Improving Li-ion interfacial transport in hybrid solid electrolytes

The development of commercial solid-state batteries has to date been hindered by the individual limitations of inorganic and organic solid electrolytes, motivating hybrid concepts. However, the room-temperature conductivity of hybrid solid electrolytes is still insufficient to support the required battery performance. A key challenge is to assess the Li-ion transport over the inorganic and organic interfaces and relate this to surface chemistry. Here we study the interphase structure and the Li-ion transport across the interface of hybrid solid electrolytes using solid-state nuclear magnetic resonance spectroscopy. In a hybrid solid polyethylene oxide polymer–inorganic electrolyte, we introduce two representative types of ionic liquid that have different miscibilities with the polymer. The poorly miscible ionic liquid wets the polymer–inorganic interface and increases the local polarizability. This lowers the diffusional barrier, resulting in an overall room-temperature conductivity of 2.47 × 10−4 S cm−1. A critical current density of 0.25 mA cm−2 versus a Li-metal anode shows improved stability, allowing cycling of a LiFePO4–Li-metal solid-state cell at room temperature with a Coulombic efficiency of 99.9%. Tailoring the local interface environment between the inorganic and organic solid electrolyte components in hybrid solid electrolytes seems to be a viable route towards designing highly conducting hybrid solid electrolytes. NMR measurements show that the interface between the inorganic and organic components can be tailored to design a highly conducting hybrid solid electrolyte.

S olid-state batteries are recognized as key candidates for next generation batteries because of their potential to improve both energy density and safety 1,2 . However, the progress in their development is hindered by the many criteria that solid electrolytes must satisfy to become commercially viable. These include high ionic conductivity, flexibility, (electro)chemical stability, compatibility with electrode materials and processability, conditions that are often hard to fulfill with an individual organic or inorganic solid electrolyte material [3][4][5][6][7] . This has led to the investigation of hybrid electrolytes that typically combine an organic and an inorganic phase [8][9][10][11] . An intensively investigated hybrid solid electrolyte (HSE) comprises inorganic filler particles embedded in a conductive organic polymer matrix. The use of polyethylene oxide (PEO) as the organic polymer component together with a Li-containing salt is attractive because of its relative stability towards lithium metal, excellent contact/adhesion with electrodes, superior mechanical properties and good flexibility, allowing facile production as thin films on a large scale [12][13][14][15][16][17] . Properties such as particle size, relative amount and morphology of the inorganic component influence the conductivity of the HSE. Typically, inorganic fillers are added to lower the glass transition temperature of PEO. This enhances the polymer chain segmental mobility and results in higher ionic conductivity 13,18-20 . More recently, HSEs with inorganic ionic conductors as additives have been investigated with the aim to provide highly conductive pathways for Li-ion transport to improve the overall conductivity of the HSE (refs. 18,[20][21][22][23][24] ). However, despite the high ionic conductivity of these inorganic fillers (for example > 1 mS cm −1 ), their room-temperature Li-ion conductivity remains far from what is demanded for all-solid-state-batteries (~1 mS cm −1 ). This raises questions about the Li-ion transport pathway through the heterogeneous HSE, and especially on the role of the interface between the organic and inorganic components. However, it is challenging to monitor the Li-ion transport in HSEs at the sub-nano scale of interfaces. Several approaches have been reported that explore the correlation between interface environment and Li-ion movement in HSEs (refs. 4,18,[25][26][27][28] ). Three-dimensional (3D) structural reconstruction of HSEs obtained from synchrotron experiments and physics-based modelling indicates that the inorganic particles are highly aggregated in the electrolyte, which would affect the internal Li-ion transport between different phases 4,25 . Four-point electrochemical impedance measurements and surface-sensitive X-ray photoelectron spectroscopy revealed decomposition reactions between the organic and inorganic phases, which may significantly affect the Li-ion transport 26,27 . Recently, combining selective isotope labelling with high-resolution solid-state nuclear magnetic resonance (NMR), Li-ion diffusion pathways were tracked within a Li 7 La 3 Zr 2 O 12 (LLZO)-PEO HSE (refs. 18,28 ). While these studies provide insight into Li-ion transport in HSEs, it is also evident that it remains a challenge to directly access the interfacial structure, correlate this to the Li-ion transport across the interface and use this to develop strategies to improve the conductivity of HSEs (ref. 10 ).
