycle at slow scan rate of 0.1 mV s−1. The CV curve of the YH2/G sample is very similar to that of pure graphite, which only shows an anodic peak A′ at 0.2 V, corresponding to delithiation from graphite.[17] On the other hand, the YH3/G sample exhibits a new pair of sharp peaks (B–B′) at about 0.18 V, which is not observed for the pure YH3 or the YH2/G electrodes. As will be shown later, the peaks are corresponding to a new lithiation/ delithiation mechanism related to the active hydrogen in YH3. The theoretical capacity of graphite is 372 mA h g−1, corresponding to the formation of Li-intercalated compound LiC6. Graphite samples in LIBs typically show capacity below 350 mA h g−1.[9,18] Higher capacity has been reported for porous carbon with high specific surface area, which is usually attributed to Li binding on the interface or within the nanoscale pores.[19] Graphene also shows higher capacity, as Li binding occurs on both sides of the graphene layer.[20] The capacity of graphite can be promoted by BM.[13,14] To estimate the effect of BM, we measure the capacity of the YH2/G-0.5/1 and NaCl/G-0.5/1 samples, which are both around 400 mA h g−1. As both YH2 and NaCl are inert in lithium storage, this is a good estimation for the capacity of BM-enhanced graphite samples. The enhanced capacity is mainly attributed to the defects introduced by BM, which provides additional Li+ binding sites. SEM images suggest that the morphology of the two samples is similar to that of YH3/G-0.5/1 (Figure S6, Supporting Information). The specific surface areas of YH2/G and NaCl/G samples prepared by BM are 356 and 336 m2 g−1, respectively, significantly enhanced compared with the pristine graphite sample (18 m2 g−1). The high specific surface area can enhance lithium storage capacity via the interface storage mechanism.[21] On the other hand, the specific surface area of the YH3/G-0.5/1 sample is only 106 m2 g−1 (see Figure S7 in the Supporting Information). Therefore, the BM-enhanced capacity of the YH3/G sample should not be higher than YH2/G. A more detailed analysis of the contribution of each component to the capacity of the YH3/G electrode is carried out. The YH3/G electrode is composed of YH3, graphite (enhanced by BM), and acetylene black (AB). AB shows a very stable capacity of 300 mA h g−1, which is typical of carbon-based materials. The potential profiles of the individual components normalized to their fraction in galvanostatic charge/discharge processes are shown in Figure 3a. The well-defined lithiation/delithiation plateaus of pure graphite are no longer observed in AB and BM-enhanced graphite samples, which is typical of disordered carbon materials.[14,22] The contribution of the YH3 component in the YH3/G-0.5/1 sample to the capacity is only 15 mA h g−1, estimated from an electrode composed of YH3 powder and AB mixed by gentle hand milling. The total contribution from individual components remains 303 mA h g−1 lower than the measured value. The potential profile of the enhanced part is shown by the dotted red curve in Figure 3a (see Table S2 in the Supporting Information for detailed derivation of the potential curve of the enhanced part). The majority of the capacity is in the low potential region (1040 mA h g−1) has been reported for N-, B-, and P-doped graphene/carbon materials.[11,23] Particularly, it has been reported that hydrogenated carbon, typically obtained by lowtemperature pyrolysis of organic precursors, also shows high lithium storage capacity.[24] Using semiempirical simulation, Papanek and Fischer have proposed that a large excess capacity may stem from Li binding at the H-terminated edges of hexa gonal carbon fragments.[25]

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Figure 3. a) Comparing the experimental potential profile (the solid red curve) of YH3/G-0.5/1 and the contributions from individual components (the dashed black curves) to show the enhanced capacity due to the active hydrogen from YH3. The solid black curve is the summation of the contributions from each component without the H-enhanced capacity. b) The potential profiles of REH3/G-0.5/1 (RE = Y, La, and Gd) during stable cycling. c) The potential profiles of the active H-enhanced capacity (represented by the number of Li per H) of the REH3/G-0.5/1 samples (RE = Y, La, and Gd). d) The stable capacity of different samples, showing the enhanced capacity due to BM and the active H from REH3.

