Li4Ti5O12 Interphase by Scanning Electron

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Study of the hydrate-melt/Li4Ti5O12 interphase by scanning electron microscopy based spectroscopy. Mitsunori Kitta, Noboru Tagichi, Chie Fukada, and Masanori Kohyama Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.7b03066 • Publication Date (Web): 16 Nov 2017 Downloaded from http://pubs.acs.org on November 20, 2017

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Study of the hydrate-melt/Li4Ti5O12 interphase by scanning electron microscopy based spectroscopy.

AUTHOR NAMES *‡Mitsunori Kitta, ‡Noboru Taguchi, Chie Fukada and Masanori Kohyama

AUTHOR ADDRESS Research Institute of Electrochemical Energy, Department of Energy and Environment, National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31, Midorigaoka, Ikeda, Osaka 563-8577, Japan

KEYWORDS Aqueous Li-ion battery, Hydrate-melt electrolyte, Li4Ti5O12, Solid-electrolyte interphase analysis, Scanning electron microscopy, Electron spectroscopy

ACS Paragon Plus Environment

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ABSTRACT

To develop safe and low-cost Li-ion batteries, recently, an aqueous-based electrolyte socalled "hydrate-melt" electrolyte is proposed. Li4Ti5O12 is a promising negative electrode material for a Li-ion battery with such a hydrate-melt electrolyte, because of its unexpected reversible Li-insertion and extraction properties without usually-inevitable water reduction. The solid-electrolyte interphase formation is one of the reasons for this stable reaction, while a detail analysis is not yet performed. Here, a Li4Ti5O12 electrode surface reacted in a hydrate-melt electrolyte is investigated by scanning electron microscopy based analysis. Surface-reaction products are clearly observed on the Li4Ti5O12 surface after the Li-insertion reaction in a hydratemelt electrolyte. Energy-dispersive X-ray spectroscopy and Auger electron spectroscopy indicated that the products do not contain any components originated from Li salts, while anionderived passivation films seem to cover a bare surface below the products. Further, the surface products are identified as Li2O by the feature of Li-K edge reflection electron energy-loss spectrum. The Li2O formation would be one of the key issues for stable Li insertion and extraction of a Li4Ti5O12 electrode in a hydrate-melt electrolyte.

INTRODUCTION In the present day, a Li-ion battery (LIB) is one of the most useful rechargeable batteries.1,2 For its highest energy density, stable cycle ability and superior energy efficiency, a LIB attracts much attention not only for portable application but also for high-power and large-


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scale energy-storage application.3 In most LIBs, a non-aqueous organic electrolyte is used so as to secure wide working potential windows. However, the usage of the non-aqueous electrolyte leads to some problems such as flammability, thermal instability, and water derived deterioration. Further, a relatively high cost is needed because of severe non-aqueous conditions required during manufacture. These disadvantages prevent rapid spread of LIBs in large-scale storage application. To address these issues, aqueous Li-ion batteries (ALIBs) using water-based electrolytes have been widely studied as a promising alternative for large-scale storage application.4,5 ALIBs have apparent advantages than conventional non-aqueous LIBs such as noflammability of water-based electrolyte, simple manufacturing conditions, environmental friendliness, and a relatively low cost. ALIBs are investigated in combination with specific electrode materials such as LiMn2O4,6-8 LiCoO2,9-11 and LiNi0.5Mn1.5O412,13 for a positive electrode and TiP2O7,14,15 LiV3O8,16,17 and TiO218 for a negative electrode. Although a lot of cell configurations of ALIBs were investigated, the most serious issue is a narrow electrochemical window of a water-based electrolyte. Actually, potential windows of water-based electrolytes are limited by a redox potential of water (1.23 V for O2 and 0 V for H2 evolution), and general operating voltages of these cells were around 1.2 V, which is rather lower than those of usual non-aqueous LIB cells. Therefore, a superior aqueous electrolyte with a wide potential window is highly needed. On the other hand, to develop stable electrolytes, recently, high Li-salt concentration solutions are actively investigated.19-23 It was reported that a high-concentrated electrolyte has unexpected redox stability,20 and it allows us to construct high-voltage Li-ion cells as a nonaqueous system.24 Further, the same concept is also applicable to an aqueous solution, and highly stable water-based electrolytes were developed, and they were applied to 2V-class aqueous Li-


