Full Discharge Capacity Research Articles

Dual functional mesoporous silica colloidal electrolyte for lithium-oxygen batteries

Dual functional mesoporous silica (mSiO2) colloidal electrolytes are promising to protect lithium anode and accelerate the reaction kinetics on cathode for lithium-oxygen batteries (LOBs).In this work, we achieved a significantly extended battery life (from 55 to 328 cycles) of LOB by using mSiO2 with a concentration of 80 mg L−1 in the colloidal electrolyte, compared with the one using conventional LiClO4/DMSO electrolyte. The rate performance and full-discharge capacity are also dramatically enhanced. The as-synthesized mSiO2 has a special ordered hexagonal mesoporous structure, with a high specific surface area of 1016.30 m2/g, which can form a stable colloid after mixing with 1.0 M LiClO4/DMSO. The side reactions of Li stripping/plating are suppressed, thus the cycling life performance of LOB is enhanced by relieving the attack of superoxide intermediates. The co-deposition of mesoporous mSiO2 and Li2O2 also effectively accelerated the decomposition of the discharge product by promoting the mass transfer at the cathode. This investigation of suppressing side reactions using non-aqueous electrolytes will shed a new light on the design and development of novel lithium metal batteries.

Facile preparation of glycine-based mesoporous graphitic carbons with embedded cobalt nanoparticles

A simple route has been developed for the preparation of mesoporous graphitic carbons with embedded cobalt nanoparticles just using glycine as a nitrogen source, cobalt nitrate and distilled water. After heating the mixture to 300 °C under magnetic stirring, a dry solid product was obtained, which was then carbonized at 900 ºC under argon atmosphere. Changing the glycine/Co molar ratio allowed controlling the size of the cobalt particles and their dispersion in the carbon matrix, the porosity of the carbon and its graphitic character. The carbon–metal composites obtained were tested as oxygen cathodes in Li–O2 batteries. Cells assembled exhibited a full discharge capacity up to 2.19 mAh cm−2 at a current of 0.05 mA cm−2 and over 39 cycles at a cutoff capacity of 0.5 mAh cm−2. This work provides a green, feasible and simple way to prepare mesoporous graphitic carbons with embedded cobalt nanoparticles without involving templates.Graphical abstract

A High‐Performance Solid‐State Na–CO2 Battery with Poly(Vinylidene Fluoride‐co‐Hexafluoropropylene)−Na3.2Zr1.9Mg0.1Si2PO12 Electrolyte

The recovery and utilization of carbon dioxide (CO2) is the key to achieve the targets of peak carbon dioxide emissions and carbon neutrality. The Na‐CO2 battery made with cheap alkali metal sodium and greenhouse gas CO2 is an effective strategy to consume CO2 and store clean renewable energy. However, the liquid electrolyte volatilization in the open battery system and inevitable dendrite growth restrict the application of Na‐CO2 batteries. In this work, magnesium‐doped Na3Zr2Si2PO12 (NZSP) was studied as a solid electrolyte for solid‐state Na‐CO2 batteries. The ionic conductivity of Na3.2Zr1.9Mg0.1Si2PO12 reaches 1.16 mS cm−1 at room temperature by replacing Zr ions in Na3Zr2Si2PO12 with Mg ions, and the structural changes are analyzed by neutron powder diffraction. The composite electrolyte consisting of highly conductive Na3.2Zr1.9Mg0.1Si2PO12 and high processability poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) is utilized for the first time to assemble a solid‐state Na‐CO2 battery. The cell shows a full discharge capacity of 7720 mAh g−1 at 200 mA g−1. The middle gap voltage is lower than 2 V after 120 cycles at 200 mA g−1 and at a cut‐off capacity of 500 mAh g−1. This work demonstrates a promising strategy to design high‐performance solid‐state Na‐CO2 batteries.

