Direct observation of Degradation in LiNi0.8Mn0.1Co0.1O2-Li6PS5Cl0.5Br0.5 Composite Electrodes for All Solid-State Batteries

Direct observation of Degradation in LiNi0.8Mn0.1Co0.1O2-Li6PS5Cl0.5Br0.5 Composite Electrodes for All Solid-State Batteries | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Direct observation of Degradation in LiNi 0.8 Mn 0.1 Co 0.1 O 2 -Li 6 PS 5 Cl 0.5 Br 0.5 Composite Electrodes for All Solid-State Batteries Jiong Ding, Takao KOKUBU, Inwoo Song, Yongjun Jang, Shigeo Mori This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8298137/v1 This work is licensed under a CC BY 4.0 License Status: Under Revision Version 1 posted 11 You are reading this latest preprint version Abstract The interfacial stability between cathodes and solid electrolytes remains a critical challenge limiting the performance of all-solid-state batteries (ASSBs). In this work, we elucidate the degradation mechanisms of LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811)-Li 6 PS 5 Cl 0.5 Br 0.5 composite electrodes during electrochemical cycling using advanced electron microscopy. In the pristine state, spherical NMC811 particles are uniformly embedded in the Argyrodite electrolyte, forming intimate interfacial contact with the LiNbO 3 coating layer. With cycling, progressive interfacial separation and crack formation occur, accompanied by a structural transformation of the electrolyte from an Argyrodite-type polycrystalline phase to β-Li 3 PS 4 . Further decomposition leads to the precipitation of Li 2 S nanocrystals, preferentially localized at the cathode-electrolyte interface. Concurrently, chlorine migrates out of the electrolyte and segregates on the NMC811 surface as Cl-rich domains, while sulfur diffuses into NMC811 particles through cracks and accumulates as Li 2 S. These findings demonstrate that interfacial degradation, electrolyte decomposition, chlorine segregation, and sulfur diffusion cause the long-term instability of NMC811-Argyrodite composite electrodes. This study provides mechanistic insights into interfacial degradation pathways and offers design guidelines for enhancing interfacial stability in future solid-state batteries. Physical sciences/Chemistry Physical sciences/Energy science and technology Physical sciences/Materials science Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Introduction All-solid-state batteries (ASSBs) are widely regarded as next-generation energy storage systems owing to their potential to deliver high energy density and enhanced safety compared with conventional liquid-electrolyte lithium-ion batteries 12 . In terms of cathode materials, LiNi x Mn y Co 1−x−y O 2 (NMC) layered oxides have received increasing attention due to their enhanced capacity and thermal stability 3 . The Ni-rich NMC (x ≥ 0.5) cathodes possess high discharge capacity and energy density 4 . Among the various solid electrolytes (SE) investigations, sulfide-based electrolytes have attracted particular attention because of their high ionic conductivity, wide electrochemical window, and favorable mechanical formability 5 6 7 8 9 10 . In particular, Argyrodite-type solid electrolytes (Li 6 PS₅X, X = Cl, Br, I) have been extensively studied due to their excellent ionic transport properties and promising compatibility with high-voltage cathode materials 11 12 13 14 15 . Interfacial property is one of the most important issues of all-solid-state batteries 16 . In composite electrodes combining Ni-rich layered oxides with Argyrodite electrolytes, side reactions, interfacial phase transformations, and elemental transition often occur during cycling, ultimately leading to capacity fading and shortened cell lifetime 17 18 19 . The chemical reactions the interface between the oxide cathode and the sulfide SE has been investigated that products such as sulfate, phosphate, elemental sulfur, lithium polysulfide, and sulfide can be obtained 20 21 . However, direct evidence of the microstructural and chemical evolution at NMC- Argyrodite interfaces during long-term cycling remains unclear. In this study, composite cathodes consisting of Ni-rich LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) and Li 6 PS 5 Cl 0.5 Br 0 . 5 (LPSClBr) were prepared and subjected to multiple charge-discharge cycles. Cross-sectional specimens of the pristine, 50th-cycle, and 200th-cycle cathodes were prepared by focus ion beam-scanning electron microscope (FIB-SEM) for morphological characterization. The FIB-SEM system was equipped with an Energy Dispersive X-ray Spectroscopy (EDS) detector to analyze the elemental distribution across the cross-sections. In addition, thin lamellae were extracted from the central region of the composite cathodes using FIB-SEM for transmission electron microscope (TEM) analysis. TEM was employed to investigate the NMC811-SE interfaces with particular emphasis on the interfacial degradation and decomposition processes during electrochemical cycling. Furthermore, scanning TEM (STEM) combined with EDS was used to resolve the elemental distributions at the interfaces. The results revealed the structural and chemical evolution of the NMC811-SE interface at different cycling stages. Specifically, electrolyte decomposition, Li 2 S precipitation, chlorine segregation, and sulfur incorporation were identified as the key processes governing interfacial degradation, leading to significant structural instability and diminished electrochemical performance. These findings provide new mechanistic insights into the degradation pathways of sulfide-based ASSBs and highlight design principles for improving interfacial stability in future solid-state battery systems. Experiment Sample preparation: All-solid-state cells were prepared using NMC811 material and LPSClBr fine powder (D50 ~ 5 µm). NMC811 was provided by Ampcera with LiNbO 3 (1wt%) coating layer 22 . LPSClBr was also provided by Ampcera with ionic conductivity of ~ 2.8 mS/cm at room temperature. The NMC811- LPSClBr composite cathodes slurry were prepared with a weight ratio of NMC811: LPSClBr : AB: binder = 70: 25: 2: 3. This slurry was applied using a doctor blade to prepare a positive electrode. 