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ion cells of LiMn2O4/Mo6S8,25 LiNi0.5Mn1.5O4/Mo6S826 and LiMn2O4/TiO227 systems. Especially, an interesting electrolyte, described as

Li(TFSI)0.7(BETI)0.3 ･ 2H2O named "hydrate-melt"

(HDM) was recently proposed by Yamada et. al.,28 who confirmed high redox stability of this electrolyte, and successfully suggested 3V-class ALIB with a LiNi0.5Mn1.5O4/Li4Ti5O12 cell configuration. In this high-voltage ALIB, stable reactions at a negative electrode of spinel lithium titanate (LTO; Li4Ti5O12) without the reduction of water seem to play a significant role for the cell performance. Indeed, Li4Ti5O12 has never been adopted as a negative electrode in conventional aqueous Li-ion cells, due to its severe reduction potential of Li insertion and extraction, as -1.48 V vs NHE. This unexpected stability of LTO reactions in a HDM electrolyte was considered to be caused by some interface mechanism, such as formation of solid-electrolyte interphase (SEI) layers or anion-derived passivation films. Actually, LiF, SOx, and sulfides were observed as decomposition products of the Li salts, by X-ray photoelectron spectroscopy (XPS) study,20,28 and these anion decomposed compounds are considered to be passivation films for preventing the reducing reaction of water.23 As mentioned above, investigation of the electrode/electrolyte interface is essentially important as well as development of electrolytes so as to attain high-voltage ALIBs. Especially, observation of morphology and chemical composition of a reacted electrode surface is highly needed for direct understanding of an electrode reaction with an electrolyte and its role on the stable performance. For this purpose, scanning electron microscopy (SEM) based spectroscopic analyses should be quite effective. Indeed, X-ray analysis, such as energy dispersive spectroscopy (EDS) combined with SEM imaging is considerably used. Although SEM-EDS analysis is highly convenient, it also has several weak points such as low energy resolution about 60 eV for analysis of carbon, low surface sensitivity with an analysis depth more than 100 nm


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and weak analysis sensitiveness in the lower energy region under 100 eV, which make Li analysis difficult. As more sensitive analysis, Auger electron spectroscopy (AES) has been applied to surface analysis, and elemental distribution of Li was clearly observed.29-32 On the other hands, generally, AES peaks are highly affected by the condition of a sample surface, and artificial peak shift is considerably observed by a charge-up effect. Further, the interpretation of AES peaks is rather complicated, and thus detail discussion of chemical states or identification of compounds is usually difficult. Complementarily with these conventional SEM-based spectroscopies, recently, Taguchi et. al. proposed SEM combined reflection electron energy loss spectroscopy (REELS) for fine material characterization, especially for Li-containing materials.33 This technique can provide detailed information on the chemical state of reacted LTO-electrode surfaces, through the reliable spectra of core-loss EELS of Li-K edge and lowloss regions.33-35 In this study, we perform detail surface characterization of HDM/LTO electrochemical reaction by the above-mentioned techniques of SEM-based spectroscopy. Here we use a prepared LTO(111) wafer sample with an atomically-flat surface for the precise characterization. Note that such a LTO-wafer sample has Li-insertion/extraction activities, similar to usual LTO powder as examined in our previous study.36 After the Li-insertion reaction of a LTO electrode wafer in the HDM electrolyte, the surface product on the LTO wafer is carefully examined, concerning the SEI formation.