Protecting lithium anode with ionic liquid modified poly(vinylidene fluoride) single ion conducting separators for iodide-assisted lithium oxygen batteries

Redox mediators (RMs) have been reported to effectively promote the sluggish decomposition of discharge products in Li-O2 batteries (LOBs), however, the attack of the oxidized RMs and other harmful species remains challenging to Li anodes. Herein, an ionic liquid modified sulfonated poly(vinylidene fluoride) (MSP) single lithium-ion conducting membrane was fabricated, which only allows the transfer of Li+ and blocks the passthrough of anions and other molecules. The ionic liquid modification apparently strengthened the conductivity of the membrane without losing its impermeability and ionic selectivity. The utility of the MSP separator significantly extended the cycle life of the LOB in comparison to the cell using a glass fiber separator, from 60 to 210 rounds at the 1.0 A g−1 and the capacity of 1000 mAh g−1. The rate performance was obviously enhanced from 44, 31 and 23 cycles to152, 129 and 107 cycles at the rates of 2.0, 3.0 and 5.0 A g−1, respectively. The full-discharge capacity was also enlarged from 3700 to 17,000 mAh g−1. The MSP separator enables the iodide-assisted cathode process and improves the deposition/dissolution of the Li anode, which are essential for the performance enhancement of aprotic LOBs.

Unveiling the Role of Tetrabutylammonium and Cesium Bulky Cations in Enhancing Na‐O2 Battery Performance

AbstractThe use of two types of bulky cations, tetrabutylammonium (TBA+) and Cs+, as electrolyte additives in Na‐O2 batteries is investigated. These cations facilitate the stabilization of sodium superoxide in the electrolyte, promoting the solution‐mediated pathway. Both the addition of TBA+ and Cs+ favor the growth of larger NaO2 cubes than in the case of the electrolyte containing only sodium salt, particularly in the case of Cs+. In terms of full discharge capacity, both additives lead to an increase in the discharge capacity, which is greater in Cs+ (50% enhancement). TBA+ also provides an improved stabilization of superoxide; nevertheless, the interaction is not as strong as in the case of Cs+ due to the steric hindrance set by the alkyl groups. The presence of these additives not only affects the NaO2 formation mechanism, but also influences the nature of the solid electrolyte interphase. The presence of Cs+ generates a more stable solid‐electrolyte interphase, which increases the cycle life of Na‐O2 batteries. Overall, new insights are provided to control the growth of the discharge products, modify the oxygen reduction reaction mechanism, and protect the Na metal anode surface by adding bulky monovalent cations in the electrolyte formulation.

Artificial Solid‐Electrolyte Interphase and Bamboo‐like N‐doped Carbon Nanotube Enabled Highly Rechargeable K‐CO2 Batteries

AbstractMetal‐CO2 (Metal = Li, Na, K) batteries demonstrate an attractive strategy for utilizing the excessively released CO2 emissions into electrochemical energy storage devices. Among them, K‐CO2 batteries represent a promising energy storage system owing to high potential (2.48 V), high energy density, and earth‐abundant K resources. The cycle stability and electrochemical mechanism are still far beyond satisfactory because of the active potassium metal, although the first rechargeable K‐CO2 battery has been reported very recently. Herein, a high‐performance K‐CO2 battery is fabricated using passivated K anodes with artificial surface film and N‐doped carbon nanotubes cathodes. The battery shows high specific full discharge capacity (9436 mAh g−1), good rate capability with small overpotential gap (0.81 V at 50 mA g−1), and long cycle life (450 cycles or 3100 h with a curtailing capacity of 500 mAh g−1). The reaction of 3CO2 + 4K ⇋ 2K2CO3 + C reversibly occurs in the charge/discharge processes. Moreover, the assembled fiber‐shaped battery demonstrates a long operation time of 57 h and stable output under different bending conditions. This work provides an option for the possible recycling utilization of the CO2 in future space exploration.