To gain deeper insight into the Li-ion transport in HSEs in conjunction with the inorganic-organic interphase structure, we employed an experimental approach using electrochemical impedance spectroscopy (EIS) and multinuclear solid-state NMR. This allows us to measure the bulk conductivity as well as directly access the interphase structure and interfacial Li-ion diffusion in an HSE comprising an LiTFSI (lithium-bis (trifluoromethane-sulfonyl) imide)-PEO organic and an argyrodite Li 6 PS 5 Cl inorganic component. We find that the ionic conductivity of the HSE is impeded by the chemical structure of the decomposition layer between the organic and inorganic phases. To overcome this the interface is 'activated' by adding an ionic liquid that settles at the organic-inorganic interface of the HSE because it is poorly miscible with PEO. This enables Li-ion diffusion over the interface, which increases the overall ionic conductivity of the HSE as visualized by two-dimensional (2D) 7 Li exchange NMR. Solid-state NMR is demonstrated to be a powerful method for resolving the sub-nano domains of the interface, which is impossible by other traditional characterization techniques. In this manner the bottleneck for Li-ion transport in HSEs is revealed and new design strategies are proposed towards future solid electrolytes.

Interphase structure and Li-ion diffusion in the hybrid LitFSI-PEo-Li 6 PS 5 Cl solid electrolyte
With the aim of improving the overall Li-ion conductivity of a LiTFSI-PEO polymer electrolyte, highly conductive micron-sized argyrodite Li 6 PS 5 Cl (5.6 mS cm −1 ) was mixed into the LiTFSI-PEO with a weight fraction of 10% (scanning electron microscope (SEM) images in Extended Data Fig. 1). For Li 6 PS 5 Cl to contribute to the bulk conductivity of this HSE, facile Li-ion diffusion over the interfaces between the LiTFSI-PEO phase and the Li 6 PS 5 Cl particles is a prerequisite. This is because a 10% weight fraction (8% volume fraction) will not result in percolating transport pathways through the Li 6 PS 5 Cl phase. Li 6 PS 5 Cl was selected as the inorganic filler to facilitate interfacial transport as it possesses both high ionic conductivity and high ductility, the latter enabling the formation of softer interfaces that facilitate interfacial Li-ion diffusion 29 . To study the Li-ion diffusion across the LiTFSI-PEO-Li 6 PS 5 Cl interface and to resolve the interphase structure between the organic and inorganic phases, magic angle spinning (MAS) 6,7 Li solid-state NMR was employed. This allows us to discriminate between Li ions in different chemical environments, in this case in the PEO and Li 6 PS 5 Cl phases 18,29 . As seen in Fig. 1a, the LiTFSI-PEO and Li 6 PS 5 Cl show two clear resonances with 7 Li chemical shifts of −1.39 and 1.44 ppm, respectively.
Based on the differences in 6,7 Li chemical shifts of the LiTFSI-PEO and Li 6 PS 5 Cl phases, 2D exchange spectroscopy (2D-EXSY) experiments provide selective and non-invasive quantification of the spontaneous Li-ion diffusion over the solid-solid interface between these phases 29,30 . Li-ion exchange between these two chemical environments would result in off-diagonal cross-peaks at the positions indicated with dotted boxes in Fig. 1b,c. Increasing the mixing time, T mix , therefore providing more time for the Li ions to diffuse from one phase to the other, as well as increasing the temperature, is expected to increase the Li-ion exchange flux and thus the intensity of the off-diagonal cross-peaks 29 . In this case the absence of cross-peaks, even for the maximum T mix and temperature (T mix = 2 s and 2.5 s, 328 K) that can be achieved, indicates that the Li-ion exchange (flux) between LiTFSI-PEO and Li 6 PS 5 Cl phases does not occur at the timescale of T mix , indicating very slow Li-ion diffusion across the interfaces within this HSE.