150 mg of SE was pelletized (13 mm diameter) at a pressure of 440 MPa. The positive electrode plate, SE, and metallic lithium were combined in that order and clamped at a pressure of 100 MPa to create an airtight cell. All of the above operations were performed in an Ar atmosphere. The full cell configuration for charge-discharge cycling was composite using Al current collectors, Li anode, LPSClBr electrolyte and NMC811- LPSClBr composite cathodes, as shown in Fig. 1 (a). Charge–discharge cycling of the battery was performed at 1 C at a temperature of 60°C, and the cycle performance profile until 200 cycles is shown in Fig. 1 (b). Characterization: Cross-sections of the composite electrode were prepared using FIB-SEM for SEM observation. The FIB-SEM instrument (JEM-4700, JEOL Co. Ltd) was equipped with a Ga ion source and W deposition. FIB-SEM was also employed to prepare specimens for TEM observation. The TEM lamellae were extracted from the central region of the cross-section of composite cathode. During TEM sample preparation, the accelerating voltage of FIB was set to 30 kV. Due to the presence of large cracks in composite cathode, the TEM observation sample were thinned to a thickness of 180 nm. The sample preparation was performed in a glovebox. A transfer vessel was used to transfer the sample from glovebox to the FIB-SEM and avoid air exposure. TEM observations were conducted using a filed-emission-type microscope JEM-2100F with an accelerated voltage of 200 kV. A vacuum transfer holder (Mel Build Co. Ltd) was employed to prevent air exposure during sample transfer from the glovebox to the TEM. The degradation behaver of the LPSClBr was examined by taking dark-field (DF) images and corresponding selected-area electron diffraction (SAED) patterns. The OneView camera (Gatan, USA) with high-sensitivity CMOS sensor, was used to capture digital TEM data. The 2D digital SAED patterns can be transformed into 1D integral intensities profiles such as a usual XRD pattern. It was possible to identify the precipitated crystalline phase by comparing the SAED pattens with XRD profiles. DF images are used to confirm the distribution of nanocrystals 23 . Results and Discussion Figure S1 presents SEM images and the corresponding SEM-EDS mapping results of the pristine NMC811- LPSClBr composite cathode. The spherical NMC811 particles are embedded in the SE and have good interfacial contact with it. Figure 2 shows the TEM observation results of the pristine NMC811- LPSClBr sample. In Fig. 2(a), the regular morphology of NMC811- LPSClBr shows a well-formed interface between NMC811. There were several cracks in the SE. The SAED pattern in Fig. 2(b) was derived from the SE region marked by a blue circle in Fig. 2(a). The SAED pattern and the corresponding intensity profile in Fig. 2(b) confirm that the electrolyte exhibits a polycrystalline Argyrodite-type structure. Figure 2(c) displays the STEM-EDS mapping result, revealing the elemental distribution across the interface region. A LiNbO 3 coating layer with a thickness of approximately 50 nm is formed at the NMC811 interface. LPSClBr shows good stability in contact with NMC811 without electrochemical operation. After 50 charge-discharge cycles, the morphology of the NMC811- LPSClBr composite cathode is shown in Figure S2. The interfacial gap between NMC811 and the SE becomes significantly enlarged. In the SEM-EDS mapping of Figure S2, the distribution of Cl within the electrolyte is no longer as uniform as in the pristine sample. Figure 3 presents the TEM results of the NMC811- LPSClBr composite cathode after 50 cycles. In Fig. 3(a), the interfacial contact between NMC811 and the electrolyte was still preserved after cycling. The SAED pattern in Fig. 3(b) was derived from the SE region marked by a blue circle in Fig. 3(a). Figure 3(b) shows the SAED pattern, and the corresponding intensity profile. The diffraction peaks in the intensity profile match those of simulated XRD patterns of Li 3 PS 4 with space group of Pnma, which also names as β-Li 3 PS 4 24 , indicating that the electrolyte has degraded. The polycrystalline Argyrodite structure has transformed into a β-Li 3 PS 4 polycrystalline structure. STEM-EDS mapping of this region is shown in Fig. 3(c). Sulfur is homogeneously distributed throughout the electrolyte. In contrast, Cl is enriched at the NMC811-SE interface and reduced in regions farther from the interface, suggesting that Cl atoms migrate toward the NMC811 surface during cycling. In addition, a small domain containing both P and O were observed. After 200 charge-discharge cycles, the morphology of the NMC811- LPSClBr composite is shown in Figure S3. In addition to the enlarged interfacial gaps between NMC811 and the SE, cracks were observed within the SE itself, and even fine cracks developed inside the NMC811 particles 25 26 . In the SEM-EDS mapping of Figure S3, sulfur is homogeneously distributed throughout the electrolyte, while a small amount of sulfur was also detected inside the NMC811 particles. This means the sulfur diffused into the NMC811 particles. Meanwhile, the Cl content in the SE decreased drastically. Figure 4 presents SEM image of a single NMC811 particle along with the corresponding EDS mapping results. Sulfur is found to