Effects of Ti substitution for Zr on the electrochemical characteristics and structure of AB2-type Laves-phase alloys as metal hydride anodes

The structural composition and electrochemical capacity of four AB2 Laves-type intermetallic alloys with various Ti/Zr ratios (TixZr1−xLa0.03Ni1.2Mn0.7V0.12Fe0.12, x = 0.12, 0.15, 0.18, and 0.22) were investigated in this study. The alloys were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. These data revealed the coexistence of the main phase of the C15-type FCC Laves-type AB2 compounds with a secondary La–Ni intermetallic that was present in minor amounts. Increasing the Ti substitution for Zr caused the gradual shrinkage of the unit cells of the C15 phase. The neutron powder diffraction studies demonstrated that in the trihydride (Ti, Zr, V)(Ni, Mn, Fe, V)2D3.2, D atoms filled A2B2 tetrahedra, whereas V atoms occupied not only conventional 16d sites but also partially replaced Zr/Ti at 8a sites. All studied alloys showed similar activation behaviors, wherein four cycles were required to realize the highest electrochemical capacity of the anodes. The Ti12/Zr88 alloy demonstrated excellent full discharge capacity that reached 466 mAh/g. The Ti22/Zr78 alloy electrode exhibited good cycling stability (retention rate of ~71%) after 500 cycles and a superior high-rate discharge capability (retention rate of ~71%) at a discharge current density of 400 mA/g. The cycling of the Ti22/Zr78 alloy electrode was studied by electrochemical impedance spectroscopy (EIS) to understand the reasons for the deterioration of cycling capacity, which was related with the pulverization of the alloys and increase in irreversible capacity.

Topological Defect‐Rich Carbon as a Metal‐Free Cathode Catalyst for High‐Performance Li‐CO2 Batteries

AbstractExploration of the highly efficient bi‐functional catalysts toward the reduction of CO2 and decomposition of Li2CO3 at the cathode is the key for high‐performance Li‐CO2 batteries. Herein, topological defect‐rich graphene (TDG) based materials are developed as metal‐free cathodes for Li‐CO2 batteries, presenting an unprecedented full discharge capacity of over 69 000 mA h g−1 at the current density of 0.5 A g−1, a relatively small voltage gap of 1.87 V (Li/Li+) even at an extremely high current density of 2.0 A g−1, and an excellent long‐term stable cycle life of up to 600 cycles at 1.0 A g−1. The outstanding performance of Li‐CO2 batteries with the TDG cathodic electrocatalyst can be attributed to the introduction of topological defects in the carbon skeleton, providing sufficient active sites for CO2 reduction and evolution to facilitate the formation/decomposition of Li2CO3 during the discharging/charging process. The density functional theory calculations reveal the superiority of the negatively charged C atoms in topological defects as the adsorption for CO2 molecules and the activation sites for the decomposition of Li2CO3, and that the heterocyclic pentagon ring (C5) has a relatively low theoretical potential gap (1.01 V) during the charge and discharge processes.

Rechargeable LiCO2 Batteries with Graphdiyne as Efficient Metal‐Free Cathode Catalysts

AbstractA rechargeable LiCO2 battery is one of the promising power sources for utilizing the greenhouse gas CO2 in a sustainable approach. However, highly efficient catalysts for reversible formation/decomposition of insulating discharge product, Li2CO3, are the main challenge, which can boost the cycle stability. Herein, 2D single‐atom‐thick graphdiyne (GDY) with abundant acetylenic bond sites is prepared by a bottom‐up cross‐coupling reaction strategy and used as metal‐free catalysts for reversible LiCO2 batteries. The prepared GDY has a rich diacetylenic unit and atomic‐level in‐plane pores in the network, which can chemically adsorb the CO2 molecules and easily promote the Li+ diffusion and thereby resulting in uniform nucleation and reversible formation/decomposition of the discharge product. The GDY hybrid cathodes show a small overpotential gap of 1.4 V at a current density of 50 mA · g−1, a high full discharge capacity of 18 416 mAh · g−1 at 100 mA · g−1, and outstanding long‐term stability of 158 cycles at 400 mA · g−1 with a curtailing capacity of 1000 mAh · g−1. Furthermore, a flexible belt‐shaped LiCO2 battery is fabricated as a proof of concept with a high gravimetric energy density of 165.5 Wh · kg−1 (based on the mass of the whole device) as well as excellent mechanical flexibility.