To discern the origin of the poor Li-ion diffusion across these interfaces, one-dimensional (1D) 6 Li cross-polarization (CP) MAS (CPMAS) and 2D 1 H- 6 Li heteronuclear correlation (HETCOR) experiments were carried out (Fig. 1d,e), allowing us to resolve the interface composition and structure. In these experiments, transfer of polarization occurs from protons ( 1 H), in this case abundantly present in the polymer, to any 6 Li environment in the near vicinity (within the range of a few bonds). This takes place during a varying time interval (contact time), typically in the range 200 µs-6 ms (Extended Data Fig. 2). With direct 6,7 Li excitation, only two peaks are resolved as shown in Fig. 1a for 7 Li (Extended Data Fig. 3 for 6 Li). However, in the 6 Li CPMAS spectrum several additional resonances between 1 ppm and −1.5 ppm (Fig. 1d) are resolved. The additional peaks are assigned to Li-containing polysulfides and phosphorus sulfide species 31,32 , based on previous literature 26, 27 . This indicates that inorganic decomposition products that could inhibit interfacial Li-ion transport accumulate at the interface. The 2D 1 H-6 Li experiment at a short contact time shows correlations between 1 H and 6 Li species either directly bonded to, or in very close proximity to, each other. At a short contact time of 0.2 ms (Fig. 1e, in Extended Data Fig. 2 peaks are also visible at 0.2 ms) the different Li species observed are in contact with a single 1 H environment at a chemical shift of ~1.6 ppm, which can be assigned to the -OCH 2 -group. This has been identified from X-ray photoelectron spectroscopy studies 26,27,33 as the main decomposition product of PEO chains when in contact with Li 6 PS 5 Cl and indicates that there are interfacial reactions between Li 6 PS 5 Cl and PEO. These reactions result in an inert environment deficient in ethereal oxygen that is known to mediate the Li-ion diffusion in PEO (Fig. 1f). The poorly Li-ion conducting interface environment is held responsible for the absence of Li-ion exchange (Fig. 1b,c), indicating sluggish Li-ion diffusion between the two electrolyte phases. These findings can potentially explain the difficulties in activating inorganic particles in HSEs (ref. 18 ), indicating that the interface needs to be improved to enhance the interfacial Li-ion diffusion.

addition of ionic liquids to enhance the conductivity of the PEo-Li 6 PS 5 Cl hybrid solid electrolyte
Based on the above findings, it is clear that an inert interface is formed between LiTFSI-PEO and Li 6 PS 5 Cl that impedes charge transport in the HSE. Traditionally, ionic liquids (ILs) have been used to enhance the segmental motion of PEO chains to increase the Li-ion mobility 9,34 . These ILs do not form strong ionic bonds between their cation and anion moieties and hence possess low solvation energies and remain in a dissociated state. It has been shown in previous studies that imidazole-based ILs are effective in improving the conductivity of PEO because of their low viscosity and high miscibility in PEO (ref. 34 ).
To determine whether an IL added to the HSE has an impact on the conductivity and interfacial charge diffusivity between the organic and inorganic phases, two ILs that differ significantly in their viscosity and miscibility with PEO were selected. The first was an imidazole-based IL, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (denoted as EMIM-TFSI) (Fig. 2a) and the second was a piperidinium-based IL, 1-methyl-1-propylpiperidinium bis(trifluoromethylsulfonyl)imide (denoted as PP13-TFSI) (Fig. 2b). These ILs each have a different miscibility in PEO (ref. 35 ) where the hypothesis is that the poorly miscible PP13-TFSI will be preferably located at the interface with the inorganic Li 6 PS 5 Cl phase, with the aim to improve the Li-ion diffusion across the interface. By contrast, the highly miscible EMIM-TFSI is anticipated to be distributed homogenously in the HSE and to not specifically influence Li-ion transport across the organic-inorganic interface. To test this, fixed amounts of EMIM-TFSI and PP13-TFSI (0.25:1 molar ratio IL:LiTFSI) were added to the LiTFSI-PEO-Li 6 PS 5 Cl mixture. The HSEs subsequently formed are henceforth referred to as HSE-EMIM and HSE-PP13, respectively.