accumulate within the cracks inside the NMC811 particle. Cl and Br migrate out of the SE and segregate on certain surface regions of the NMC811. Although Cl and Br tend to migrate toward the NMC811 surface, they do not form a Cl- or Br-rich layer on the surface. Instead, they continue to accumulate into discrete regions enriched in Cl and Br. Figure 5 presents the TEM results of the NMC811-Argyrodite composite after 200 cycles. In Fig. 5(a), the morphology image shows that the NMC811 and the electrolyte still maintain intimate interfacial contact. Selected area apertures were inserted at the NMC811-SE interface and within the electrolyte, as indicated in Figure S4(a). The corresponding SAED patterns and intensity profiles are shown in Figures S4(b) and (c). By inserting the objective aperture at the circled region in Figure S4(b), the corresponding DF image (Fig. 5(b)) reveals the high contrast spots at the interface, which are identified as the β-Li 3 PS 4 decomposed to Li 2 S nanocrystals and precipitated at the NMC811-SE interface. Similarly, the DF image obtained from the circled region in Figure S4(c), shown in Fig. 5(c), displays the high contrast areas corresponding to β-Li 3 PS 4 nanocrystals within the electrolyte. These observations indicate that structural degradation and decomposition of β-Li 3 PS 4 preferentially occur at the NMC811-SE interface. The STEM-EDS mapping of this interfacial region is displayed in Fig. 5(d). Sulfur is not only homogeneously distributed in the SE but also diffuses into the interior of the NMC811 particles, which is consistent with the SEM results. In contrast, Cl and Br are scarcely detected in this region, and no evidence of Cl and Br segregation was observed. A small domain enriched in both P and O was identified. High-magnification STEM-EDS results are provided in Figure S5. Figure 6 shows the TEM image of the interior of an NMC811 particle. The initially large, spherical NMC811 particle was fragmented into smaller grains with diameters of approximately 300 nm. The appearance of those cracks inside the NMC811 particle is responsible for the lower deliverable capacity of NMC811. STEM-EDS elemental mapping confirmed that sulfur diffused into the NMC811 particle along these cracks and accumulated at the boundary of fragmented NMC811 particles. The degradation process of the NMC811- LPSClBr composite electrode during cycling can be summarized as follows. Before cycling, a well-formed NMC811- LiNbO 3 -SE interfacial contact was established, with all constituent elements homogeneously distributed across the electrolyte and electrode, which means that LPSClBr has good stability in contact with NMC811. As charge-discharge cycling progressed, the interfacial gap between NMC811 and SE gradually enlarged due to the lattice volume changes associated with lithium insertion and extraction 27 . Eventually, cracks developed within both the NMC811 and SE phases. Regarding SE degradation, LPSClBr first underwent structural decomposition into β-Li 3 PS 4 11 . During this process, chlorine tended to migrate out of the SE and accumulate on the NMC811 surface. Subsequently, β-Li 3 PS 4 further decomposed into Li 2 S, which precipitated as nanocrystals on the surface of NMC811 particles. In Fig. 1(b), the discharge capacity progressively approaches and eventually exceeds the charge capacity during cycling. This abnormal capacity rise indicates the presence of parasitic reactions. A plausible origin of this phenomenon is the decomposition of the SE accompanied by the diffusion of sulfur species into the NMC811 phase 28 . Under electrochemical driving forces, Cl and Br gradually depart from the SE and migrate toward the NMC811/SE interface, where they eventually accumulate and form localized Cl/Br-rich regions, which, according to previous reports, predominantly correspond to LiCl and LiBr. The degradation of the SE leads to a reduction in ionic conductivity, thereby impeding Li-ion transport during cycling and ultimately deteriorating the overall electrochemical performance of the battery. Conclusion In this study, we investigated the structural and chemical evolution of NMC811- LPSClBr composite electrodes during electrochemical cycling using SEM, TEM, and EDS analyses. The results demonstrate that the initially well-formed NMC811-LiNbO 3 -SE interfaces progressively deteriorate with cycling, leading to interfacial separation and crack formation in both the electrode and electrolyte phases. The SE undergoes structural degradation, transforming from an Argyrodite-type polycrystalline phase into β-Li 3 PS 4 , and further decomposes with the precipitation of Li 2 S nanocrystals at the interface. Concurrently, chlorine migrates out of the electrolyte and segregates on the NMC811 surface as LiCl, while sulfur diffused into the NMC811 particles through cracks and accumulates as Li 2 S. These results highlight that long-term electrochemical instability in NMC811-Argyrodite composite electrodes is predominantly driven by interfacial degradation and accompanied by phase decomposition and elemental redistribution. Strategies to suppress electrolyte decomposition and inhibit halogen and sulfur migration will be critical for achieving durable solid-state batteries. Declarations Author Contribution JIONG DING collected experimental data and wrote the main manuscript text. Takao Kokubu, Inwoo Song and Yongjun Jang prepared the sample. All authors reviewed the manuscript. 