Atomic-Scale Cryo-TEM Studies of the Electrochemistry of Redox Mediator in Li-O2 Batteries.

Rechargeable aprotic lithium (Li)-oxygen battery (LOB) is a potential next-generation energy storage technology because of its high theoretical specific energy. However, the role of redox mediator on the oxide electrochemistry remains unclear. This is partly due to the intrinsic complexity of the battery chemistry and the lack of in-depth studies of oxygen electrodes at the atomic level by reliable techniques. Herein, cryo-transmission electron microscopy (cryo-TEM) is used to study how the redox mediator LiI affects the oxygen electrochemistry in LOBs. It is revealed that with or without LiI in the electrolyte, the discharge products are plate-like LiOH or toroidal Li2 O2 , respectively. The I2 assists the decomposition of LiOH via the formation of LiIO3 in the charge process. In addition, a LiI protective layer is formed on the Li anode surface by the shuttle of I3 - , which inhibits the parasitic Li/electrolyte reaction and improves the cycle performance of the LOBs. The LOBs returned to 2e- oxygen reduction reaction (ORR) to produce Li2 O2 after the LiI in the electrolyte is consumed. This work provides new insight on the role of redox mediator on the complex electrochemistry in LOBs which may aid the design LOBs for practical applications.

Pb-rich Cu grain boundary sites for selective CO-to-n-propanol electroconversion.

Electrochemical carbon monoxide (CO) reduction to high-energy-density fuels provides a potential way for chemical production and intermittent energy storage. As a valuable C3 species, n-propanol still suffers from a relatively low Faradaic efficiency (FE), sluggish conversion rate and poor stability. Herein, we introduce an "atomic size misfit" strategy to modulate active sites, and report a facile synthesis of a Pb-doped Cu catalyst with numerous atomic Pb-concentrated grain boundaries. Operando spectroscopy studies demonstrate that these Pb-rich Cu-grain boundary sites exhibit stable low coordination and can achieve a stronger CO adsorption for a higher surface CO coverage. Using this Pb-Cu catalyst, we achieve a CO-to-n-propanol FE (FEpropanol) of 47 ± 3% and a half-cell energy conversion efficiency (EE) of 25% in a flow cell. When applied in a membrane electrode assembly (MEA) device, a stable FEpropanol above 30% and the corresponding full-cell EE of over 16% are maintained for over 100 h with the n-propanol partial current above 300 mA (5 cm2 electrode). Furthermore, operando X-ray absorption spectroscopy and theoretical studies reveal that the structurally-flexible Pb-Cu surface can adaptively stabilize the key intermediates, which strengthens the *CO binding while maintaining the C-C coupling ability, thus promoting the CO-to-n-propanol conversion.

Novel hypoxia-related gene signature for predicting prognoses that correlate with the tumor immune microenvironment in NSCLC.

Background: Intratumoral hypoxia is widely associated with the development of malignancy, treatment resistance, and worse prognoses. The global influence of hypoxia-related genes (HRGs) on prognostic significance, tumor microenvironment characteristics, and therapeutic response is unclear in patients with non-small cell lung cancer (NSCLC). Method: RNA-seq and clinical data for NSCLC patients were derived from The Cancer Genome Atlas (TCGA) database, and a group of HRGs was obtained from the MSigDB. The differentially expressed HRGs were determined using the limma package; prognostic HRGs were identified via univariate Cox regression. Using the least absolute shrinkage and selection operator (LASSO) and multivariate Cox regression, an optimized prognostic model consisting of nine HRGs was constructed. The prognostic model's capacity was evaluated by Kaplan‒Meier survival curve analysis and receiver operating characteristic (ROC) curve analysis in the TCGA (training set) and GEO (validation set) cohorts. Moreover, a potential biological pathway and immune infiltration differences were explained. Results: A prognostic model containing nine HRGs (STC2, ALDOA, MIF, LDHA, EXT1, PGM2, ENO3, INHA, and RORA) was developed. NSCLC patients were separated into two risk categories according to the risk score generated by the hypoxia model. The model-based risk score had better predictive power than the clinicopathological method. Patients in the high-risk category had poor recurrence-free survival in the TCGA (HR: 1.426; 95% CI: 0.997-2.042; p = 0.046) and GEO (HR: 2.4; 95% CI: 1.7-3.2; p < 0.0001) cohorts. The overall survival of the high-risk category was also inferior to that of the low-risk category in the TCGA (HR: 1.8; 95% CI: 1.5-2.2; p < 0.0001) and GEO (HR: 1.8; 95% CI: 1.4-2.3; p < 0.0001) cohorts. Additionally, we discovered a notable distinction in the enrichment of immune-related pathways, immune cell abundance, and immune checkpoint gene expression between the two subcategories. Conclusion: The proposed 9-HRG signature is a promising indicator for predicting NSCLC patient prognosis and may be potentially applicable in checkpoint therapy efficiency prediction.