Enhancement of the electrochemical performance of free-standing graphene electrodes with manganese dioxide and ruthenium nanocatalysts for lithium-oxygen batteries

Hybrid ternary Graphene/Ruthenium/α-MnO2 (rGO/Ru/α-MnO2) flexible nanocomposite cathodes were fabricated via controlling both reduction and vacuum filtration processes without using a binder and conductive carbon additives for flexible Li-air battery system. To compare the electrochemical performance of the Graphene/Ruthenium/α-MnO2 cathodes, bare rGO and rGO/Ru free-standing cathodes were also manufactured. rGO cathodes with well-dispersed α-MnO2 nanowires and ruthenium nanoparticles were successfully synthesized and shown to dramatically increase (decrease) oxygen reduction (evolution) reactions. The enhancement on the electrochemical performance of the synthesized cathodes was attributed not only to catalysis effect of ruthenium and α-MnO2 but also well-stacked morphology of the nanocomposite architecture which enables increased oxygen flow between the layers and, hence boosted reaction kinetics.Physical characterization of the cathodes was carried out using FESEM, EDS, TEM, XRD, XPS and Raman spectroscopy. The discharge product of the cathodes was also evaluated using TEM and XPS. Electrochemical performances of the cathodes were evaluated by means of CV, EIS, galvanostatic charge-discharge and electrochemical cycling tests. Thanks to the synergetic effect of Ruthenium and α-MnO2 catalysts, our ternary rGO/Ru/α-MnO2 cathodes were shown to serve full discharge capacity of 2225 mAh/g while rGO/Ru can deliver only 1670 mAh/g. Besides, the cycling stability of the ternary rGO/Ru/α-MnO2 cathodes was shown for 50 cycles at 650 mAh/g capacity limited tests in assembled Li–O2 batteries.

Impact of a Gold Nanocolloid Electrolyte on Li2O2 Morphology and Performance of a Lithium-Oxygen Battery.

Aprotic lithium-oxygen batteries currently suffer from poor cyclic stability and low achievable energy density. Herein, gold nanoparticles capped with mercaptosuccinic acid are dispersed in 1.0 M LiClO4/dimethyl sulfoxide (DMSO) as a novel electrolyte for lithium-oxygen batteries. Morphological and electrochemical analyses indicate that film-like amorphous lithium peroxide is formed using the gold nanocolloid electrolyte instead of bulk crystals in battery discharging, which apparently increases the conductivity and accelerates the decomposition kinetics of discharge products in recharging, accompanied by the release of incorporated gold nanoparticles with the decomposition of lithium peroxide into the electrolyte. Experiments and theoretical calculations further demonstrate that the suspended gold nanoparticles in the electrolyte can adsorb some intermediates generated by an oxygen reduction reaction, which effectively alleviates the cleavage of the electrolyte and impedes the corrosion of the lithium anode. As a result, the life span of lithium-oxygen batteries is dramatically increased from 55 to 438 cycles, and the rate performance and full-discharge capacity are also massively enhanced. The battery failure is attributed to the degradation of gold nanocolloid electrolytes, and further studies on improvement of colloid stability during battery cycling are underway.