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Supplementary Files Supplementary.pdf Cite Share Download PDF Status: Under Revision Version 1 posted Editorial decision: Revision requested 21 Jan, 2026 Reviews received at journal 03 Jan, 2026 Reviews received at journal 27 Dec, 2025 Reviewers agreed at journal 27 Dec, 2025 Reviewers agreed at journal 21 Dec, 2025 Reviewers agreed at journal 20 Dec, 2025 Reviewers invited by journal 19 Dec, 2025 Editor assigned by journal 17 Dec, 2025 Editor invited by journal 17 Dec, 2025 Submission checks completed at journal 16 Dec, 2025 First submitted to journal 15 Dec, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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16:30:17","extension":"xml","order_by":6,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":59574,"visible":true,"origin":"","legend":"","description":"","filename":"9cd349798e6a4aad9ae627f07c65fc781structuring.xml","url":"https://assets-eu.researchsquare.com/files/rs-8298137/v1/64d9e44a554896ab48c920c0.xml"},{"id":99307242,"identity":"e0cb45e3-1e77-4b96-99e8-4cbc62bd60f9","added_by":"auto","created_at":"2025-12-31 16:05:50","extension":"html","order_by":7,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":69076,"visible":true,"origin":"","legend":"","description":"","filename":"earlyproof.html","url":"https://assets-eu.researchsquare.com/files/rs-8298137/v1/3480a48934cadf38cfd1461d.html"},{"id":99307616,"identity":"ee0fe866-2ddc-452d-af8d-1988d044da3d","added_by":"auto","created_at":"2025-12-31 16:06:27","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":55848,"visible":true,"origin":"","legend":"\u003cp\u003e(a) the schematic diagram of full cell pellet. (b) the cycle performance profile until 200 cycles\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-8298137/v1/3272d87b70021cf143576aa0.png"},{"id":98816904,"identity":"28060555-cbe8-4c3d-8d70-070cea7e7f7f","added_by":"auto","created_at":"2025-12-22 16:30:17","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":1171841,"visible":true,"origin":"","legend":"\u003cp\u003e(a) the morphological image of pristine NMC811-LPSClBr at interface. (b) the SAED pattern and its intensity profile of SE (c) STEM-EDS mapping results at the interface of NMC811-LPSClBr\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-8298137/v1/35f9ff7b75e5fece63c39746.png"},{"id":98816905,"identity":"9118934a-e710-4eb2-ac22-4b8beb3a4b6b","added_by":"auto","created_at":"2025-12-22 16:30:17","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":1254335,"visible":true,"origin":"","legend":"\u003cp\u003e(a) the morphological image of NMC811-LPSClBr at interface after 50 cycles. (b) the SAED pattern and its intensity profile of SE (c) STEM-EDS mapping results at the interface of NMC811-LPSClBr\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-8298137/v1/b148e88ffbde65a528174136.png"},{"id":99307119,"identity":"d0288f56-6448-433c-890c-02b4949d59c4","added_by":"auto","created_at":"2025-12-31 16:05:39","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":1004676,"visible":true,"origin":"","legend":"\u003cp\u003eThe cross-sectional SEM image of NMC811-LPSClBr after 200 cycles with the SEM-EDS mapping results.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-8298137/v1/0ae524479b291feb63ce42bf.png"},{"id":99307659,"identity":"f4759bd5-d1b7-4938-9e61-8313d134634a","added_by":"auto","created_at":"2025-12-31 16:06:29","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":1162763,"visible":true,"origin":"","legend":"\u003cp\u003eTEM observation results of NMC811-LPSClBr at interface after 200 cycles. (a) the morphological image. (b) the DF image focus on the distribution of Li\u003csub\u003e2\u003c/sub\u003eS nanocrystals. (c) the DF image focus on the distribution of β-Li\u003csub\u003e3\u003c/sub\u003ePS\u003csub\u003e4\u003c/sub\u003e nanocrystals. (d) STEM-EDS mapping results\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-8298137/v1/e0889ef3aa13c0ca43738ca3.png"},{"id":98816912,"identity":"1b86e49e-1ba9-467e-9d0f-f46c0c16eac5","added_by":"auto","created_at":"2025-12-22 16:30:17","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":835941,"visible":true,"origin":"","legend":"\u003cp\u003eTEM observation results of NMC811-LPSClBr inside the NMC811 particle after 200 cycles. (a) the morphological image of NMC811 and SE. (b) the morphological image inside NMC811 and corresponding (c) STEM-EDS mapping results inside the NMC811 particle\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-8298137/v1/e1d2882c841d2fd96eeea77e.png"},{"id":99788043,"identity":"d0b05c9e-52be-41b9-8873-401e8bf71b20","added_by":"auto","created_at":"2026-01-08 12:43:46","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":5086717,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8298137/v1/f2d53ab1-5864-4a53-bf20-189b28417bbf.pdf"},{"id":98816911,"identity":"afe76a1c-c3ae-44bf-b4c7-df1b679075ea","added_by":"auto","created_at":"2025-12-22 16:30:17","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":1914959,"visible":true,"origin":"","legend":"","description":"","filename":"Supplementary.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8298137/v1/fcaa7363f7105c06051b3d2b.