Multiplicative Attacks with Essential Stealthiness in Sensor and Actuator Loops against Cyber-Physical Systems.

Stealthy attacks in sensor and actuator loops are the research priorities in the security of cyber-physical systems. Existing attacks define the stealthiness conditions against the Chi-square or Kullback-Leibler divergence detectors and parameterize the attack model based on additive signals. Such conditions ignore the potential anomalies of the vulnerable outputs in the control layer, and the attack sequences need to be generated online, increasing the hardware and software costs. This paper investigates a type of multiplicative attack with essential stealthiness where the employed model is a novel form. The advantage is that the parameters can be designed in a constant form without having to be generated online. An essential stealthiness condition is proposed for the first time and complements the existing ones. Two sufficient conditions for the existence of constant attack matrices are given in the form of theorems, where two methods for decoupling the unknown variables are particularly considered. A quadruple-tank process, an experimental platform for attack and defense, is developed to verify the theoretical results. The experiments indicate that the proposed attack strategy can fulfill both the attack performance and stealthiness conditions.

Cryo-EM Revealing the Origin of Excessive Capacity of the Se Cathode in Sulfide-Based All-Solid-State Li-Se Batteries.

Selenium (Se), whose electronic conductivity is nearly 25 orders higher than that of sulfur (S) and whose theoretical volumetric capacity is 3254 mAh cm-3, is considered as a potential alternative to S to overcome the poor electronic conductivity issue of the S cathode in the lithium (Li)-S battery. However, the study of the Li-Se battery, particularly a Li-Se all-solid-state battery (ASSB), is still in its infancy. Herein, we report the performance of Li-Se ASSBs at both room temperature (RT) and high temperature (HT, 50 °C), using a Li10Si0.3PS6.9Cl1.8 (LSPSCl) solid-state electrolyte and Li-In anode. With a Se loading of 7.6 mg cm-2, the Li-Se battery displayed a record high reversible capacity of 6.8 mAh cm-2 after 50 cycles at HT, which exceeds the theoretical areal capacity of 5.2 mAh cm-2 for Se. Moreover, the RT Li-Se ASSB delivered an initial areal capacity of about 2 mAh cm-2 at a current density of 1 A g-1 for 1200 cycles with a capacity retention of 67%. Cryo-electron microscopy revealed that the excessive capacity of Se at HT can be attributed to the formation of a previously unknown S5Se4 phase during charging, which participated reversibly in a subsequent redox reaction. The formation of the S5Se4 phase originated from the reaction of Se with S, which was generated by the decomposition of LSPSCl at HT. These results unlock the electrochemistry of a Li-Se ASSB, suggesting that a Li-Se ASSB is a viable alternative to a Li-S battery for energy storage applications.

Exploiting the Iron Difluoride Electrochemistry by Constructing Hierarchical Electron Pathways and Cathode Electrolyte Interface.

Conversion-type cathodes such as metal fluorides, especially FeF2 and FeF3 , are potential candidates to replace intercalation cathodes for the next generation of lithium ion batteries. However, the application of iron fluorides is impeded by their poor electronic conductivity, iron/fluorine dissolution, and unstable cathode electrolyte interfaces (CEIs). A facile route to fabricate a mechanical strong electrode with hierarchical electron pathways for FeF2 nanoparticles is reported here. The FeF2 /Li cell demonstrates remarkable cycle performances with a capacity of 300 mAh g-1 after a record long 4500 cycles at 1C. Meanwhile, a record stable high area capacity of over 6 mAh cm-2 is achieved. Furthermore, ultra-high rate capabilities at 20C and 6C for electrodes with low and high mass loading, respectively, are attained. Advanced electron microscopy reveals the formation of stable CEIs. The results demonstrate that the construction of viable electronic connections and favorable CEIs are the key to boost the electrochemical performances of FeF2 cathode.

An All-Solid-State Battery Based on Sulfide and PEO Composite Electrolyte.