To establish how the addition of the ILs improves the macroscopic conductivity of the PEO electrolyte (no Li 6 PS 5 Cl added) and of the HSEs, EIS measurements were performed. Figure 2c,  polymer electrolyte (SPE) with EMIM-TFSI (SPE-EMIM) is higher than that of the mixture with PP13-TFSI (SPE-PP13), as expected due to the high miscibility of EMIM-TFSI with PEO and in good agreement with previous literature 34 . However, when Li 6 PS 5 Cl is introduced into the system, the opposite result is found. HSE-PP13 displays a higher conductivity compared to HSE-EMIM and we should also note that both the HSEs have a higher conductivity than the materials without Li 6 PS 5 Cl. Additionally, the activation energy indicates better conductivity for the HSE-PP13 electrolyte, where the various temperature measurements shown in Fig. 2e give a lower activation energy for HSE-PP13. Clearly, introduction of the inorganic Li 6 PS 5 Cl in the PEO matrix improved the overall conductivity, indicating that the Li 6 PS 5 Cl actively contributes to the conductivity 10 . Notably, the poorly miscible PP13-TFSI IL results in a higher conductivity of the HSE as compared to the more miscible EMIM-TFSI IL. This improves the PEO conductivity.

Impact of the ionic liquid on the bulk PEo and PEo-Li 6 PS 5 Cl interphase structure
To understand the improved conductivity of the HSE upon addition of the poorly miscible PP13-TFSI IL, the structure and kinetics of the PEO-Li 6 PS 5 Cl interface, which appears to play a critical role in activating the high conductivity of the Li 6 PS 5 Cl phase, were investigated. The impact of adding the ILs to the bulk PEO structure was investigated first by comparing the 1 H and 13 C NMR spectra of the individual components. As shown in Fig. 3a, the 1 H resonances of EMIM in HSE-EMIM for the peak positions between 6 to 10 ppm show a clear shift compared to pristine EMIM-TFSI, indicating a change in the 1 H environments on the imidazole ring 36 . No change is observed for PP13 (Fig. 3b), reflecting the better miscibility of EMIM-TFSI in PEO. The chemical shifts in the 13 C CPMAS spectra (Fig. 3c,d) indicate less crystalline PEO in HSE-EMIM (70 ppm) compared to HSE-PP13 (72 ppm). This is consistent with the better miscibility of EMIM-TFSI in PEO (ref. 37 ) and this is further confirmed by the larger decrease in melting temperature when EMIM-TFSI was added (Supplementary Text 1 and Extended Data Fig. 4).
To understand the role of the IL in activating the LiTFSI-PEO-Li 6 PS 5 Cl interface, the interphase structure was explored using 2D 1 H-1 H nuclear Overhauser effect spectroscopy (NOESY) NMR measurements (Fig. 4a-f). NOESY is a commonly used method to elucidate polymer structures and configurations 38 . The cross-peaks that arise, especially for short mixing times, are typically between protons that are in close spatial proximity (<1 nm) to each other. As seen from Fig. 4a-c, all the cross-peaks between EMIM-TFSI and LiTFSI-PEO appear at nearly the same mixing time (Extended Data Fig. 5), indicating that there is no preferred orientation of the EMIM-TFSI species with respect to PEO, confirming the good miscibility and that the EMIM-TFSI is mobile. Interestingly, for HSE-PP13 the 1 H-1 H correlations are first observed (short mixing times) between 1 H resonances at positions a and b on the piperidine ring of PP13-TFSI and the -OCH 2 -protons from PEO ( Fig. 4d-f). This is especially clear from the intensity buildup shown in Extended Data atom on the piperidine ring and the functional groups it carries are oriented away from the PEO segments. Next, the interface environments in both HSEs were explored using 2D 1 H-6 Li HETCOR measurements (Fig. 4g,h). This technique makes it possible to establish which Li-containing species are in proximity to the protons present in PEO and the ILs. For HSE-EMIM (Fig. 4g) a strong correlation is found between PEO and LiTFSI, consistent with the solvation of EMIM in the PEO matrix. Additionally, PEO and EMIM (Fig. 2a) correlate with the decomposed Li 6 PS 5 Cl surface species (observed for the HSE without IL, Fig. 1d), indicating that a fraction of the PEO + EMIM is in contact with the Li 6 PS 5 Cl particles. For HSE-PP13 (Fig. 4h), no correlations between PEO and LiTFSI or the decomposed Li 6 PS 5 Cl species are observed, the former consistent with poor solvation of this IL in PEO. However, correlations between the protons on the piperidine ring (Fig. 2b) and LiTFSI as well as between the same protons of PP13 with the decomposed Li 6 PS 5 Cl surface environments are observed, indicating that PP13 is in contact with Li 6 PS 5 Cl. Finally, the PEO-Li 6 PS 5 Cl interface was further probed using 1 H-7 Li CPMAS experiments (Fig. 4i), indicating the proximity of protons near the Li 6 PS 5 Cl interface for both HSE-PP13 and HSE-EMIM but that there is a difference in proton kinetics between the two interfaces (Supplementary Text 2, Extended Data Fig. 6 and Supplementary Table 1).