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"\u003cp\u003e\u003cstrong\u003eDirect observation of Degradation in LiNi\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e0.8\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eMn\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e0.1\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCo\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e0.1\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eO\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e2\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e-Li\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e6\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003ePS\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e5\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eCl\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e0.5\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003eBr\u003c/strong\u003e\u003csub\u003e\u003cstrong\u003e0.5\u003c/strong\u003e\u003c/sub\u003e\u003cstrong\u003e Composite Electrodes for All Solid-State Batteries\u003c/strong\u003e\u003c/p\u003e","fulltext":[{"header":"Introduction","content":"\u003cp\u003eAll-solid-state batteries (ASSBs) are widely regarded as next-generation energy storage systems owing to their potential to deliver high energy density and enhanced safety compared with conventional liquid-electrolyte lithium-ion batteries \u003csup\u003e\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e. In terms of cathode materials, LiNi\u003csub\u003ex\u003c/sub\u003eMn\u003csub\u003ey\u003c/sub\u003eCo\u003csub\u003e1\u0026minus;x\u0026minus;y\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e (NMC) layered oxides have received increasing attention due to their enhanced capacity and thermal stability \u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e. The Ni-rich NMC (x\u0026thinsp;\u0026ge;\u0026thinsp;0.5) cathodes possess high discharge capacity and energy density \u003csup\u003e\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u003c/sup\u003e. Among the various solid electrolytes (SE) investigations, sulfide-based electrolytes have attracted particular attention because of their high ionic conductivity, wide electrochemical window, and favorable mechanical formability \u003csup\u003e5 6 7 8 9 10\u003c/sup\u003e. In particular, Argyrodite-type solid electrolytes (Li\u003csub\u003e6\u003c/sub\u003ePS₅X, X\u0026thinsp;=\u0026thinsp;Cl, Br, I) have been extensively studied due to their excellent ionic transport properties and promising compatibility with high-voltage cathode materials \u003csup\u003e11 12 13 14 15\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eInterfacial property is one of the most important issues of all-solid-state batteries \u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e\u003c/sup\u003e. In composite electrodes combining Ni-rich layered oxides with Argyrodite electrolytes, side reactions, interfacial phase transformations, and elemental transition often occur during cycling, ultimately leading to capacity fading and shortened cell lifetime \u003csup\u003e17 18 19\u003c/sup\u003e. The chemical reactions the interface between the oxide cathode and the sulfide SE has been investigated that products such as sulfate, phosphate, elemental sulfur, lithium polysulfide, and sulfide can be obtained \u003csup\u003e20 21\u003c/sup\u003e. However, direct evidence of the microstructural and chemical evolution at NMC- Argyrodite interfaces during long-term cycling remains unclear.\u003c/p\u003e \u003cp\u003eIn this study, composite cathodes consisting of Ni-rich LiNi\u003csub\u003e0.8\u003c/sub\u003eMn\u003csub\u003e0.1\u003c/sub\u003eCo\u003csub\u003e0.1\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e (NMC811) and Li\u003csub\u003e6\u003c/sub\u003ePS\u003csub\u003e5\u003c/sub\u003eCl\u003csub\u003e0.5\u003c/sub\u003eBr\u003csub\u003e0\u003c/sub\u003e.\u003csub\u003e5\u003c/sub\u003e (LPSClBr) were prepared and subjected to multiple charge-discharge cycles. Cross-sectional specimens of the pristine, 50th-cycle, and 200th-cycle cathodes were prepared by focus ion beam-scanning electron microscope (FIB-SEM) for morphological characterization. The FIB-SEM system was equipped with an Energy Dispersive X-ray Spectroscopy (EDS) detector to analyze the elemental distribution across the cross-sections. In addition, thin lamellae were extracted from the central region of the composite cathodes using FIB-SEM for transmission electron microscope (TEM) analysis. TEM was employed to investigate the NMC811-SE interfaces with particular emphasis on the interfacial degradation and decomposition processes during electrochemical cycling. Furthermore, scanning TEM (STEM) combined with EDS was used to resolve the elemental distributions at the interfaces. The results revealed the structural and chemical evolution of the NMC811-SE interface at different cycling stages. Specifically, electrolyte decomposition, Li\u003csub\u003e2\u003c/sub\u003eS precipitation, chlorine segregation, and sulfur incorporation were identified as the key processes governing interfacial degradation, leading to significant structural instability and diminished electrochemical performance. These findings provide new mechanistic insights into the degradation pathways of sulfide-based ASSBs and highlight design principles for improving interfacial stability in future solid-state battery systems.\u003c/p\u003e"},{"header":"Experiment","content":"\u003cp\u003eSample preparation: All-solid-state cells were prepared using NMC811 material and LPSClBr fine powder (D50\u0026thinsp;~\u0026thinsp;5 \u0026micro;m). NMC811 was provided by Ampcera with LiNbO\u003csub\u003e3\u003c/sub\u003e (1wt%) coating layer \u003csup\u003e\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u003c/sup\u003e. LPSClBr was also provided by Ampcera with ionic conductivity of ~\u0026thinsp;2.8 mS/cm at room temperature. The NMC811- LPSClBr composite cathodes slurry were prepared with a weight ratio of NMC811: LPSClBr : AB: binder\u0026thinsp;=\u0026thinsp;70: 25: 2: 3. This slurry was applied using a doctor blade to prepare a positive electrode. 150 mg of SE was pelletized (13 mm diameter) at a pressure of 440 MPa. The positive electrode plate, SE, and metallic lithium were combined in that order and clamped at a pressure of 100 MPa to create an airtight cell. All of the above operations were performed in an Ar atmosphere. The full cell configuration for charge-discharge cycling was composite using Al current collectors, Li anode, LPSClBr electrolyte and NMC811- LPSClBr composite cathodes, as shown in Fig.