Replacing liquid electrolytes with solid polymer electrolytes (SPEs) is considered as a vital approach to developing sulfur (S)-based cathodes. However, the polysulfides shuttle and the growth of lithium (Li) dendrites are still the major challenges in polyethylene oxide (PEO)-based electrolyte. Here, an all-solid-state Li metal battery with flexible PEO-Li10 Si0.3 PS6.7 Cl1.8 (LSPSCl)-C-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) composite cathode (FCC) and PEO-LSPSCl-LiTFSI composite electrolyte (S-CPE) is designed. The initial capacity of the Li|S-CPE|FCC battery is 414 mAh g-1 with 97.8% capacity retention after 100 cycles at 0.1 A g-1 . Moreover, the battery displays remarkable capacity retention of 80% after 500 cycles at 0.4 A g-1 . Cryo-transmission electron microscopy (Cryo-TEM) reveals rich large-sized Li2 CO3 particles at the Li/PEO interface blocking the Li+ transport, but the layer with rich Li2 O nanocrystals, amorphous LiF and Li2 S at the Li/S-CPE interface suppresses the growth of lithium dendrite and stabilizes the interface. In situ optical microscopy demonstrates that the excellent cyclic stability of FCC is ascribed to the reversible shuttle of P-S-P species, resulting from the movement of ether backbone in PEO. This study provides strategies to mitigate the polysulfide shuttle effect and Li dendrite formation in designing high energy density solid-state Li-S-based batteries.

Enabling Long Cycle Life and High Rate Iron Difluoride Based Lithium Batteries by In Situ Cathode Surface Modification.

Metals fluorides (MFs) are potential conversion cathodes to replace commercial intercalation cathodes. However, the application of MFs is impeded by their poor electronic/ionic conductivity and severe decomposition of electrolyte. Here, a composite cathode of FeF2 and polymer-derived carbon (FeF2 @PDC) with excellent cycling performance is reported. The composite cathode is composed of nanorod-shaped FeF2 embedded in PDC matrix with excellent mechanical strength and electronic/ionic conductivity. The FeF2 @PDC enables a reversible capacity of 500 mAh g-1 with a record long cycle lifetime of 1900 cycles. Remarkably, the FeF2 @PDC can be cycled at a record rate of 60 C with a reversible capacity of 107 mAh g-1 after 500 cycles. Advanced electron microscopy reveals that the in situ formation of stable Fe3 O4 layers on the surface of FeF2 prevents the electrolyte decomposition and leaching of iron (Fe), thus enhancing the cyclability. The results provide a new understanding to FeF2 electrochemistry, and a strategy to radically improve the electrochemical performance of FeF2 cathode for lithium-ion battery applications.

Size-Dependent Chemomechanical Failure of Sulfide Solid Electrolyte Particles during Electrochemical Reaction with Lithium.

The very high ionic conductivity of Li10GeP2S12 (LGPS) solid electrolyte (SE) makes it a promising candidate SE for solid-state batteries in electrical vehicles. However, chemomechanical failure, whose mechanism remains unclear, has plagued its widespread applications. Here, we report in situ imaging lithiation-induced failure of LGPS SE. We revealed a strong size effect in the chemomechanical failure of LGPS particles: namely, when the particle size is greater than 3 µm, fracture/pulverization occurred; when the particle size is between 1 and 3 µm, microcracks emerged; when the particle size is less than 1 µm, no chemomechanical failure was observed. This strong size effect is interpreted by the interplay between elastic energy storage and dissipation. Our finding has important implications for the design of high-performance LGPS SE, for example, by reducing the particle size to less than 1 µm the chemomechanical failure of LGPS SE can be mitigated.

In Situ Visualization of Lithium Penetration through Solid Electrolyte and Dead Lithium Dynamics in Solid-State Lithium Metal Batteries.

The two biggest promises of solid-state lithium (Li) metal batteries (SSLMBs) are the suppression of Li dendrites by solid-state electrolyte (SSE) and the realization of a high-energy-density Li anode. However, LMBs have not met their expectations due to Li dendrite growth causing short-circuiting. In fact, Li dendrites grow even more easily in SSE than in liquid electrolyte, but the reason for this remains unclear. Here we report in situ transmission electron microscopy observations of Li dendrite penetration through SSE and "dead" Li formation dynamics in SSLMBs. We show direct evidence that large electrochemomechanical stress generates cracks in the SSE and drives Li through the SSE directly. We revealed that fresh Li nucleation sites emerged in every discharge cycle, creating new "dead" Li in the following charging cycle and becoming the dominant Coulombic efficiency decay mechanism in SSLMBs. These results indicate that engineering flaw size and reducing electronic conductivity in SSEs are essential to improve the performance of SSLMBs.

