Strategies to improve the ionic conductivity of quasi-solid-state electrolytes based on metal-organic frameworks.

The low ionic conductivity of quasi-solid-state electrolytes (QSSEs) at ambient temperature is a barrier to the development of solid-state batteries (SSBs). Conversely, metal-organic frameworks (MOFs) with porous structure and metal sites show great potential for the fabrication of QSSEs. Numerous studies have proven that the structure and functional groups of MOFs could significantly impact the ionic conductivity of QSSEs based on MOFs (MOFs-QSSEs). This review introduces the transport mechanism of lithium ions in various MOFs-QSSEs, and then analyses how to construct an effective and consistent lithium ions pathway from the perspective of MOFs modification. It is shown that the ion conductivity could be enhanced by modifying the morphology and functional groups, as well as applying amorphous MOFs. Lastly, some issues and future perspectives for MOFs-QSSEs are examined. The primary objective of this review is to enhance the comprehension of the mechanisms and performance optimization methods of MOFs-QSSEs. Consequently, this would guide the design and synthesis of QSSEs with high ionic conductivity, and ultimately enhance the performance of commercial SSBs.

A lithium-oxygen battery based on lithium superoxide.

Batteries based on sodium superoxide and on potassium superoxide have recently been reported. However, there have been no reports of a battery based on lithium superoxide (LiO2), despite much research into the lithium-oxygen (Li-O2) battery because of its potential high energy density. Several studies of Li-O2 batteries have found evidence of LiO2 being formed as one component of the discharge product along with lithium peroxide (Li2O2). In addition, theoretical calculations have indicated that some forms of LiO2 may have a long lifetime. These studies also suggest that it might be possible to form LiO2 alone for use in a battery. However, solid LiO2 has been difficult to synthesize in pure form because it is thermodynamically unstable with respect to disproportionation, giving Li2O2 (refs 19, 20). Here we show that crystalline LiO2 can be stabilized in a Li-O2 battery by using a suitable graphene-based cathode. Various characterization techniques reveal no evidence for the presence of Li2O2. A novel templating growth mechanism involving the use of iridium nanoparticles on the cathode surface may be responsible for the growth of crystalline LiO2. Our results demonstrate that the LiO2 formed in the Li-O2 battery is stable enough for the battery to be repeatedly charged and discharged with a very low charge potential (about 3.2 volts). We anticipate that this discovery will lead to methods of synthesizing and stabilizing LiO2, which could open the way to high-energy-density batteries based on LiO2 as well as to other possible uses of this compound, such as oxygen storage.

In Situ Formed Ir3Li Nanoparticles as Active Cathode Material in Li-Oxygen Batteries.

Lithium-oxygen (Li-O2) batteries are a promising class of rechargeable Li batteries with a potentially very high achievable energy density. One of the major challenges for Li-O2 batteries is the high charge overpotential, which results in a low energy efficiency. In this work size-selected subnanometer Ir clusters are used to investigate cathode materials that can help control lithium superoxide formation during discharge, which has good electronic conductivity needed for low charge potentials. It is found that Ir particles can lead to lithium superoxide formation as the discharge product with Ir particle sizes of ∼1.5 nm giving the lowest charge potentials. During discharge these 1.5 nm Ir nanoparticles surprisingly evolve to larger ones while incorporating Li to form core-shell structures with Ir3Li shells, which probably act as templates for growth of lithium superoxide during discharge. Various characterization techniques including DEMS, Raman, titration, and HRTEM are used to characterize the LiO2 discharge product and the evolution of the Ir nanoparticles. Density functional calculations are used to provide insight into the mechanism for formation of the core-shell Ir3Li particles. The in situ formed Ir3Li core-shell nanoparticles discovered here provide a new direction for active cathode materials that can reduce charge overpotentials in Li-O2 batteries.

Insight into the Catalytic Mechanism of Bimetallic Platinum-Copper Core-Shell Nanostructures for Nonaqueous Oxygen Evolution Reactions.