EXPERIMENTAL


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Hydrate-melt electrolyte was prepared by 0.7 mol of Lithium bis(trifluoro methanesulfonyl)imide

[LiTFSI;

LiN(SO2CF3)2],

0.3

mol

of

Lithium

Bis(pentafluoroethanesulfonyl)imide [LiBETI; LiN(SO2CF2CF3)2] and 2.0 mol of deionized water. LiTFSI and LiBETI were purchased by Kishida Chemical Co., Ltd. and Tokyo Chemical Industry Co., Ltd., respectively. These components were mixed and heated 40-50 ℃ for liquefaction. After the formation of hydrate-melt (HDM), the solution was stable in a liquid state at around 30℃. LTO(111) wafers were prepared by Li-vapor induction growth method.36,37 2×2 ×0.5 mm3 of TiO2(111) wafer was heated with 0.5 mg of LiOH･H2O granular (Wako chemical) in air at 1173K for 15h using Al2O3 crucible. A prepared LTO(111) wafer in contact with Limetal foil was soaked into a HDM electrolyte for 5 min to perform Li-insertion reaction. The color of the LTO wafer quickly turned from white to black within 10 seconds, and the color change became steady in 1 min. A movie recording this color change in the Li-insertion reaction process of a 2×4×0.5 mm3 wafer is presented in Supporting Information Movie S1. It is clear that the Li-insertion reaction, involving HDM/LTO interface reactions, is completed enough in 5 min. Another LTO(111) wafer was also soaked into a HDM electrolyte for the same time without contact to Li metal, as a control sample of no Li-insertion reaction. After the Li-insertion reaction, all the LTO(111) wafers were soaked in propylene carbonate (PC) solvent to eliminate residual salts from a HDM electrolyte on the surface, and washed with dimethyl carbonate (DMC) solvent before SEM experiment. Surface observation and EDS analysis were performed by FE-SEM (S-5500, HITACHI) at 10 kV of accelerated voltage for all the samples. A cylindrical mirror analyzer (∆E / E = 0.5%) with a thermal field emission electron gun was used for AES and REELS analysis (PHI 700Xi, ULVAC-PHI, Inc.). AES analysis was performed at 5 kV of accelerated voltage. The beam


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current was 1 nA. AES spectrum was acquired for 10 -1000 eV of energy range with 0.2 eV/ch steps. REELS spectra were acquired successively with AES experiment in the same field of view. The accelerated voltage was 500 V and beam current was 0.5 nA in the REELS experiment. Spectra were acquired at 10 - 520 eV of energy range, with 0.1 eV/ch steps.

RESULTS AND DISCUSSION Fig. 1 shows SEM images of LTO(111) wafer sample surfaces. Fig. 1(a) is the surface of the control sample of no Li-insertion reaction, simply soaked in a HDM electrolyte, showing no specific contrast on the surface, indicating that residual Li salts from a HDM electrolyte could be completely washed out. Fig. 1(b) shows a LTO(111) surface of the wafer sample with Li insertion in a HDM electrolyte. Characteristic surface products are clearly observed. These surface products are not observed in the control sample at all. Therefore, these surface products should not be Li salts from a HDM electrolyte, but should be formed associated with a Liinsertion reaction in a HDM electrolyte. In Supporting Information Figure S1, a SEM image of a low magnified field of view for the Li-inserted LTO wafer clearly shows that the greater part of the reacted LTO(111) surface is covered with the surface product, while there are some areas with a lot of crevices in the product, showing both the surface-product and bare-surface regions. In the present study, we deal with such an area so as to make direct comparison between the two regions.


