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Sulfide‐based all‐solid‐state lithium‐ion batteries (LIBs) are promising replacements for conventional liquid electrolyte LIBs. However, their degradation mechanisms and analysis methods are poorly understood. Herein, the degradation mechanism of an argyrodite‐type sulfide‐based all‐solid‐state prototype LIB cell is reported. Furthermore, an analysis method for all‐solid‐state batteries using charge/discharge cycle tests at 100°C followed by the disassembly analysis of cells before and after accelerated degradation tests is reported. Based on the findings of this study, the degradation of the prototype cell is classified as follows: (i) solid electrolyte (SE) oxidation in the positive electrode, which recovers battery capacity and increases resistance; (ii) SE reduction in the negative electrode, which decreases capacity; (iii) lithium deposition on/in the negative electrode, which decreases capacity; and (iv) capacity loss of the positive electrode, which decreases capacity. These degradation reactions appear to occur simultaneously. These findings are expected to aid the development of sulfide‐based solid‐electrolyte LIBs with improved safety and energy densities. The degradation of all‐solid‐state lithium‐ion batteries was assessed using charge/discharge cycle tests and accelerated degradation experiments. Degradation is attributed to four factors: (i) solid electrolyte (SE) oxidation in the positive electrode, (ii) SE reduction in the negative electrode, (iii) lithium deposition on/in the negative electrode, and (iv) the capacity loss of the positive electrode.

Full exhaustion in specific energy/energy density of state‐of‐the‐art LiNi x Co y Mn z O 2 (NCM)‐based Li‐ion batteries (LIB) is currently limited for reasons of NCM stability by upper cut‐off voltages (UCV) below 4.3 V. At higher UCV, structural decomposition triggers electrode crosstalk in the course of enhanced transition metal dissolution and leads to severe specific capacity/energy fade; in the worst case to a sudden death phenomenon (roll‐over failure). The additive lithium difluorophosphate (LiDFP) is known to suppress this by scavenging dissolved metals, but at the cost of enhanced toxicity due to the formation of organofluorophosphates (OFPs). Addition of film‐forming electrolyte additives like vinylene carbonate (VC) can intrinsically decrease OFP formation in thermally aged LiDFP‐containing electrolytes, though the benefit of this dual‐additive approach can be questioned at higher UCVs. In this work, VC is shown to decrease the formation of potentially toxic OFPs within the electrolyte during cycling at conventional UCVs but triggers OFP formation at higher UCVs. The electrolyte contains soluble VC‐polymerization products. These products are formed at the cathode during VC oxidation (and are found within the cathode electrolyte interphase (CEI), suggesting an OFP electrode crosstalk of VC decomposition species, as the OFP‐precursor molecules are shown to be formed at the anode.

Plasma electrolytic oxidation (PEO) is normally carried out under conditions with electrolyte cooling. However, the effect of the temperature of the electrolytes on the PEO behavior and properties of the resulting coatings is seldom investigated. In this study, PEO of pure Al was carried out in a dilute aluminate electrolyte with the electrolyte temperature being controlled under low (~10–30 °C), medium (~40–50 °C) and high (~70–80 °C) temperature ranges, respectively. The morphology, microstructure, composition and phase component of the coatings fabricated under the different temperature ranges were analyzed by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The corrosion resistances of the coatings were evaluated by electrochemical methods. The hardness of the coatings and substrate following the PEO treatment in the different electrolyte temperature ranges were also tested. It was found that a higher electrolyte temperature resulted in a higher growth rate and rougher coatings. Moreover, the α-Al2O3 content was reduced as the electrolyte temperature increased. The highest corrosion resistance was registered for the coating obtained under the lowest temperature range, whereas the corrosion resistance of the coating obtained under the highest temperature range was the worst. The higher growth rate under high electrolyte temperatures was associated with the increased kinetics of the PEO reactions. However, the temperature of the electrolyte should be controlled under a suitable range to ensure reasonable coating properties.