The oxygen evolution reaction (OER) plays a critical role in multiple energy conversion and storage applications. However, its sluggish kinetics usually results in large voltage polarization and unnecessary energy loss. Therefore, designing efficient catalysts that could facilitate this process has become an emerging topic. Here, we present a unique Pt-Cu core-shell nanostructure for catalyzing the nonaqueous OER. The catalysts were systematically investigated with comprehensive spectroscopic techniques, and applied in nonaqueous Li-O2 electrochemical cells, which exhibited dramatically reduced charging overpotential (<0.2 V). The superior performance is explained by the robust Cu(I) surface sites stabilized by the Pt core in the nanostructure. The insights into the catalytic mechanism of the unique Pt-Cu core-shell nanostructure gained in this work are expected to serve as a guide for future design of other nanostructured bimetallic OER catalysts.

Study on the Catalytic Activity of Noble Metal Nanoparticles on Reduced Graphene Oxide for Oxygen Evolution Reactions in Lithium-Air Batteries.

Among many challenges present in Li-air batteries, one of the main reasons of low efficiency is the high charge overpotential due to the slow oxygen evolution reaction (OER). Here, we present systematic evaluation of Pt, Pd, and Ru nanoparticles supported on rGO as OER electrocatalysts in Li-air cell cathodes with LiCF3SO3-tetra(ethylene glycol) dimethyl ether (TEGDME) salt-electrolyte system. All of the noble metals explored could lower the charge overpotentials, and among them, Ru-rGO hybrids exhibited the most stable cycling performance and the lowest charge overpotentials. Role of Ru nanoparticles in boosting oxidation kinetics of the discharge products were investigated. Apparent behavior of Ru nanoparticles was different from the conventional electrocatalysts that lower activation barrier through electron transfer, because the major contribution of Ru nanoparticles in lowering charge overpotential is to control the nature of the discharge products. Ru nanoparticles facilitated thin film-like or nanoparticulate Li2O2 formation during oxygen reduction reaction (ORR), which decomposes at lower potentials during charge, although the conventional role as electrocatalysts during OER cannot be ruled out. Pt-and Pd-rGO hybrids showed fluctuating potential profiles during the cycling. Although Pt- and Pd-rGO decomposed the electrolyte after electrochemical cycling, no electrolyte instability was observed with Ru-rGO hybrids. This study provides the possibility of screening selective electrocatalysts for Li-air cells while maintaining electrolyte stability.

Pd nanoparticles on ZnO-passivated porous carbon by atomic layer deposition: an effective electrochemical catalyst for Li-O2 battery.

Uniformly dispersed Pd nanoparticles on ZnO-passivated porous carbon were synthesized via an atomic layer deposition (ALD) technique, which was tested as a cathode material in a rechargeable Li-O2 battery, showing a highly active catalytic effect toward the electrochemical reactions-in particular, the oxygen evolution reaction. Transmission electron microscopy (TEM) showed discrete crystalline nanoparticles decorating the surface of the ZnO-passivated porous carbon support in which the size could be controlled in the range of 3-6 nm, depending on the number of Pd ALD cycles performed. X-ray absorption spectroscopy (XAS) at the Pd K-edge revealed that the carbon-supported Pd existed in a mixed phase of metallic palladium and palladium oxide. The ZnO-passivated layer effectively blocks the defect sites on the carbon surface, minimizing the electrolyte decomposition. Our results suggest that ALD is a promising technique for tailoring the surface composition and structure of nanoporous supports for Li-O2 batteries.

Molecular-level insights into the reactivity of siloxane-based electrolytes at a lithium-metal anode.

A molecular-level understanding of the reactions that occur at the lithium-metal anode/electrolyte interphase is essential to improve the performance of Li-O(2) batteries. Experimental and computational techniques are applied to explore the reactivity of tri(ethylene glycol)-substituted trimethylsilane (1NM3), a siloxane-based ether electrolyte, at the lithium-metal anode. In situ/ex situ X-ray diffraction and Fourier-transform infrared spectroscopy studies provide evidence of the formation of lithium hydroxide and lithium carbonates at the anode upon gradual degradation of the metallic lithium anode and the solvent molecules in the presence of oxygen. Density functional calculations performed to obtain a mechanistic understanding of the reductive decomposition of 1NM3 indicate that the decomposition does not require any apparent barrier to produce lithium hydroxide and lithium carbonates when the reduced 1NM3 solvent molecules interact with the oxygen crossing over from the cathode. This study indicates that degradation may be more significant in the case of the 1NM3 solvent, compared to linear ethers such as tetraglyme or dioxalone, because of its relatively high electron affinity. Also, both protection of the lithium metal and prevention of oxygen crossover to the anode are essential for minimizing electrolyte and anode decomposition.