However, this mechanism is questionable to apply to the REH3/G system. In the hydrogenated carbon, the H atoms are covalently bonded to carbon. However, CH covalent binding is absent in the REH3/G samples. The CH stretching modes (2900–3100 cm−1) are absent in the Fourier transform infrared spectrometry (FT-IR) spectra of the three REH3/G samples (Figure S13, Supporting Information). All the three REH3/G samples exhibit a sharp resonance peak at 1.84 ppm in the 1H NMR spectra and a broad peak centered at 116 ppm in the 13C NMR spectra, respectively (Figure S14, Supporting Information). These features are corresponding to the hydrogen in metal hydrides and the CC signal in pure graphite, respectively.[26] In the X-ray photoelectron spectroscopy (XPS) spectra of the YH3/G-0.5/1 sample (Figure S15, Supporting Information), the binding energy is 284.8 eV for C 1s and 158.3 eV for Y 3d5/2,

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which is close to that of pure graphite and pure YH3, respectively.[27] The above spectroscopic characterizations confirm the absence of CH binding in the REH3/G samples. Defects related to sp3 type carbon are identified in the Raman spectra, as indicated by the higher ratio of the G/D peaks, slight blue shift of the G peak and the emergence of the D′ peak at around 1608 cm−1. However, the defects should be attributed to the BM rather than the CH binding, as almost the same features are also observed for the YH2/G and NaCl/G samples (Figure S16, Supporting Information).[28] Moreover, the hydrogenated carbon typically shows large hysteresis in charge/discharge. Most lithiation occurs in the high potential region (>1.0 V).[29] However, the hysteresis observed in the YH3/G is mainly due to the BM effect. The enhanced capacity due to the synergism shows very low hysteresis at low charge/discharge plateau (≈0.15 V).

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Figure 4. a) Schematics illustration of the lithiation process of pure graphite and REH3/graphite composites, together with the schematic illustration of the fully lithiated structure on a single graphene layer. b) The charge density distribution of the optimized Li5C16H structure. The Mulliken charge of H and Li calculated by DFT is labeled by the numbers. Please note that the Mulliken charge is only a formal description of the partial charge and cannot be regarded as the true physical charge. c) The Gibbs free energy change (ΔG) to form LixC16 and LixC16H (3 ≤ x ≤ 7) is calculated by DFT. The maximum number of Li that can be stably bonded (ΔG < 0) is 3 and 5 for each structure.

Therefore, we propose a new mechanism for the enhanced Li binding to the graphene layer by the active H from REH3, as schematically illustrated in Figure 4a. The H in this configuration does not form conventional CH bonds to the carbon matrix. It is of hydridic nature, which provides a negatively charged center for enhanced Li binding. This proposed H-enhanced lithiation mechanism can be verified by density functional theory (DFT) calculation. We use a graphene sheet composed of 16 C atoms and 1 H atom to simulate the optimal composition YH3/G. To facilitate the calculation, the active H is represented by a solvated ion pair of Li+–H− in dimethyl carbonate (DMC). The lithiation reaction is given by C16 +DMC–LiH + ( x − 1) Li → Li x C16 H+DMC

(2)

The Gibbs free energy change to form the lithiated product LixC16H is given by Equation (3) ∆G ( Li x C16 H) = E ( Li x C16 H) − E ( C16 ) (3) − [E ( DMC − LiH) − E ( DMC )] − ( x − 1) E ( Li ) + ∆E ’

where ΔE′ is the energy to form the Li+–H− ion pair in DMC (LiH–DMC) from REH3, which can be calculated from the energy of the following reactions (Equations (4) and (5)) YH3 (s) + Li (s) → YH2 (s) + LiH (s) LiH ( s) + DMC → DMC–LiH

(4) (5)

ΔG for Equation (4) is −0.517 eV, which can be calculated from the thermodynamics data.[30]

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For comparison, the graphite sample without YH3 is simulated by a pure graphene sheet composed of 16 C atoms. The Gibbs free energy change of the lithiated product (LixC16) is given by ∆G (Li x C16 ) = E (Li x C16 ) − E (C16 ) − x E (Li )

(6)

The calculation results are summarized in Table S1 in the Supporting Information, and the optimized structure of the lithiated products is shown in Figure S16 in the Supporting Information. The calculated ΔG is plotted versus the number of Li binding to the system, as shown in Figure 4c. Lithium binding is thermodynamically favorable for negative ΔG. As a general trend, ΔG becomes more positive with the increasing number of Li for the C16 unit, indicating that Li binding is increasingly more difficult. This is quite easy to understand as the introduced Li always occupies the energetically most favorable position. The repulsive interactions between the introduced Li will also make further Li binding more difficult. For the pure C16 unit, ΔG becomes positive for Li4C16, indicating that the maximum number of Li binding is less than 4. This value is in good agreement with the theoretical fully lithiated composition of pure graphite LiC6. As shown in the optimized structure in Figure 4a, for the pure graphene layer, the Li atoms are located at the center of the hexagonal ring. The neighboring hexagonal rings cannot be occupied by Li simultaneously to minimize the repulsive Li–Li interaction, which yields the maximum lithiation to LiC6 for infinitely large graphene layers. On the other hand, with the active H from REH3, ΔG remains negative up to Li5C16H. Binding an additional Li will cause only slight energy increase to a very low positive value. Thus, the maximum number of Li bonded to each active H is 5–6, which is in good agreement with the measured capacity.