\u0026nbsp;1 (a). Charge\u0026ndash;discharge cycling of the battery was performed at 1 C at a temperature of 60\u0026deg;C, and the cycle performance profile until 200 cycles is shown in Fig.\u0026nbsp;1 (b).\u003c/p\u003e \u003cp\u003eCharacterization: Cross-sections of the composite electrode were prepared using FIB-SEM for SEM observation. The FIB-SEM instrument (JEM-4700, JEOL Co. Ltd) was equipped with a Ga ion source and W deposition. FIB-SEM was also employed to prepare specimens for TEM observation. The TEM lamellae were extracted from the central region of the cross-section of composite cathode. During TEM sample preparation, the accelerating voltage of FIB was set to 30 kV. Due to the presence of large cracks in composite cathode, the TEM observation sample were thinned to a thickness of 180 nm. The sample preparation was performed in a glovebox. A transfer vessel was used to transfer the sample from glovebox to the FIB-SEM and avoid air exposure.\u003c/p\u003e \u003cp\u003eTEM observations were conducted using a filed-emission-type microscope JEM-2100F with an accelerated voltage of 200 kV. A vacuum transfer holder (Mel Build Co. Ltd) was employed to prevent air exposure during sample transfer from the glovebox to the TEM. The degradation behaver of the LPSClBr was examined by taking dark-field (DF) images and corresponding selected-area electron diffraction (SAED) patterns. The OneView camera (Gatan, USA) with high-sensitivity CMOS sensor, was used to capture digital TEM data. The 2D digital SAED patterns can be transformed into 1D integral intensities profiles such as a usual XRD pattern. It was possible to identify the precipitated crystalline phase by comparing the SAED pattens with XRD profiles. DF images are used to confirm the distribution of nanocrystals \u003csup\u003e\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e"},{"header":"Results and Discussion","content":"\u003cp\u003eFigure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e presents SEM images and the corresponding SEM-EDS mapping results of the pristine NMC811- LPSClBr composite cathode. The spherical NMC811 particles are embedded in the SE and have good interfacial contact with it. Figure\u0026nbsp;2 shows the TEM observation results of the pristine NMC811- LPSClBr sample. In Fig.\u0026nbsp;2(a), the regular morphology of NMC811- LPSClBr shows a well-formed interface between NMC811. There were several cracks in the SE. The SAED pattern in Fig.\u0026nbsp;2(b) was derived from the SE region marked by a blue circle in Fig.\u0026nbsp;2(a). The SAED pattern and the corresponding intensity profile in Fig.\u0026nbsp;2(b) confirm that the electrolyte exhibits a polycrystalline Argyrodite-type structure. Figure\u0026nbsp;2(c) displays the STEM-EDS mapping result, revealing the elemental distribution across the interface region. A LiNbO\u003csub\u003e3\u003c/sub\u003e coating layer with a thickness of approximately 50 nm is formed at the NMC811 interface. LPSClBr shows good stability in contact with NMC811 without electrochemical operation.\u003c/p\u003e \u003cp\u003eAfter 50 charge-discharge cycles, the morphology of the NMC811- LPSClBr composite cathode is shown in Figure S2. The interfacial gap between NMC811 and the SE becomes significantly enlarged. In the SEM-EDS mapping of Figure S2, the distribution of Cl within the electrolyte is no longer as uniform as in the pristine sample. Figure\u0026nbsp;3 presents the TEM results of the NMC811- LPSClBr composite cathode after 50 cycles. In Fig.\u0026nbsp;3(a), the interfacial contact between NMC811 and the electrolyte was still preserved after cycling. The SAED pattern in Fig.\u0026nbsp;3(b) was derived from the SE region marked by a blue circle in Fig.\u0026nbsp;3(a). Figure\u0026nbsp;3(b) shows the SAED pattern, and the corresponding intensity profile. The diffraction peaks in the intensity profile match those of simulated XRD patterns of Li\u003csub\u003e3\u003c/sub\u003ePS\u003csub\u003e4\u003c/sub\u003e with space group of Pnma, which also names as β-Li\u003csub\u003e3\u003c/sub\u003ePS\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e24\u003c/sup\u003e, indicating that the electrolyte has degraded. The polycrystalline Argyrodite structure has transformed into a β-Li\u003csub\u003e3\u003c/sub\u003ePS\u003csub\u003e4\u003c/sub\u003e polycrystalline structure. STEM-EDS mapping of this region is shown in Fig.\u0026nbsp;3(c). Sulfur is homogeneously distributed throughout the electrolyte. In contrast, Cl is enriched at the NMC811-SE interface and reduced in regions farther from the interface, suggesting that Cl atoms migrate toward the NMC811 surface during cycling. In addition, a small domain containing both P and O were observed.\u003c/p\u003e \u003cp\u003eAfter 200 charge-discharge cycles, the morphology of the NMC811- LPSClBr composite is shown in Figure S3. In addition to the enlarged interfacial gaps between NMC811 and the SE, cracks were observed within the SE itself, and even fine cracks developed inside the NMC811 particles \u003csup\u003e25 26\u003c/sup\u003e. In the SEM-EDS mapping of Figure S3, sulfur is homogeneously distributed throughout the electrolyte, while a small amount of sulfur was also detected inside the NMC811 particles. This means the sulfur diffused into the NMC811 particles. Meanwhile, the Cl content in the SE decreased drastically. Figure\u0026nbsp;4 presents SEM image of a single NMC811 particle along with the corresponding EDS mapping results. Sulfur is found to accumulate within the cracks inside the NMC811 particle. Cl and Br migrate out of the SE and segregate on certain surface regions of the NMC811. Although Cl and Br tend to migrate toward the NMC811 surface, they do not form a Cl- or Br-rich layer on the surface. Instead, they continue to accumulate into discrete regions enriched in Cl and Br.