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To acquire rough elemental information, we performed EDS analysis for the same field of Fig. 1(b). The EDS results are summarized in Fig. 2. In Fig. 2(a), the EDS spectra from blue and red rectangle areas are shown by blue and red solid lines, respectively. We assume that the blue and red rectangle areas correspond to a bare-surface region with relatively bright contrast and a surface-product region with relatively dark contrast, respectively, while the bare-surface region may possibly be covered by thin flat films as mentioned later. In the blue rectangle region, two clear peaks are observed at 530 eV and 4.5 keV, assigned to O-K and Ti-K peaks, of which the intensities are similar to each other. On the other hand, in the surface-product region, the O-K and Ti-K peaks show quite different intensities. The O-K peak intensity is considerably larger than the Ti-K peak intensity, indicating that the elemental composition of O and Ti in the surface product is greatly different from the bare-surface region. This point is more apparent in EDS mapping in Fig. 2(b), where the intensities of Ti and O are completely reverse in these two kinds of regions. From these results, it can be said that the surface product has a quite different chemical composition from the bare surface, at least in the average of the depth over 100 nm. In order to acquire more detailed information of surface products, we performed AES and REELS analysis of the same LTO(111) sample with Li insertion in a HDM electrolyte [HDMLi(+) wafer], as shown in Fig. 3. Fig. 3(a) shows AES spectra of bare-surface (blue solid line) and surface-product (red solid line) regions, respectively. The contrasts of these two regions in a SEM image seem to be opposite from Fig. 2, which would be caused by a charge-up effect in a different acceleration voltage condition. In the spectrum of a bare-surface region, Auger peaks of S-LVV and C-KVV are observed clearly. These components, especially S-based component should be originated from the Li-salt anions in a HDM electrolyte, as observed in the previous XPS study.28 Therefore, the bare-surface region should be covered with anion-derived


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passivation films as previously reported.23,28 On the other hand, a LTO(111) wafer just soaked in a HDM electrolyte without Li-metal contact [HDM-Li(-) wafer] did not show any S-LVV signal, as shown in Supporting Information Figure S2. This suggests that the anion-derived passivation film should be formed associated with the Li-insertion reaction, and that residual salt components could be completely eliminated with PC and DMC solvent washing. Here we did not observe F-KVV signals in either HDM-Li(+) or HDM-Li(+) sample. Since AES can easily detect F signals, this suggests that F components of salt residual or surface films were completely washed away. Note that the main component of F in anion-derived passivation films was characterized as LiF,23,28 which should be washed out with PC and DMC solvent. In the spectrum of the bare-surface region in Fig. 3(a), Ti-LVV signals, overwrapped with the energy position of N-KVV peak, are also observed, while the signal is quite weak in comparison with the HDM-Li(-) wafer and our previous AES analysis of LTO.33 This is consistent with the coverage of a thin passivation film. The AES signals are originated from a few nm depth region of the surface, and thus the thickness of this passivation film should be a few nm. The signals of anionderived elements in such a thin passivation film were not detected by prior EDS analysis in Fig. 2(a), because of being buried by the background of bulk wafer signals of X-ray counts in the EDS spectrum. As for the AES spectrum of the surface-product region in Fig. 3 (a), no peaks assigned to S, C and N are observed, while the Li-KVV and O-KVV peaks are clearly observed. The Ti-LVV AES peak is not confirmed, indicating that the surface product does not contain Ti. Therefore, the surface product is presumed as some lithium oxide or lithium hydroxide, but direct identification of the product could not be performed in the AES spectrum. To identify the surface product directly, we performed REELS analysis, following the AES analysis. The results are summarized in Fig. 3(b). A remarkably strong sharp peak,


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observed at 500 eV, corresponding to the zero-loss peak (ZLP) which is originated from the elastically backscattered electrons (BSE). The features of a low-loss region for both bare-surface (blue) and surface-product (red) regions are magnified in inset. A clear peak is observed at around 440 eV of energy position in both the spectra. These peaks should be assigned as Li-K edge core loss signals due to the loss energy of 60 eV (= 500 - 440 eV), corresponding to the LiK edge energy loss region of conventional transmission electron energy loss spectroscopy (TEELS) analysis. The Li-K edge spectrum of the surface-product region is completely different from the bare-surface region, and two peaks assigned as a1 (441.3 eV equal to 58.7 eV for TEELS) and a2 (436.5 eV equal to 63.5 eV for TEELS) are observed. This feature is in good agreement with the Li-K edge feature of Li2O,38,39 while this does not well agree with lithium peroxide (Li2O2),39,40 lithium hydroxide (LiOH or LiOH ･ H2O)33,41 or other lithium compounds.33,39-42 Therefore, the surface product on the Li-inserted LTO wafer in a HDM electrolyte should be Li2O. The surface product, Li2O, should be formed by the water related reduction reaction as follows, H2O + 2Li+ + 2e- → Li2O + H2↑