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The thermodynamic lithiation potential calculated from the calculated is 0.219 V (vs Li+/Li) for Li4C16H and 0.029 V for Li5C16H, respectively, which are in quite good agreement with the new peaks in the CV curves (Figure 2e) and the fact that the majority of the enhanced capacity is in the low potential region (Figure 1c). In the optimized Li5C16H structure, H is located at the center of a hexagonal ring, and all the neighboring hexagonal rings are occupied by Li. The Mulliken charge of H is −0.83, which is in agreement with the intuition that the H is of hydridic nature. The hydridic H mitigates the repulsive interactions of the positively charged Li and allows more Li binding. The calculated Mulliken charge of Li is around 1.0, which is in very good agreement with the Li containing systems reported literature.[31] The charge density distribution profile of Li5C16H calculated by DFT also suggests that the electrons are mainly localized around the H atom (Figure 4b). It is worth noting that ΔG reaches minimum at the composition Li4C16H (Figure 4c), indicating that sufficient number of Li+ is required to maximize the stabilization effect of the negatively charged H. The H-enhanced Li-binding model requires both graphene layers to provide binding sites for Li and active H to enhance Li binding. As shown in the optimized structure (Figure 4c), each hexagonal ring in the graphene layer can only accommodate one H or Li. Thus, the strong dependence of the lithium storage capacity on the YH3/G ratio in Figure 2d can be well understood. For low YH3/G ratio, the Li storage capacity is limited by the active H. On the other hand, when the YH3/G ratio exceeds the optimal value, there are insufficient accommodation sites on the graphene layers for Li binding, which again leads to lower lithium storage capacity. A missing link is how the active H is extracted from the hydride particles. Sufficiently, fast H diffusion in hydrides is required to achieve effective utilization of the active H. We note that slightly higher Li-binding number per active H is found for LaH3, despite the highly similar lithium storage behavior of the three REH3/G (RE = Y, La, and Gd) samples. This may be attributed to faster H diffusion in LaH3, as La has the largest atomic radius, which allows higher utilization of the active H. During the lithiation process, the hydrogen extraction may be driven by the electrochemical potential. Metal hydrides have been extensively used as the negative electrode in nickel–metal hydride (Ni–MH) batteries. As quite high current density can be achieved in Ni–MH batteries, the electrochemical-driven hydrogen diffusion should have reasonably fast kinetics at room temperature. Moreover, the REH3/G samples are prepared by BM in hydrogen atmosphere. The dynamic hydrogen absorption/desorption during the milling process may facilitate pulverization of the hydride particles. As a result, the primary particle size of the REH3 hydrides is only around 20 nm, which is also favorable for the electrochemical extraction of the active H. An interesting question is why such synergism was not observed for other hydrides such as MgH2. A possible reason is that the enhanced capacity cannot be distinguished from the intrinsically high capacity of MgH2 through the conventional conversion mechanism (theoretical capacity 2038 mA h g−1). Moreover, in the conversion mechanism, LiH is generally accepted as the lithiated product. However, formation of LiH is only supported by very weak diffraction peaks in XRD.[3,5] Thus, the H-enhanced Li-binding mechanism proposed here cannot

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be fully excluded for MgH2. Generally, the capacity enhancement due to the active H is closely associated with the nature of H in the hydrides, such as energy, charge state, and mobility. Further study is certainly required to understand the correlation between the nature of hydrogen in metal hydrides and their behaviors in lithium storage. We experimentally verify that the REH3–REH2 (RE = Y, La, and Gd) conversion will provide an active H to enhance the lithium storage capacity in graphite. Enhanced lithium storage capacity up to more than three Li+ per active H is observed through the synergism with graphite, which is very similar for RE = Y, La, and Gd. The YH3/G-0.5/1 exhibits high reversible capacity of 720 mA h g−1 after 250 cycles. DFT calculation suggests that the active H from REH3 provides a negatively charged center, which mitigates the repulsive Li–Li interaction and allows more Li binding to graphite. This unprecedented phenomenon provides the first experimental evidence for H-enhanced lithiation, which is illuminating for designing new anode materials for LIBs.

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

Acknowledgements X.Z. and C.Y. contributed equally to this work. The authors acknowledge the financial support from the National Science Foundation of China (NSFC, Nos. 51431001, U1607126, 11375020, and 21321001).

Conflict of Interest The authors declare no conflict of interest.

Keywords anodes, graphite, hydride, lithium-ion batteries, rare earths Received: August 2, 2017 Revised: September 28, 2017 Published online:

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