\u003c/p\u003e \u003cp\u003eFigure 5 presents the TEM results of the NMC811-Argyrodite composite after 200 cycles. In Fig.\u0026nbsp;5(a), the morphology image shows that the NMC811 and the electrolyte still maintain intimate interfacial contact. Selected area apertures were inserted at the NMC811-SE interface and within the electrolyte, as indicated in Figure S4(a). The corresponding SAED patterns and intensity profiles are shown in Figures S4(b) and (c). By inserting the objective aperture at the circled region in Figure S4(b), the corresponding DF image (Fig.\u0026nbsp;5(b)) reveals the high contrast spots at the interface, which are identified as the β-Li\u003csub\u003e3\u003c/sub\u003ePS\u003csub\u003e4\u003c/sub\u003e decomposed to Li\u003csub\u003e2\u003c/sub\u003eS nanocrystals and precipitated at the NMC811-SE interface. Similarly, the DF image obtained from the circled region in Figure S4(c), shown in Fig.\u0026nbsp;5(c), displays the high contrast areas corresponding to β-Li\u003csub\u003e3\u003c/sub\u003ePS\u003csub\u003e4\u003c/sub\u003e nanocrystals within the electrolyte. These observations indicate that structural degradation and decomposition of β-Li\u003csub\u003e3\u003c/sub\u003ePS\u003csub\u003e4\u003c/sub\u003e preferentially occur at the NMC811-SE interface.\u003c/p\u003e \u003cp\u003eThe STEM-EDS mapping of this interfacial region is displayed in Fig.\u0026nbsp;5(d). Sulfur is not only homogeneously distributed in the SE but also diffuses into the interior of the NMC811 particles, which is consistent with the SEM results. In contrast, Cl and Br are scarcely detected in this region, and no evidence of Cl and Br segregation was observed. A small domain enriched in both P and O was identified. High-magnification STEM-EDS results are provided in Figure S5.\u003c/p\u003e \u003cp\u003eFigure 6 shows the TEM image of the interior of an NMC811 particle. The initially large, spherical NMC811 particle was fragmented into smaller grains with diameters of approximately 300 nm. The appearance of those cracks inside the NMC811 particle is responsible for the lower deliverable capacity of NMC811. STEM-EDS elemental mapping confirmed that sulfur diffused into the NMC811 particle along these cracks and accumulated at the boundary of fragmented NMC811 particles.\u003c/p\u003e \u003cp\u003eThe degradation process of the NMC811- LPSClBr composite electrode during cycling can be summarized as follows. Before cycling, a well-formed NMC811- LiNbO\u003csub\u003e3\u003c/sub\u003e-SE interfacial contact was established, with all constituent elements homogeneously distributed across the electrolyte and electrode, which means that LPSClBr has good stability in contact with NMC811. As charge-discharge cycling progressed, the interfacial gap between NMC811 and SE gradually enlarged due to the lattice volume changes associated with lithium insertion and extraction \u003csup\u003e\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e\u003c/sup\u003e. Eventually, cracks developed within both the NMC811 and SE phases. Regarding SE degradation, LPSClBr first underwent structural decomposition into β-Li\u003csub\u003e3\u003c/sub\u003ePS\u003csub\u003e4\u003c/sub\u003e \u003csup\u003e11\u003c/sup\u003e. During this process, chlorine tended to migrate out of the SE and accumulate on the NMC811 surface. Subsequently, β-Li\u003csub\u003e3\u003c/sub\u003ePS\u003csub\u003e4\u003c/sub\u003e further decomposed into Li\u003csub\u003e2\u003c/sub\u003eS, which precipitated as nanocrystals on the surface of NMC811 particles. In Fig.\u0026nbsp;1(b), the discharge capacity progressively approaches and eventually exceeds the charge capacity during cycling. This abnormal capacity rise indicates the presence of parasitic reactions. A plausible origin of this phenomenon is the decomposition of the SE accompanied by the diffusion of sulfur species into the NMC811 phase \u003csup\u003e\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e\u003c/sup\u003e. Under electrochemical driving forces, Cl and Br gradually depart from the SE and migrate toward the NMC811/SE interface, where they eventually accumulate and form localized Cl/Br-rich regions, which, according to previous reports, predominantly correspond to LiCl and LiBr. The degradation of the SE leads to a reduction in ionic conductivity, thereby impeding Li-ion transport during cycling and ultimately deteriorating the overall electrochemical performance of the battery.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn this study, we investigated the structural and chemical evolution of NMC811- LPSClBr composite electrodes during electrochemical cycling using SEM, TEM, and EDS analyses. The results demonstrate that the initially well-formed NMC811-LiNbO\u003csub\u003e3\u003c/sub\u003e-SE interfaces progressively deteriorate with cycling, leading to interfacial separation and crack formation in both the electrode and electrolyte phases. The SE undergoes structural degradation, transforming from an Argyrodite-type polycrystalline phase into β-Li\u003csub\u003e3\u003c/sub\u003ePS\u003csub\u003e4\u003c/sub\u003e, and further decomposes with the precipitation of Li\u003csub\u003e2\u003c/sub\u003eS nanocrystals at the interface. Concurrently, chlorine migrates out of the electrolyte and segregates on the NMC811 surface as LiCl, while sulfur diffused into the NMC811 particles through cracks and accumulates as Li\u003csub\u003e2\u003c/sub\u003eS. These results highlight that long-term electrochemical instability in NMC811-Argyrodite composite electrodes is predominantly driven by interfacial degradation and accompanied by phase decomposition and elemental redistribution. Strategies to suppress electrolyte decomposition and inhibit halogen and sulfur migration will be critical for achieving durable solid-state batteries.