Magnesium alloys, due to their unique properties, low density and high strength properties, are becoming more frequently used in industrial applications. However, a limitation of their use may be the need to ensure high abrasive wear resistance and corrosion resistance. Therefore, magnesium alloys are often protected by applying protective coatings. The paper presents the influence of the modification of the electrolyte composition, with or without the addition of borax, on the morphology (observed by SEM method) and phase composition (analyzed by EDS and XRD) of the formed layers on the AZ91 magnesium alloy, and their abrasive wear (determined with Ball-on-Disc method) and corrosion resistance (evaluated using the immersion method and by electrochemical tests), especially in chloride solutions. It has been clearly demonstrated that the modification of the electrolyte composition significantly impacts the final properties of the protective coatings on the AZ91 alloy formed by the plasma electrolytic oxidation (PEO) process. On the basis of the results, it was found that the new type of PEO coatings with the borax addition, compared to base PEO coatings, showed significantly higher abrasion resistance and an order of magnitude lower corrosion rate.

Lithium-ion batteries (LIBs) have come to hold ever greater significance across diverse fields. However, thermal runaway and associated fire incidents have undeniably constrained the application and development of LIBs. Consequently, gaining a profound understanding of the reaction mechanisms of LIB electrolytes during thermal runaway is of critical importance for ensuring the fire protection of LIBs. In this study, quantum chemical calculations were employed to construct oxidation reaction models of electrolytes, and a comprehensive summary of the sources of fire gas generation during the thermal runaway of LIBs is presented. During the sequence of oxidation reactions, the -COH functional group emerged as the most critical intermediate product. Under conditions of low oxygen availability, it was prone to decompose into CO, whereas in the presence of sufficient oxygen, it could undergo further oxidation to form -COOH and subsequently decompose into CO2. Moreover, the reaction chains associated with electrolyte oxidation were found to be highly intricate, characterized by multiple branches and a wide variety of intermediate products. Furthermore, an in-depth analysis was carried out on the generation mechanisms of several typical fire gases. The analysis revealed that CH3OH and C2H5OH could be considered as the characteristic products of the oxidation reactions of DMC and DEC, respectively. It is anticipated that this research will provide a robust theoretical foundation for elucidating the complex reactions involved in LIB fires and offer reaction models for fire simulation purposes, thereby contributing to the enhancement of the safety and reliability of LIBs in various applications.

Because Mg-Ca-Zn alloys are biodegradable and obviate secondary implant removal, they are especially beneficial for pediatric patients. We examined the degradation performance of Mg-Ca-Zn alloys depending on the surface modification and investigated the in vivo effects on the growth plate in a skeletally immature rabbit model. Either plasma electrolyte oxidation (PEO)-coated (n = 18) or non-coated (n = 18) Mg-Ca-Zn alloy was inserted at the distal femoral physis. We measured the degradation performance and femoral segment lengths using micro-CT. In addition, we analyzed the histomorphometric and histopathologic characteristics of the growth plate. Although there were no acute, chronic inflammatory reactions in either group, they differed significantly in the tissue reactions to their degradation performance and physeal responses. Compared to non-coated alloys, PEO-coated alloys degraded significantly slowly with diminished hydrogen gas formation. Depending on the degradation rate, large bone bridge formation and premature physeal arrest occurred primarily in the non-coated group, whereas only a small-sized bone bridge formed in the PEO-coated group. This difference ultimately led to significant shortening of the femoral segment in the non-coated group. This study suggests that optimal degradation could be achieved with PEO-coated Mg-Ca-Zn alloys, making them promising and safe biodegradable materials with no growth plate damage.

In this study, the influence of cathodic polarization on the plasma electrolytic oxidation (PEO) behaviors of pure magnesium and AZ31 and AZ91 magnesium alloys with varied Al alloying contents was systematically examined in a dilute alkaline silicate electrolyte by adjusting the cathodic-to-anodic current density ratio (R = jc/ja) from 0 to 3.2. The results show that moderate cathodic polarization (R = 0.6) led to the thickest coatings on the Mg and Mg alloys, and the coatings grew in an outward-and-inward mode compared with the inward growth at R = 0. Excessive cathodic polarization (high R ratios) differently influenced the PEO behaviors of the magnesium alloys. For the pure magnesium and AZ31 alloy, the coatings blistered or peeled off when the R ≥ 0.9. However, the tolerance to cathodic polarization was significantly improved for the AZ91 Mg alloy. The coatings were undamaged even with the highest R ratio of 3.2, and their compactness was further improved as the R ratio increased to 0.9 and 1.2. An increase in cathodic polarization led to a reduction in the anodic potential and spark softening but did not result in an improvement in the coating quality. Optical emission spectroscopy identified two spectral lines at 559.79 and 570.11 nm, which are assigned to the Mg species but not found in databases or the literature. The corrosion and wear resistance of the PEO coatings were also investigated. The coating formed on the AZ91 magnesium alloy at R = 1.2 displayed the narrowest wear track due to its high compactness.