To summarize, addition of EMIM-TFSI and PP13-TFSI results in very different PEO bulk and interphase structures in the HSE. 1 H and 13 C NMR, as well as differential scanning calorimetry (DSC) measurements, demonstrate that EMIM resides dominantly within

Impact of the ionic liquid on the interfacial diffusion between LitFSI-PEo and Li 6 PS 5 Cl
To understand how the Li-ion diffusion (due to equilibrium charge transfer) over the PEO-Li 6 PS 5 Cl interface of the HSE is affected by both ILs, 6,7 Li-6,7 Li 2D-EXSY NMR measurements were conducted, remembering that for the HSE without IL no Li-ion diffusion could be detected (Fig. 1b,c). For HSE-EMIM (Extended Data Fig. 7a,b), no cross-peaks are observed with mixing times as long as 2 s, indicating that there is no significant Li-ion diffusion over the LiTFSI-PEO-Li 6 PS 5 Cl interface at this timescale. By contrast, clear cross-peaks, corresponding to Li-ion diffusion between the LiTFSI-PEO and Li 6 PS 5 Cl phases, appear for HSE-PP13 ( Fig. 5 and Extended Data Fig. 7c,d). This indicates more facile diffusion over the organic-inorganic interface in the HSE-PP13, which is associated with the presence of the PP13 at the PEO-Li 6 PS 5 Cl interface established in the previous section.  7 Li EXSY spectra of the mixture of LiTFSI-pEO-Li 6 pS 5 Cl with pp13-TFSI IL measured at a spinning speed of 5 kHz at 298 K with mixing times T mix of 0.1, 0.25 and 1.5 s (a-c) and at 308 (d) and 328 K (e) with a T mix of 0.1 s. f, Evolution of cross-peak intensity as a function of T mix obtained from the 2D-EXSY measurements performed at the temperatures indicated in the graph. The line passing through the symbols is a guide to the eye. The inset figure is the dependence of the diffusion coefficient (D) obtained from fitting the data in f to a diffusion model described by us in detail elsewhere 30 . The normalized intensity is denoted in arbitrary units (a.u.). These can be fitted with the Arrhenius law, yielding an activation energy (E a ) of 0.126 eV. g, proposed mechanism for Li-ion diffusion in HSEs with EMIM-TFSI and pp13-TFSI IL additives. Intensity from low to high is shown from blue to red in a-e.
Upon increasing the mixing time and the temperature, a clear increase in cross-peak intensity is observed (Fig. 5a-e). The Li-ion exchange between the LiTFSI-PEO and Li 6 PS 5 Cl phases was quantified by fitting the evolution of the cross-peak intensity as a function of T mix (Supplementary Text 3 and Fig. 5f) to a diffusion model derived from Fick's law, described elsewere 29,30,39 . The diffusion coefficient as a function of temperature obtained from the fit (inset Fig. 5f), reflects the Li-ion self-diffusion across the LiTFSI-PEO-Li 6 PS 5 Cl interface. Fitting with an Arrhenius law yields an activation energy of 0.126 eV for diffusion between the organic and inorganic components, significantly lower than that reported with impedance measurements 26,27 . This suggests that addition of the PP13-TFSI IL 'activates' the LiTFSI-PEO-Li 6 PS 5 Cl interface, even though micron-sized inorganic argyrodite filler particles are used in the HSE. Thus, there is a relatively small ionic contact area.
Based on these observations, we can now link the PEO-Li 6 PS 5 Cl interface nanostructure with the Li-ion mobility over the interface.