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eJIONG DING collected experimental data and wrote the main manuscript text. Takao Kokubu, Inwoo Song and Yongjun Jang prepared the sample. All authors reviewed the manuscript.\u003c/p\u003e\u003ch2\u003eData Availability\u003c/h2\u003e\u003cp\u003eThe datasets used and/or analyzed during the current study are available from the corresponding author on reasonable request.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eMa, M. et al. A review of all-solid-state electrolytes for lithium batteries: high-voltage cathode materials, solid-state electrolytes and electrode\u0026ndash;electrolyte interfaces. \u003cem\u003eMater. Chem. 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Direct observation of Li6PS5Cl\u0026ndash;NMC electrochemical reactivity in all-solid-state cells. \u003cem\u003eEnergy Storage Mater.\u003c/em\u003e \u003cb\u003e75\u003c/b\u003e, 104050 (2025).\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-8298137/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8298137/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe interfacial stability between cathodes and solid electrolytes remains a critical challenge limiting the performance of all-solid-state batteries (ASSBs). In this work, we elucidate the degradation mechanisms of LiNi\u003csub\u003e0.8\u003c/sub\u003eMn\u003csub\u003e0.1\u003c/sub\u003eCo\u003csub\u003e0.1\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e(NMC811)-Li\u003csub\u003e6\u003c/sub\u003ePS\u003csub\u003e5\u003c/sub\u003eCl\u003csub\u003e0.5\u003c/sub\u003eBr\u003csub\u003e0.5\u003c/sub\u003e\u003csub\u003e\u003cstrong\u003e \u003c/strong\u003e\u003c/sub\u003ecomposite electrodes during electrochemical cycling using advanced electron microscopy. In the pristine state, spherical NMC811 particles are uniformly embedded in the Argyrodite electrolyte, forming intimate interfacial contact with the LiNbO\u003csub\u003e3\u003c/sub\u003e coating layer. With cycling, progressive interfacial separation and crack formation occur, accompanied by a structural transformation of the electrolyte from an Argyrodite-type polycrystalline phase to β-Li\u003csub\u003e3\u003c/sub\u003ePS\u003csub\u003e4\u003c/sub\u003e. Further decomposition leads to the precipitation of Li\u003csub\u003e2\u003c/sub\u003eS nanocrystals, preferentially localized at the cathode-electrolyte interface. Concurrently, chlorine migrates out of the electrolyte and segregates on the NMC811 surface as Cl-rich domains, while sulfur diffuses into NMC811 particles through cracks and accumulates as Li\u003csub\u003e2\u003c/sub\u003eS. These findings demonstrate that interfacial degradation, electrolyte decomposition, chlorine segregation, and sulfur diffusion cause the long-term instability of NMC811-Argyrodite composite electrodes. This study provides mechanistic insights into interfacial degradation pathways and offers design guidelines for enhancing interfacial stability in future solid-state batteries.\u003c/p\u003e","manuscriptTitle":"Direct observation of Degradation in LiNi0.8Mn0.1Co0.1O2-Li6PS5Cl0.5Br0.5 Composite Electrodes for All Solid-State Batteries","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-12-22 16:30:12","doi":"10.21203/rs.3.rs-8298137/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2026-01-21T07:22:37+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-01-03T08:25:48+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-12-28T01:34:55+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"160333499445124533751965078629072164829","date":"2025-12-28T01:33:55+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"211811079836920985862768822348613877699","date":"2025-12-21T21:06:43+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"163974039771220770667489848911853303617","date":"2025-12-20T12:22:05+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-12-19T12:30:20+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-12-17T13:13:01+00:00","index":"","fulltext":""},{"type":"editorInvited","content":"","date":"2025-12-17T12:44:47+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-12-16T12:08:37+00:00","index":"","fulltext":""},{"type":"submitted","content":"Scientific Reports","date":"2025-12-15T08:11:36+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"scientific-reports","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"scirep","sideBox":"Learn more about [Scientific Reports](http://www.nature.com/srep/)","snPcode":"","submissionUrl":"","title":"Scientific Reports","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Scientific Reports","inReviewEnabled":true,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"e56a8a7c-df6a-4b15-aa83-d6252c66ab75","owner":[],"postedDate":"December 22nd, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"in-revision","subjectAreas":[{"id":60080661,"name":"Physical sciences/Chemistry"},{"id":60080662,"name":"Physical sciences/Energy science and technology"},{"id":60080663,"name":"Physical sciences/Materials science"}],"tags":[],"updatedAt":"2026-01-21T07:52:52+00:00","versionOfRecord":[],"versionCreatedAt":"2025-12-22 16:30:12","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8298137","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8298137","identity":"rs-8298137","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}