Ultrastable Anode/Electrolyte Interface in Solid-State Lithium-Metal Batteries Using LiCux Nanowire Network Host.

High interfacial resistance and uncontrollable lithium (Li) dendrite are major challenges in solid-state Li-metal batteries (SSLMBs), as they lead to premature short-circuiting and failure of SSLMBs. Here, we report the synthesis of a composite anode comprising a three-dimensional LiCux nanowire network host infiltrated with Li (Li* anode) with low interfacial impedance and superior electrochemical performance. The Li* anode is fabricated by dissolving Cu foil into molten Li followed by solidification. The Li* anode exhibits good wettability with Li6.4La3Zr1.4Ta0.6O12 (LLZTO) and high mechanical strength, rendering low Li*/LLZTO interfacial impedance, homogeneous deposition of Li, and suppression of Li dendrites. Consequently, the Li* anode-based symmetric cells and full cells with LiNi0.88Co0.1Al0.02O2 (NCA), LiFePO4 (LFP), and FeF2 cathodes deliver remarkable electrochemical performance. Specifically, the Li*/LLZTO/Li* symmetrical cell achieves a remarkably long cycle lifetime of 10 000 h with 0.1 mA·cm-2; the Li*/LLZTO/NCA full cell maintains capacity retention of 73.4% after 500 cycles at 0.5C; and all-solid-state Li*/LLZTO/FeF2 full cell achieves a reversible capacity of 147 mAh·g-1 after 500 cycles at 100 mA·g-1. This work demonstrates potential design tactics for an ultrastable Li*/garnet interface to enable high-performance SSLMBs.

In Situ Measurements of the Mechanical Properties of Electrochemically Deposited Li2CO3 and Li2O Nanorods.

Solid-electrolyte interface (SEI) is "the most important but least understood (component) in rechargeable Li-ion batteries". The ideal SEI requires high elastic strength and can resist the penetration of a Li dendrite mechanically, which is vital for inhibiting the dendrite growth in lithium batteries. Even though Li2CO3 and Li2O are identified as the major components of SEI, their mechanical properties are not well understood. Herein, SEI-related materials such as Li2CO3 and Li2O were electrochemically deposited using an environmental transmission electron microscopy (ETEM), and their mechanical properties were assessed by in situ atomic force microscopy (AFM) and inverse finite element simulations. Both Li2CO3 and Li2O exhibit nanocrystalline structures and good plasticity. The ultimate strength of Li2CO3 ranges from 192 to 330 MPa, while that of Li2O is less than 100 MPa. These results provide a new understanding of the SEI and its related dendritic problems in lithium batteries.

Lithium Deposition-Induced Fracture of Carbon Nanotubes and Its Implication to Solid-State Batteries.

The increasing demand for safe and dense energy storage has shifted research focus from liquid electrolyte-based Li-ion batteries toward solid-state batteries (SSBs). However, the application of SSBs is impeded by uncontrollable Li dendrite growth and short circuiting, the mechanism of which remains elusive. Herein, we conceptualize a scheme to visualize Li deposition in the confined space inside carbon nanotubes (CNTs) to mimic Li deposition dynamics inside solid electrolyte (SE) cracks, where the high-strength CNT walls mimic the mechanically strong SEs. We observed that the deposited Li propagates as a creeping solid in the CNTs, presenting an effective pathway for stress relaxation. When the stress-relaxation pathway is blocked, the Li deposition-induced stress reaches the gigapascal level and causes CNT fracture. Mechanics analysis suggests that interfacial lithiophilicity critically governs Li deposition dynamics and stress relaxation. Our study offers critical strategies for suppressing Li dendritic growth and constructing high-energy-density, electrochemically and mechanically robust SSBs.

In situ observation of cracking and self-healing of solid electrolyte interphases during lithium deposition.

The growth of lithium (Li) whiskers is detrimental to Li batteries. However, it remains a challenge to directly track Li whisker growth. Here we report in situ observations of electrochemically induced Li deposition under a CO2 atmosphere inside an environmental transmission electron microscope. We find that the morphology of individual Li deposits is strongly influenced by the competing processes of cracking and self-healing of the solid electrolyte interphase (SEI). When cracking overwhelms self-healing, the directional growth of Li whiskers predominates. In contrast, when self-healing dominates over cracking, the isotropic growth of round Li particles prevails. The Li deposition rate and SEI constituent can be tuned to control the Li morphologies. We reveal a new "weak-spot" mode of Li dendrite growth, which is attributed to the operation of the Bardeen-Herring growth mechanism in the whisker's cross section. This work has implications for the control of Li dendrite growth in Li batteries.