This study elucidates the presence of a cathode electrolyte interphase (CEI) at graphite positive electrodes (PEs) and assesses its impact on the performance of dual‐ion batteries, being promising candidates for cost‐efficient and sustainable stationary energy storage. Indeed, electrolyte oxidation increases during charge (5 V vs Li|Li+) for decreased C rates, that is longer duration at high state‐of‐charges (SOC) , but effective protection and evidence for CEI formation is missing as no increase in Coulombic efficiencies is observed, even with literature‐known electrolyte additives like vinylene carbonate, fluoroethylene carbonate, or ethylene sulfite in a highly concentrated base electrolyte (4.0 m LiPF6 in dimethyl carbonate) as reference. Via studying charged and pristine PEs by X‐ray photoelectron spectroscopy, PF6−‐graphite intercalation compounds and cointercalated solvent molecules are identified, while indications for CEI are absent within 1000 charge/discharge cycles. Nevertheless, a high capacity retention of ≈94% (referring to 0.1C) is demonstrated. Affirmed by Raman spectroscopy and scanning electron microscopy, the active material remains structurally stable, suggesting capacity fading to be dominated by resistance rise at the PE, likely due to an electronic contact resistance from active material grain boundaries and/or from the interface between electrode particles and the current collector in course of high volume changes; as systematically derived by impedance spectroscopy. In dual‐ion batteries (5 V), electrolyte oxidation and formation of cathode electrolyte interphase (CEI) can be reasonably assumed. However, neither a protective “passivation” effect with varied electrolyte additives is observed within direct current applications, nor any hints for a surface layer via X‐ray photoelectron spectroscopy or electrochemical impedance spectroscopy, rendering presence of CEI unlikely.

Crystal structure of oxide ceramic coatings obtained on AK9M2 and AK12 alloys is determined. Already after 5 min of processing the AK9M2 alloy by plasma electrolyte oxidation (PEO) method in a standard electrolyte (KOH (3 g/L), Na 2 SiO 3 (2 g/L)), aluminum and silicon form a compound Al 3.21 Si 0.47 . The thermal stability of compounds with the Al 2 O 3 ∙SiO 2 composition is analyzed. A scheme for converting intermediate oxides into mullite is proposed. The obtained results show that with the increase of silicon content in alloys the amount of sillimanite in the corresponding coatings increases. Increase of the PEO process of silumins processing to 2 h causes a partial transformation of sillimanite into mullite. The maximum content of mullite in coatings is approximately 4 mass%.

To regulate the degradation rate and improve the surface biocompatibility of the AZ31B magnesium alloy, three different coating systems were produced via plasma electrolytic oxidation (PEO): simple PEO, PEO incorporating multi-walled carbon nanotubes (PEO + CNT), and a duplex coating that included a polycaprolactone top layer (PEO + CNT/PCL). Surfaces were characterized by chemical content, roughness, topography, and wettability. Biological properties analysis included cell metabolism and adhesion. PEO ± CNT resulted in an augmented surface roughness compared with the base material (BM), while PCL deposition produced the smoothest surface. All surfaces had a contact angle below 90°. The exposure of gFib-TERT and bmMSC to culture media collected after 3 or 24 h did not affect their metabolism. A decrease in metabolic activity of 9% and 14% for bmMSC and of 14% and 29% for gFib-TERT was observed after 3 and 7 days, respectively. All cells died after 7 days of exposure to BM and after 15 days of exposure to coated surfaces. Saos-2 and gFib-TERT adhered poorly to BM, in contrast to bmMSC. All cells on PEO anchored into the pores with filopodia, exhibited tiny adhesion protrusions on PEO + CNT, and presented a web-like spreading with lamellipodia on PEO + CNT/PCL. The smooth and homogenous surface of the duplex PEO + CNT/PCL coating decreased magnesium corrosion and led to better biological functionality.