Synthesis of porous carbon supported palladium nanoparticle catalysts by atomic layer deposition: application for rechargeable lithium-O2 battery.

In this study, atomic layer deposition (ALD) was used to deposit nanostructured palladium on porous carbon as the cathode material for Li-O2 cells. Scanning transmission electron microscopy showed discrete crystalline nanoparticles decorating the surface of the porous carbon support, where the size could be controlled in the range of 2-8 nm and depended on the number of Pd ALD cycles performed. X-ray absorption spectroscopy at the Pd K-edge revealed that the carbon supported Pd existed in a mixed phase of metallic palladium and palladium oxide. The conformality of ALD allowed us to uniformly disperse the Pd catalyst onto the carbon support while preserving the initial porous structure. As a result, the charging and discharging performance of the oxygen cathode in a Li-O2 cell was improved. Our results suggest that ALD is a promising technique for tailoring the surface composition and structure of nanoporous supports in energy storage devices.

Compatibility of lithium salts with solvent of the non-aqueous electrolyte in Li-O2 batteries.

The stability of lithium salts, especially in the presence of reduced oxygen species, O2 and H2O (even in a small amount), plays an important role in the cyclability and capacity of Li-O2 cells. This combined experimental and computational study provides evidence that the stability of the electrolyte used in Li-O2 cells strongly depends on the compatibility of lithium salts with solvent. In the case of the LiPF6-1NM3 electrolyte, the decomposition of LiPF6 occurs in the cell as evidenced by in situ XRD, FT-IR and XPS analysis, which triggers the decomposition of 1NM3 solvent due to formation of HF from the decomposition of LiPF6. These reactions lead to degradation of the electrolyte and cause poor cyclability of the cell. The same reactions are not observed when LiTFSI and LiCF3SO3 are used as the lithium salts in 1NM3 solvent, or LiPF6 is used in TEGDME solvent.

Expression of PD-1/PD-L1 in peripheral blood and tumor tissues of patients with classical Hodgkin's lymphoma.

Significant biomarkers can predict and estimate the response to chemotherapy for different types of lymphoma. Classical Hodgkin's lymphoma (cHL) and peripheral T-cell lymphoma (PTCL) belong to different types of lymphoma, their prognosis is very different, programmed cell death receptor 1 (PD-1) and its ligand (PD-L1) have been studied in these 2 types of diseases. However, few studies have involved the difference in PD-1/PD-L1 levels between cHL and PTCL. To find out the difference and relevant clinical application value, we collected blood samples of 29 newly diagnosed cHL patients and 11 newly diagnosed PTCL ones. At the same time, tumor tissue paraffin sections of 13 patients with cHL were collected at the initial diagnosis. Flow cytometry, enzyme-linked immunosorbent assay, and immunohistochemical staining were used to detect PD-1/PD-L1 levels in peripheral blood T cells, plasma, and tumor tissues, and the relationship between the above results and clinical data of patients in patients with cHL were investigated. The levels of PD-1 on CD4+ T cells, PD-L1 on CD4+ T cells and PD-1 on CD8+ T cells in peripheral blood of cHL and PTCL patients were higher than those of healthy controls, the level of PD-1 in CD4+ T cells from peripheral blood was higher from cHL patients with stage III-IV (P = .0178), B symptoms (P = .0398), higher lactate dehydrogenase (P = .0056), higher international prognostic index score (P = .0349), and relapsed in later stages (P = .0306). The expression level of soluble PD-L1 (sPD-L1) from cHL (P < .001) and PTCL (P < .0001) patients was higher than that of the healthy control group, and there was higher sPD-L1 level in patients with higher international prognostic index scores (P = .0016). The dynamic detection of sPD-L1 showed that after 2 courses of chemotherapy, the sPD-L1 level in cHL patients with complete remission declined, but the level of sPD-L1 from patients with incomplete remission was not significantly changed (P > .05). In tumor tissues of cHL patients, PD-1(+) was 77%, PD-L1(+) was 69%, PD-1 and PD-L1 expression levels were high. Our results suggest that PD-1 levels in peripheral blood CD4+ T cells are helpful for the stage of disease in patients with cHL, and the dynamic detection of sPD-L1 level is helpful for the judgment of patients with cHL.