In situ imaging electrocatalytic CO2 reduction and evolution reactions in all-solid-state Li-CO2 nanobatteries.

Li-CO2 batteries are promising energy storage devices owing to their high energy density and possible applications for CO2 capture. However, still some critical issues, such as high charging overpotential and poor cycling stability caused by the sluggish decomposition of Li2CO3 discharge products, need to be addressed before the practical applications of Li-CO2 batteries. Exploring highly efficient catalysts and understanding their catalytic mechanisms for the CO2 reduction reaction (CORR) and evolution reaction (COER) are critical for the application of Li-CO2 batteries. However, the direct imaging of electrocatalysis during CORR and COER is still elusive. Herein, we report the in situ imaging of electrocatalysis during CORR and COER in a Li-CO2 nanobattery using a Ni-Ru-coated α-MnO2 nanowire (Ni-Ru/MnO2) cathode in an advanced aberration corrected environmental transmission electron microscope. During the CORR, a thick Li2CO3 and carbon mixture layer was formed on the surface of the Ni-Ru/MnO2 nanowires via 4Li+ + 3CO2 + 4e-→ 2Li2CO3 + C. During the COER, the as-formed Li2CO3 decomposed via 2Li2CO3→ 2CO2 + O2 + 4Li+ + 4e-, while the as-formed amorphous carbon remained. In contrast, the decomposition of Li2CO3 on bare MnO2 nanowires was difficult, underscoring the important Ni-Ru bimetal electrocatalytic role in facilitating the COER. Our results provide an important understanding of the CO2 chemistry in Li-CO2 batteries, possibly helping in the designing of Li-CO2 batteries for energy storage applications.

In Situ Electrochemical Study of Na-O2/CO2 Batteries in an Environmental Transmission Electron Microscope.

Metal-air batteries are potential candidates for post-lithium energy storage devices due to their high theoretical energy densities. However, our understanding of the electrochemistry of metal-air batteries is still in its infancy. Herein we report in situ studies of Na-O2/CO2 (O2 and CO2 mixture) and Na-O2 batteries with either carbon nanotubes (CNTs) or Ag nanowires as the air cathode medium in an advanced aberration corrected environmental transmission electron microscope. In the Na-O2/CO2-CNT nanobattery, the discharge reactions occurred in two steps: (1) 2Na+ + 2e- + O2 → Na2O2; (2) Na2O2+ CO2 → Na2CO3 + O2; concurrently a parasitic Na plating reaction took place. The charge reaction proceeded via (3) 2Na2CO3 + C → 4Na+ + 3CO2 + 4e-. In the Na-O2/CO2-Ag nanobattery, the discharge reactions were essentially the same as those for the Na-O2/CO2-CNT nanobattery; however, the charge reaction in the former was very sluggish, suggesting that direct decomposition of Na2CO3 is difficult. In the Na-O2 battery, the discharge reaction occurred via reaction 1, but the reverse reaction was very difficult, indicating the sluggish decomposition of Na2O2. Overall the Na-O2/CO2-CNT nanobattery exhibited much better cyclability and performance than the Na-O2/CO2-Ag and the Na-O2-CNT nanobatteries, underscoring the importance of carbon and CO2 in facilitating the Na-O2 nanobatteries. Our study provides important understanding of the electrochemistry of the Na-O2/CO2 and Na-O2 nanobatteries, which may aid the development of high performance Na-O2/CO2 and Na-O2 batteries for energy storage applications.

Deguelin inhibits HCV replication through suppressing cellular autophagy via down regulation of Beclin1 expression in human hepatoma cells.