The poor Li-ion diffusivity over the interface between PEO and Li 6 PS 5 Cl in the HSE can be rationalized by the observed -OCH 2groups at the interface (Fig. 1) that annihilate the conducting ethereal oxygen positions that mediate the Li-ion conductivity in PEO. The consequence is that Li-ion transport will be forced though the polymer phase and will not utilize the high conductivity of the Li 6 PS 5 Cl phase (Fig. 1f). In contrast to the miscible EMIM-TFSI, which improves the conductivity of the PEO, the much less miscible PP13-TFSI settles at the interface with the Li 6 PS 5 Cl phase (Fig.  5g) where it leads to a higher local mobility. This is held responsible for the facile Li-ion diffusivity over the PEO-Li 6 PS 5 Cl interface as quantified by the 2D-EXSY experiments in Fig. 5 and can be explained by the higher local mobility induced by the PP13-TFSI IL. The higher dielectric constant of the IL (ε > 20) compared to that of PEO (ε ∼ 5) may also play a role 40  Li-ion transport can now make use of the much higher conductivity of the Li 6 PS 5 Cl phase (Fig. 5g). This explains the higher overall conductivity of the HSE-PP13 electrolyte observed with EIS (Fig. 2c,d).

Electrochemical evaluation of the hybrid solid electrolyte upon introduction of ionic liquids
As Li metal is the ultimate anode from the perspective of battery energy density, the impact of the IL on the interface of the HSE with Li metal was evaluated in Li-metal symmetrical cells for both HSE-PP13 and HSE-EMIM electrolytes (Fig. 6). The overpotential of the symmetrical cell is an indicative parameter of the interface stability and ability to conduct Li ions 25 . In Fig. 6a, the Li/HSE-EMIM/ Li cell shows a continuous increase in overpotential when the current density is higher than 0.05 mA cm −2 , indicating insufficient Li-ion conductivity. By contrast, the Li/HSE-PP13/Li cell shows a much more stable overpotential, increasing with current density up to a relatively small value not exceeding 200 mV at 0.1 mA cm −2 .
A similar trend is observed upon cycling (Extended Data Fig. 8).
Taking it one step further, we can assume that in the HSE-PP13 electrolyte the conductivity is no longer limited by the PEO-Li 6 PS 5 Cl interface due to the presence of PP13 but by the polymer phase.
To evaluate this, an HSE was prepared with both the PP13-TFSI and EMIM-TFSI additives. In this HSE, PP13-TFSI will enhance the interfacial Li-ion diffusivity while EMIM-TFSI is expected to enhance the Li-ion diffusivity in the PEO phase by improving the chain mobility. Indeed, the small fraction of IL mixture increases the ionic conductivity to 2.47 × 10 −4 S cm −1 at 25 °C as measured by EIS (Extended Data Fig. 9). The higher conductivity upon adding both ILs is accompanied by a higher critical current density of 0.25 mA cm −2 (Fig. 6b) as compared to addition of the individual IL additives (Fig. 6a). In theory, a critical current density of 0.25 mA cm −2 could already enable a solid-state battery using Li-S as the cathode having an energy density of more than 500 Wh kg −1 (ref. 41 ). The HSE with both ILs added demonstrates a critical current density that can be compared to those of state-of-the-art solid-state electrolytes reported in the literature (Supplementary Table 2), although it should be realized that our result is achieved using a small fraction of a liquid (IL) phase. Finally, the HSE with the dual IL additives was electrochemically cycled in a Li-metal battery in combination with a LiFePO 4 cathode (Fig. 6c,d). The battery delivers a capacity of more than 0.8 mAh (120 mAh g −1 ) after 50 cycles, with an average Coulombic efficiency of ~99.9% and an overpotential of 150 mV, indicating the feasibility of this HSE to function as a solid-state electrolyte for a room-temperature Li-metal battery.

Conclusions
In conclusion, we propose that the bottleneck for Li-ion transport in HSEs comprising PEO polymer and inorganic solid electrolyte phases is across the organic-inorganic phase boundaries, where the deficiency of ethereal oxygen species and absence of local mobility are held responsible for the poor local Li-ion conductivity at the interface. The interface diffusivity can be improved by making use of an IL additive as a wetting agent, in this case PP13-TFSI, whose low miscibility in PEO forces it to be positioned at the phase boundaries where it functions as a bridge for Li-ion transport. The multinuclear solid-state NMR investigation revealed the structure of the interface between the organic and inorganic phases in the HSE and how this affects the Li-ion diffusion pathway. This sheds light on the development of interface strategies, such as the one proposed with non-miscible ILs, leading to improved conductivities and compatibility with Li-metal anodes.

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