This means that the water reduction occurred on the LTO-wafer surface. On the other hand, as confirmed by the AES analysis mentioned above, a LTO wafer have been covered with anionderived passivation film, and Li2O exists on it. This indicates that this passivation film may not be sufficient enough for preventing the reducing reaction of water. Here, Li2O may be unstable in a conventional water solution electrolyte due to the high reactivity of Li2O with H2O. However Li2O is specifically stable in a HDM electrolyte as shown in Supporting Information


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Figure S3. In a HDM electrolyte, all the water molecules are hydrated at Li+ and anions. 28 In other words, there are no free water molecules, reactive with Li2O. This is one of the possible reasons for the enhanced stability of Li2O. A LTO electrode shows good cycle stability in a HDM electrolyte, as shown in references of Yamada, et. al.,

23,28

, where more than 90% of

charge-discharge capacity was retained till 200 cycles in Li4Ti5O12/LiCoO2 full-cell configuration with a HDM electrolyte. Therefore, we propose that a Li2O layer formed on the LTO surface would possibly work as a kind of SEI to prevent the H2O reducing reaction, and enhance the stability. Note that the nature of Li2O as high Li-ion conductivity and low electronic conductivity should be quite effective as SEI, for example. Indeed, the Li2O layer is often characterized as a kind of SEI within the water contained non-aqueous cells,43-48 and reported to play a role of high cycle stability.45,47,48 Of course, the electrochemical performance of HDM/LTO system may be controlled not only by a Li2O layer but also by other chemical or physical factors such as some surface catalytic mechanism of LTO in the H2 generation or the energy level shifts of anion or water molecules in the high-concentrated solution with specific hydration condition of HDM.23 All the effects of these possibilities should be investigated carefully as well as the effects of Li2O layers in the near future, where detail surface characterization using SEM-based analysis should be quite effective.

CONCLUSIONS Li-inserted LTO-wafer surfaces, soaked in a HDM electrolyte, were investigated by SEM-based spectroscopy with EDS, AES and REELS. The surface products were clearly


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observed on the Li-inserted LTO wafer. EDS characterization showed that the composition of O and Ti in surface-product regions is quite different from that in bare-surface regions on the wafer. AES characterization revealed that the bare-surface region is covered with films of few nm thickness, derived from Li-salt anion decomposition, while the surface-product region is only composed of Li and O. The surface product was clearly identified as Li2O by REELS investigation. We propose a reaction mechanism of Li2O-layer formation through the water reduction by Li ions from Li-metal foil on the wafer surface, after the coverage by anion-derived passivation films, indicating that anion-derived films would not be sufficient to prevent such water reduction, while a Li2O-layer itself seem to be effective to prevent further water reduction and to proceed with Li-ion insertion as a SEI layer of a HDM/LTO electrochemical system.


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FIGURES

Figure 1. SEM images of LTO(111) wafer surfaces, (a) soaked in a HDM electrolyte without Limetal contact, (b) soaked in a HDM electrolyte in contact with Li-metal foil. All the scale bar represents 5 µm.


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Figure 2. EDS analysis of a Li-inserted LTO surface, soaked in a HDM electrolyte [HDM-Li(+) wafer]. (a) EDS spectra from bare-surface and surface-product regions indicated by blue and red rectangles in the SEM image are plotted by blue and red lines, respectively. (b) EDS intensity mapping of Ti-K (purple) and O-K (cyan) signals.