Effects of V substitution and annealing on Zr-based AB2 alloys as anode material of metal hydride batteries

Present paper investigates Ti0.25Zr0.75Ni1.35-xMn0.65Vx (x = 0, 0.05, 0.1, and 0.15) alloys as anode active materials of metal hydride batteries. The AB2 Laves-type alloys are prepared using arc melting and annealing. The as-cast alloys contain the major C15 and/or C14 intermetallic compounds together with the Ti–Ni and Zr–Ni secondary phases. The annealing promotes the homogeneity of the alloys and dismisses the non-Laves phases. As the V contents increase, the C15-type Laves phase transforms to the C14 structure. In addition, the unit cells of the Laves phase increase as the V contents in the alloys increase. All the studied alloy electrodes reach their maximum discharge capacities during the first 10 activation cycles. After charge/discharge 100 cycles at 300 mAg−1, the discharge capacity retentions of all the studied alloy electrodes keep more than 75%. Annealing treatment and V substitution increase the full discharge capacity from ~230 mAg−1 for N1 alloy to ~430 mAhg−1 for A4 alloy. The synthetic effects between V substitution and annealing are studied on improving the phase structure and the electrochemical properties of AB2-type Laves phase alloys.

Highly dispersed silver nanoparticles for performance-enhanced lithium oxygen batteries

Aprotic lithium-oxygen batteries possess ultrahigh energy density but suffer from the sluggish decomposition of discharge product, quick depletion of Li anode and cleavage of electrolyte, in close association with oxygen reduction reaction at the cathode. Herein, highly dispersed silver nanoparticles are used to enhance the lithium-oxygen battery with 1.0 M lithium perchlorate in dimethyl sulfoxide. It is observed that film-like amorphous lithium peroxide is formed through surface pathway instead of bulk crystals, due to the incorporation of silver nanoparticles dispersed in the electrolyte, which subsequently accelerates the decomposition of the discharge product by offering more active sites and improved conductivity. The released silver nanoparticles after battery charging can be re-used in the following cycles. Experiments and theoretical calculation further indicate that the suspended silver nanoparticles can adsorb the soluble oxygen reduction intermediates, which are responsible for the alleviation of oxidative cleavage of electrolyte and corrosion of lithium anode. The lifespan of lithium oxygen batteries is therefore significantly extended from 55 to 390 cycles, and the rate performance and full-discharge capacity are also largely enhanced. The battery failure is attributed to the coalescence and growth of silver nanoparticles in the electrolyte, and further improvement on colloid stability is underway.

Biologically synthesized TiO2 nanoparticles and their application as lithium-air battery cathodes

Electrocatalysts represent a sustainable solution for lithium-air batteries by eliminating side reactions. Herein, TiO2 nanoparticles were biosynthesized via the green method and investigated as air cathodes for lithium-air batteries. TiO2 nanoparticles were also synthesized via the facile sol-gel method to compare the efficiency of this green method. The flower extract of Matricaria chamomilla was utilized to biosynthesize the TiO2 nanoparticles. The particle size of the biosynthesized TiO2 nanoparticles was further controlled by manipulating the pH of the solution. In this way, the influence of pH on the nanoparticle’s properties could be evaluated. The phase structures, surface morphology, and elemental composition of the synthesized TiO2 nanoparticles were characterized as well. Additionally, the TiO2 cathodes were prepared on nickel foam, and their electrochemical performances were evaluated via an ECC-Air test cell using cyclic voltammetry, electrochemical impedance measurements, and galvanostatic charge-discharge tests. Consequently, the Bio-TiO2 air cathode showed a full discharge capacity of 2000 mAh g−1 and a specific capacity of 500 mAh g−1 for 30 stable cycles.