Exceptionally High Ionic Conductivity in Na3 P0.62 As0.38 S4 with Improved Moisture Stability for Solid-State Sodium-Ion Batteries.

A Na-ion solid-state electrolyte, Na3 P0.62 As0.38 S4 , is developed with an exceptionally high conductivity of 1.46 mS cm-1 at 25 °C and enhanced moisture stability. Dual effects of alloying element As (lattice expansion and a weaker AsS bond strength) are responsible for the superior conductivity. Improved moisture stability is regulated by shifting low-energy moisture reactions to high-energy ones due to As.

Holey two-dimensional transition metal oxide nanosheets for efficient energy storage.

Transition metal oxide nanomaterials are promising electrodes for alkali-ion batteries owing to their distinct reaction mechanism, abundant active sites and shortened ion diffusion distance. However, detailed conversion reaction processes in terms of the oxidation state evolution and chemical/mechanical stability of the electrodes are still poorly understood. Herein we explore a general synthetic strategy for versatile synthesis of various holey transition metal oxide nanosheets with adjustable hole sizes that enable greatly enhanced alkali-ion storage properties. We employ in-situ transmission electron microscopy and operando X-ray absorption structures to study the mechanical properties, morphology evolution and oxidation state changes during electrochemical processes. We find that these holey oxide nanosheets exhibit strong mechanical stability inherited from graphene oxide, displaying minimal structural changes during lithiation/delithiation processes. These holey oxide nanosheets represent a promising material platform for in-situ probing the electrochemical processes, and could open up opportunities in many energy storage and conversion systems.

Protocol of Electrochemical Test and Characterization of Aprotic Li-O2 Battery.

We demonstrate a method for electrochemical testing of an aprotic Li-O2 battery. An aprotic Li-O2 battery is made of a Li-metal anode, an aprotic electrolyte, and an O2-breathing cathode. The aprotic electrolyte is a solution of lithium salt with aprotic solvent; and porous carbon is commonly used as the cathode substrate. To improve the performance, an electrocatalyst is deposited onto the porous carbon substrate by certain deposition methods, such as atomic layer deposition (ALD) and wet-chemistry reaction. The as-prepared cathode materials are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray absorption near edge structure (XANES). A Swagelok-type cell, sealed in a glass chamber filled with pure O2, is used for the electrochemical test on a battery test system. The cells are tested under either capacity-controlled mode or voltage controlled mode. The reaction products are investigated by electron microscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, and Raman spectroscopy to study the possible pathway of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). This protocol demonstrates a systematic and efficient arrangement of routine tests of the aprotic Li-O2 battery, including the electrochemical test and characterization of battery materials.

Mesocarbon Microbead Carbon-Supported Magnesium Hydroxide Nanoparticles: Turning Spent Li-ion Battery Anode into a Highly Efficient Phosphate Adsorbent for Wastewater Treatment.

Phosphorus in water eutrophication has become a serious problem threatening the environment. However, the development of efficient adsorbents for phosphate removal from water is lagging. In this work, we recovered the waste material, graphitized carbon, from spent lithium ion batteries and modified it with nanostructured Mg(OH)2 on the surface to treat excess phosphate. This phosphate adsorbent shows one of the highest phosphate adsorption capacities to date, 588.4 mg/g (1 order of magnitude higher than previously reported carbon-based adsorbents), and exhibits decent stability. A heterogeneous multilayer adsorption mechanism was proposed on the basis of multiple adsorption results. This highly efficient adsorbent from spent Li-ion batteries displays great potential to be utilized in industry, and the mechanism study paved a way for further design of the adsorbent for phosphate adsorption.

The influence of large cations on the electrochemical properties of tunnel-structured metal oxides.