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Figure 3. AES and REELS analysis of a Li-inserted LTO surface, soaked in a HDM electrolyte. (a) AES spectra of bare-surface and surface-product regions indicated by blue and red circles in SEM image are plotted by blue and red lines, respectively. (b) REELS spectra acquired from the same areas of the AES analysis. Low-loss region of 420-485 eV is magnified in inset. The colors of spectra are the same as the AES analysis.


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ASSOCIATED CONTENT Supporting Information An AVI-movie (movie S1) of the Li-insertion reaction experiment is available. Supporting figures (Fig. S1 - Fig. S3) are also available in single PDF file.

AUTHOR INFORMATION Corresponding Author *Mitsunori Kitta E-mail: [email protected] TEL: +81-72-751-8703 Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. ‡M. K. and ‡N. T. contributed equally.

ACKNOWLEDGMENT This work was partly supported by JSPS KAKENHI (16K17523).


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(10) Tang, W.; Liu, L. L.; Tian, S.; Li, L.; Yue, Y. B.; Wu, Y. P.; Guan, S. Y.; Zhu, K. NanoLiCoO2 as cathode material of large capacity and high rate capability for aqueous rechargeable lithium batteries. Electrochem. Commun. 2010, 12, 1524-1526. (11) Ruffo, R.; Mantia, F. L.; Wessells, C.; Huggins, R. A.; Cui, Y. Electrochemical characterization of LiCoO2 as rechargeable electrode in aqueous LiNO3 electrolyte. Solid State Ion. 2011, 192, 289-292. (12) Mi, C. H.; Zhang, X. G.; Li, H. L. Electrochemical behaviors of solid LiNi0.5Mn1.5O4 and Li0.99Nb0.01FePO4 in Li2SO4 aqueous electrolyte. J. Electroanal. Chem. 2007, 602, 245-254. (13) Porcher, W.; Lestriez, B.; Jouanneau, S.; Guyomard, D. Design of Aqueous Processed Thick LiNi0.5Mn1.5O4 Composite Electrodes for High-Energy Lithium Battery. J. Electrochem. Soc. 2009, 156, A133-A144. (14) Wang, H.; Huanga, K.; Zeng, Y.; Yang, S.; Chen, L. Electrochemical properties of TiP2O7 and LiTi2(PO4)3 as anode material for lithium ion battery with aqueous solution electrolyte. Electrochim. Acta 2007, 52, 3280-3285. (15) H. Manjunatha, H.; & T. V. Venkatesha, T. V.; & G. S. Suresh, G. S. Electrochemical studies of LiMnPO4 as aqueous rechargeable lithium–ion battery electrode. J. Solid State Electrocehm. 2012, 16, 1941-1952. (16) Köhler, J.; Makihara, H.; Uegaito, H.; Inoue, H.; Toki, M. LiV3O8: characterization as anode material for an aqueous rechargeable Li-ion battery system. Electrochim. Acta 2000, 46, 59-65. (17) Wang, G. J.; Qu, Q. T.; Wang, B.; Shi, Y.; Tian, S.; Wu, Y. P.; Holze, R. Electrochemical intercalation of lithium ions into LiV3O8 in an aqueous electrolyte. J. Power Sources 2009, 189, 503-506. (18) Liu, S.; Ye, S. H.; Li, C. Z.; Pan, G. L.; Gao, X. P. Rechargeable Aqueous Lithium-Ion Battery of TiO2/LiMn2O4 with a High Voltage. J. Electrochem. Soc. 2011, 158, A1490-A1497.


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BRIEFS A Li2O layer on a salt-derived passivation film was characterized as a probable candidate of a SEI for stable electrochemical performance of a hydrate-melt/LTO system.

SYNOPSIS

Hydrate-melt Li+

Li+

Li2O

SEI

Salt-derived passivation film Li+

Li4Ti5O12

Li+


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Li4Ti5O12 Interphase by Scanning Electron

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