AIMS: Deguelin, a natural compound derived from Mundulea sericea (Leguminosae) and some other plants exhibits an activity to inhibit autophagy, a cellular machinery required for hepatitis C virus (HCV) replication. This study aimed to illuminate the impact of deguelin on HCV replication and mechanism(s) involved. METHODS: HCV JFH-1-Huh7 infectious system was used for the investigation. Real time RT-PCR, Western blot, fluorescent microscopy assay were used to measure the expression levels of viral or cellular factors. Overexpression and silencing expression techniques were used to determine the role of key cellular factors. RESULTS: Deguelin treatment of Huh7 cells significantly inhibited HCV JFH-1 replication in a dose- and time-dependent manner. Deguelin treatment suppressed autophagy in Huh7 cells, evidenced by the decrease of LC3B-II levels, the conversion of LC3B-I to LC3B-II, and the formation of GFP-LC3 puncta as well as the increase of p62 level in deguelin-treated cells compared with control cells. HCV infection could induce autophagy which was also suppressed by deguelin treatment. Mechanism research reveals that deguelin inhibited expression of Beclin1, which is a key cellular factor for the initiation of the autophagosome formation in autophagy. Overexpression or silencing expression of Beclin1 in deguelin-treated Huh7 cells could weaken or enhance the inhibitory effect on autophagy by deguelin, respectively, and thus partially recover or further inhibit HCV replication correspondingly. CONCLUSIONS: Deguelin may serve as a novel anti-HCV compound via its inhibitory effect on autophagy, which warrants further investigation as a potential therapeutic agent for HCV infection.

Lithium whisker growth and stress generation in an in situ atomic force microscope-environmental transmission electron microscope set-up.

Lithium metal is considered the ultimate anode material for future rechargeable batteries1,2, but the development of Li metal-based rechargeable batteries has achieved only limited success due to uncontrollable Li dendrite growth3-7. In a broad class of all-solid-state Li batteries, one approach to suppress Li dendrite growth has been the use of mechanically stiff solid electrolytes8,9. However, Li dendrites still grow through them10,11. Resolving this issue requires a fundamental understanding of the growth and associated electro-chemo-mechanical behaviour of Li dendrites. Here, we report in situ growth observation and stress measurement of individual Li whiskers, the primary Li dendrite morphologies12. We combine an atomic force microscope with an environmental transmission electron microscope in a novel experimental set-up. At room temperature, a submicrometre whisker grows under an applied voltage (overpotential) against the atomic force microscope tip, generating a growth stress up to 130 MPa; this value is substantially higher than the stresses previously reported for bulk13 and micrometre-sized Li14. The measured yield strength of Li whiskers under pure mechanical loading reaches as high as 244 MPa. Our results provide quantitative benchmarks for the design of Li dendrite growth suppression strategies in all-solid-state batteries.

Air-Stable Lithium Spheres Produced by Electrochemical Plating.

Lithium metal is an ideal anode for next-generation lithium batteries owing to its very high theoretical specific capacity of 3860 mAh g-1 but very reactive upon exposure to ambient air, rendering it difficult to handle and transport. Air-stable lithium spheres (ASLSs) were produced by electrochemical plating under CO2 atmosphere inside an advanced aberration-corrected environmental transmission electron microscope. The ASLSs exhibit a core-shell structure with a Li core and a Li2 CO3 shell. In ambient air, the ASLSs do not react with moisture and maintain their core-shell structures. Furthermore, the ASLSs can be used as anodes in lithium-ion batteries, and they exhibit similar electrochemical behavior to metallic Li, indicating that the surface Li2 CO3 layer is a good Li+ ion conductor. The air stability of the ASLSs is attributed to the surface Li2 CO3 layer, which is barely soluble in water and does not react with oxygen and nitrogen in air at room temperature, thus passivating the Li core.

In Situ Imaging the Oxygen Reduction Reactions of Solid State Na-O2 Batteries with CuO Nanowires as the Air Cathode.

We report real time imaging of the oxygen reduction reactions (ORRs) in all solid state sodium oxygen batteries (SOBs) with CuO nanowires (NWs) as the air cathode in an aberration-corrected environmental transmission electron microscope under an oxygen environment. The ORR occurred in a distinct two-step reaction, namely, a first conversion reaction followed by a second multiple ORR. In the former, CuO was first converted to Cu2O and then to Cu; in the latter, NaO2 formed first, followed by its disproportionation to Na2O2 and O2. Concurrent with the two distinct electrochemical reactions, the CuO NWs experienced multiple consecutive large volume expansions. It is evident that the freshly formed ultrafine-grained Cu in the conversion reaction catalyzed the latter one-electron-transfer ORR, leading to the formation of NaO2. Remarkably, no carbonate formation was detected in the oxygen cathode after cycling due to the absence of carbon source in the whole battery setup. These results provide fundamental understanding into the oxygen chemistry in the carbonless air cathode in all solid state Na-O2 batteries.