The Stabilization Effect of CO2 in Lithium–Oxygen/CO2 Batteries

AbstractThe lithium (Li)–air battery has an ultrahigh theoretical specific energy, however, even in pure oxygen (O2), the vulnerability of conventional organic electrolytes and carbon cathodes towards reaction intermediates, especially O2−, and corrosive oxidation and crack/pulverization of Li metal anode lead to poor cycling stability of the Li‐air battery. Even worse, the water and/or CO2 in air bring parasitic reactions and safety issues. Therefore, applying such systems in open‐air environment is challenging. Herein, contrary to previous assertions, we have found that CO2 can improve the stability of both anode and electrolyte, and a high‐performance rechargeable Li–O2/CO2 battery is developed. The CO2 not only facilitates the in situ formation of a passivated protective Li2CO3 film on the Li anode, but also restrains side reactions involving electrolyte and cathode by capturing O2−. Moreover, the Pd/CNT catalyst in the cathode can extend the battery lifespan by effectively tuning the product morphology and catalyzing the decomposition of Li2CO3. The Li–O2/CO2 battery achieves a full discharge capacity of 6628 mAh g−1 and a long life of 715 cycles, which is even better than those of pure Li–O2 batteries.

The Stabilization Effect of CO2 in Lithium-Oxygen/CO2 Batteries.

The lithium (Li)-air battery has an ultrahigh theoretical specific energy, however, even in pure oxygen (O2 ), the vulnerability of conventional organic electrolytes and carbon cathodes towards reaction intermediates, especially O2 - , and corrosive oxidation and crack/pulverization of Li metal anode lead to poor cycling stability of the Li-air battery. Even worse, the water and/or CO2 in air bring parasitic reactions and safety issues. Therefore, applying such systems in open-air environment is challenging. Herein, contrary to previous assertions, we have found that CO2 can improve the stability of both anode and electrolyte, and a high-performance rechargeable Li-O2 /CO2 battery is developed. The CO2 not only facilitates the in situ formation of a passivated protective Li2 CO3 film on the Li anode, but also restrains side reactions involving electrolyte and cathode by capturing O2 - . Moreover, the Pd/CNT catalyst in the cathode can extend the battery lifespan by effectively tuning the product morphology and catalyzing the decomposition of Li2 CO3 . The Li-O2 /CO2 battery achieves a full discharge capacity of 6628 mAh g-1 and a long life of 715 cycles, which is even better than those of pure Li-O2 batteries.

Understanding the Dual-Phase Synergy Mechanism in Mn2O3-Mn3O4 Catalyst for Efficient Li-CO2 Batteries.

Rechargeable Li-CO2 batteries have been receiving intense interest because of their high theoretical energy density and environmentally friendly CO2 fixation ability. However, due to the sluggish CO2 reduction/evolution reaction (CRR/CER) kinetics, the current Li-CO2 batteries still suffer from severe polarization and poor cycling stability. Herein, we designed and in situ synthesized sea urchinlike Mn2O3-Mn3O4 nanocomposite and explored the synergistic effect between Mn2O3 and Mn3O4 during charge-discharge process in Li-CO2 batteries. It is found that Mn3O4 can effectively promote the kinetics of CRR process, and Mn2O3 can induce the nucleation of Li2CO3 and promote its decomposition (CER). Benefiting from the dual-phase synergy, the Mn2O3-Mn3O4 cathode combines the respective catalytic advantages of the both and delivers a high full discharge capacity of 19 024 mAh g-1, a low potential gap of 1.24 V, and durable cycling stability (1380 h) at a current density of 100 mA g-1. Moreover, based on experimental results and density functional theory (DFT) calculations, a charge-discharge process model of the Mn2O3-Mn3O4 cathode was established to display the electrochemical reaction mechanism. We hope that this design strategy can encourage further studies for efficient cathode catalysts to accelerate the practical application of Li-CO2 batteries and even the metal-air batteries.

Rechargeable Na–SO2Battery with Ethylenediamine Additive in Ether‐Based Electrolyte

AbstractRechargeable metal–SO2batteries have drawn tremendous attention because it can accelerate SO2fixation/utilization and offer high energy density. Herein, a rechargeable Na–SO2battery based on an ether‐based liquid electrolyte with an ethylenediamine (EDA) additive is realized via the reversible formation/decomposition of Na2S2O4. Experimental investigations reveal that the EDA additive provides three benefits by simultaneously decreasing the overall electrode polarization, increasing the full discharge capacity, and improving battery cyclability. At a current density of 250 mA g−1, the full discharge capacity of the battery with the EDA additive is more than twice of a similar system in the absence of EDA. In addition to the significantly enhanced capacity, the as‐assembled Na–SO2battery demonstrates excellent cyclic stability after 200 cycles, which is equivalent to a total duration of 1600 h. Moreover, the corrosion resistance of Na anode is strengthened with the aid of EDA in the SO2‐containing liquid electrolyte. This work will pave the way for Na–SO2batteries as a promising battery technology toward both pollutant gas utilization and energy storage.