Metal oxides with a tunnelled structure are attractive as charge storage materials for rechargeable batteries and supercapacitors, since the tunnels enable fast reversible insertion/extraction of charge carriers (for example, lithium ions). Common synthesis methods can introduce large cations such as potassium, barium and ammonium ions into the tunnels, but how these cations affect charge storage performance is not fully understood. Here, we report the role of tunnel cations in governing the electrochemical properties of electrode materials by focusing on potassium ions in α-MnO2. We show that the presence of cations inside 2 × 2 tunnels of manganese dioxide increases the electronic conductivity, and improves lithium ion diffusivity. In addition, transmission electron microscopy analysis indicates that the tunnels remain intact whether cations are present in the tunnels or not. Our systematic study shows that cation addition to α-MnO2 has a strong beneficial effect on the electrochemical performance of this material.

Kinetic Study of Parasitic Reactions in Lithium-Ion Batteries: A Case Study on LiNi(0.6)Mn(0.2)Co(0.2)O2.

The side reactions between the electrode materials and the nonaqueous electrolytes have been the major contributor to the degradation of electrochemical performance of lithium-ion batteries. A home-built high-precision leakage current measuring system was deployed to investigate the reaction kinetics between the delithiated LiNi(0.6)Mn(0.2)Co(0.2)O2 and a conventional nonaqueous electrolyte. It was found that the rate of parasitic reaction had strong dependence on the upper cutoff potential of the cathode material. The kinetic data also indicated a change of reaction mode at about 4.5 V vs Li(+)/Li.

Binder-free V2O5 cathode for greener rechargeable aluminum battery.

This letter reports on the investigation of a binder-free cathode material to be used in rechargeable aluminum batteries. This cathode is synthesized by directly depositing V2O5 on a Ni foam current collector. Rechargeable aluminum coin cells fabricated using the as-synthesized binder-free cathode delivered an initial discharge capacity of 239 mAh/g, which is much higher than that of batteries fabricated using a cathode composed of V2O5 nanowires and binder. An obvious discharge voltage plateau appeared at 0.6 V in the discharge curves of the Ni-V2O5 cathode, which is slightly higher than that of the V2O5 nanowire cathodes with common binders. This improvement is attributed to reduced electrochemical polarization.

Effect of the size-selective silver clusters on lithium peroxide morphology in lithium-oxygen batteries.

Lithium-oxygen batteries have the potential needed for long-range electric vehicles, but the charge and discharge chemistries are complex and not well understood. The active sites on cathode surfaces and their role in electrochemical reactions in aprotic lithium-oxygen cells are difficult to ascertain because the exact nature of the sites is unknown. Here we report the deposition of subnanometre silver clusters of exact size and number of atoms on passivated carbon to study the discharge process in lithium-oxygen cells. The results reveal dramatically different morphologies of the electrochemically grown lithium peroxide dependent on the size of the clusters. This dependence is found to be due to the influence of the cluster size on the formation mechanism, which also affects the charge process. The results of this study suggest that precise control of subnanometre surface structure on cathodes can be used as a means to improve the performance of lithium-oxygen cells.

The effect of oxygen crossover on the anode of a Li-O(2) battery using an ether-based solvent: insights from experimental and computational studies.

Crosstown traffic: Further development of Li-O(2) batteries may eventually lead to their use in transportation applications. One problem that needs to be addressed is electrolyte decomposition, which has been partially mitigated by using ether- rather than carbonate-based solvents. The influence of oxygen crossover from the cathode to the anode on electrolyte, and lithium anode, decomposition in ether-based Li-O(2) batteries is investigated.

A nanostructured cathode architecture for low charge overpotential in lithium-oxygen batteries.

The lithium-oxygen battery, of much interest because of its very high-energy density, presents many challenges, one of which is a high-charge overpotential that results in large inefficiencies. Here we report a cathode architecture based on nanoscale components that results in a dramatic reduction in charge overpotential to ~0.2 V. The cathode utilizes atomic layer deposition of palladium nanoparticles on a carbon surface with an alumina coating for passivation of carbon defect sites. The low charge potential is enabled by the combination of palladium nanoparticles attached to the carbon cathode surface, a nanocrystalline form of lithium peroxide with grain boundaries, and the alumina coating preventing electrolyte decomposition on carbon. High-resolution transmission electron microscopy provides evidence for the nanocrystalline form of lithium peroxide. The new cathode material architecture provides the basis for future development of lithium-oxygen cathode materials that can be used to improve the efficiency and to extend cycle life.