Spinel Zinc Cobalt Oxide (ZnCo2O4) Porous Nanorods as a Cathode Material for Highly Durable Li-CO2 Batteries.

Li-CO2 batteries are of great interest among researchers due to their high energy density and utilization of the greenhouse gas CO2 to produce energy. However, several shortcomings have been encountered in the practical applications of Li-CO2 batteries, among which their poor cyclability and high charge overpotential necessary to decompose the highly insulating discharge product (Li2CO3) are the most important. Herein, the spinel zinc cobalt oxide porous nanorods with carbon nanotubes (ZnCo2O4@CNTs) composite is employed as a cathode material in Li-CO2 batteries to improve the latter's cycling performance. The ZnCo2O4@CNT cathode-based Li-CO2 battery exhibited a full discharge capacity of 4275 mAh g-1 and excellent cycling performance over 200 cycles with a charge overpotential below 4.3 V when operated at a current density of 100 mA g-1 and fixed capacity of 500 mAh g-1. The superior performance of the ZnCo2O4@CNT cathode composite was attributed to the synergistic effects of ZnCo2O4 and CNT. The highly porous ZnCo2O4 nanorod structures in the ZnCo2O4@CNT catalyst showed enhanced catalytic activity/stability, which effectively promoted CO2 diffusion during the discharging process and accelerated Li2CO3 decomposition at a low charge overpotential.

Metal–organic framework-derived MnO/CoMn2O4@N–C nanorods with nanoparticle interstitial decoration in core@shell structure as improved bifunctional electrocatalytic cathodes for Li–O2 batteries

Core@shell-structured, hierarchically porous manganese oxide/cobalt manganite@nitrogen-doped carbon (MnO/CoMn2O4@N–C) nanorods with interstitially decorated CoMn2O4 nanoparticles are synthesized via one-step carbonization of metal–organic framework (MOF)-coated α˗manganese oxide (α-MnO2@ZIF-67) nanorods and are evaluated as bifunctional electrocatalytic cathodes for Li–O2 batteries (LOBs) to improve the bifunctionality, specific discharge capacity, and cyclability of α˗MnO2 nanorod cathode-based LOBs. The MnO/CoMn2O4@N–C nanorods feature a MnO nanorod core with CoMn2O4 nanoparticle interstitial decoration, both coated by an N–C conductive shell. The MnO core renders Mn active sites and oxygen vacancies, while the CoMn2O4 interstitial decoration gives additional Mn, Co active sites, thereby enhancing bifunctional electrocatalytic ORR–OER. The N–C shell increases electronic conductivity, hierarchical porosity, specific surface area, and protects the core and interstitial decoration against lithium peroxide (Li2O2) passivation. The improved structural features allow the MnO/CoMn2O4@N–C nanorod cathode-based LOB cells to exhibit superior full specific discharge capacity of 8,625 mAh·g−1 and cyclability of 48 discharge–charge cycles at 200 mA·g−1 specific current and 2000 mAhg−1 limited specific discharge capacity compared to their α˗MnO2 nanorod counterparts. An ORR–OER mechanism is proposed to describe the interesting formation of particle- and film-type Li2O2 deposits at different cycles for the MnO/CoMn2O4@N–C nanorod cathodes. Such MOF-derived, interstitial nanoparticle-decorated nanoarchitectures can lead to high-performance tunable bifunctional electrocatalysts.