Minimizing Undesired Side Reactions Induced by Nanoscale Conductive Carbon Enables Stable Cycling of Semi-Solid Li-Ion Full Batteries.

Semi-solid lithium-ion batteries (SSLIBs) based on "slurry-like" electrodes hold great promise to enable low-cost and sustainable energy storage. However, the development of the SSLIBs has long been hindered by the lack of high-performance anodes. Here the origin of low initial Coulombic efficiency (iCE, typically <60%) is elucidated in the graphite-based semi-solid anodes (in the non-flowing mode) and develop rational strategies to minimize the irreversible capacity loss. It is discovered that Ketjen black (KB), a nanoscale conductive additive widely used in SSLIB research, induces severe electrolyte decomposition during battery charge due to its large surface area and abundant surface defects. High iCEs up to 92% are achieved for the semi-solid graphite anodes by replacing KB with other low surface-area, low-defect conductive additives. A semi-solid full battery (LiFePO4 vs graphite, in the non-flowing mode) is further demonstrated with stable cycle performance over 100 cycles at a large areal capacity of 6 mAh cm-2 and a pouch-type semi-solid full cell that remains functional even when it is mechanically abused. This work demystifies the SSLIBs and provides useful physical insights to further improve their performance and durability.

Ultrafast Charge-Discharge Capable and Long-Life Na3.9 Mn0.95 Zr0.05 V(PO4 )3 /C Cathode Material for Advanced Sodium-Ion Batteries.

Na4 MnV(PO4 )3 /C (NMVP) has been considered an attractive cathode for sodium-ion batteries with higher working voltage and lower cost than Na3 V2 (PO4 )3 /C. However, the poor intrinsic electronic conductivity and Jahn-Teller distortion caused by Mn3+ inhibit its practical application. In this work, the remarkable effects of Zr-substitution on prompting electronic and Na-ion conductivity and also structural stabilization are reported. The optimized Na3.9 Mn0.95 Zr0.05 V(PO4 )3 /C sample shows ultrafast charge-discharge capability with discharge capacities of 108.8, 103.1, 99.1, and 88.0 mAh g-1 at 0.2, 1, 20, and 50 C, respectively, which is the best result for cation substituted NMVP samples reported so far. This sample also shows excellent cycling stability with a capacity retention of 81.2% at 1 C after 500 cycles. XRD analyses confirm the introduction of Zr into the lattice structure which expands the lattice volume and facilitates the Na+ diffusion. First-principle calculation indicates that Zr modification reduces the band gap energy and leads to increased electronic conductivity. In situ XRD analyses confirm the same structure evolution mechanism of the Zr-modified sample as pristine NMVP, however the strong ZrO bond obviously stabilizes the structure framework that ensures long-term cycling stability.

Insight into Ca-Substitution Effects on O3-Type NaNi1/3 Fe1/3 Mn1/3 O2 Cathode Materials for Sodium-Ion Batteries Application.

O3-type NaNi1/3 Fe1/3 Mn1/3 O2 (NaNFM) is well investigated as a promising cathode material for sodium-ion batteries (SIBs), but the cycling stability of NaNFM still needs to be improved by using novel electrolytes or optimizing their structure with the substitution of different elements sites. To enlarge the alkali-layer distance inside the layer structure of NaNFM may benefit Na+ diffusion. Herein, the effect of Ca-substitution is reported in Na sites on the structural and electrochemical properties of Na1-x Cax/2 NFM (x = 0, 0.05, 0.1). X-ray diffraction (XRD) patterns of the prepared Na1-x Cax/2 NFM samples show single α-NaFeO2 type phase with slightly increased alkali-layer distance as Ca content increases. The cycling stabilities of Ca-substituted samples are remarkably improved. The Na0.9 Ca0.05 Ni1/3 Fe1/3 Mn1/3 O2 (Na0.9 Ca0.05 NFM) cathode delivers a capacity of 116.3 mAh g-1 with capacity retention of 92% after 200 cycles at 1C rate. In operando XRD indicates a reversible structural evolution through an O3-P3-P3-O3 sequence of Na0.9 Ca0.05 NFM cathode during cycling. Compared to NaNMF, the Na0.9 Ca0.05 NFM cathode shows a wider voltage range in pure P3 phase state during the charge/discharge process and exhibits better structure recoverability after cycling. The superior cycling stability of Na0.9 Ca0.05 NFM makes it a promising material for practical applications in sodium-ion batteries.

Graphene-wrapped yolk-shell of silica-cobalt oxide as high-performing anode for lithium-ion batteries.

Silica (SiO2) shows promise as anode material for lithium-ion batteries due to its low cost, comparable lithium storage discharge potential and high theoretical capacity (approximately 1961 mA h g-1). However, it is plagued by issues of low electrochemical activity, low conductivity and severe volume expansion. To address these challenges, we initially coat SiO2 with CoO, followed by introducing SiO2@CoO into graphene sheets to fabricate an anode composite material (SiO2@CoO/GS) with uniformly dispersed particles and a 3D graphene wrapped yolk-shell structure. The coating of CoO on SiO2 converted the negative surface charge of SiO2 to positive, enabling effective electrostatic interactions between SiO2@CoO and graphene oxide sheets, which provided essential prerequisites for synthesizing composite materials with uniformly dispersed particles and good coating effects. Furthermore, the Co-metal formed during the charge-discharge process can act as a catalyst and electron transfer medium, activating the lithium storage activity of SiO2 and enhancing the conductivity of the electrode, conclusively achieving a higher lithium storage capacity. Ultimately, due to the activation of SiO2 by Co-metal during cycling and the excellent synergistic effect between SiO2@CoO and graphene, SiO2@CoO/GS delivers a high reversible capacity of 738 mA h g-1 after 500 cycles at 200 mA g-1. The product also demonstrates excellent rate performance with a reversible capacity of 206 mA h g-1 at a high specific current of 12.8 A g-1. The outstanding rate performance of SiO2@CoO/GS may be ascribed to the pseudo-capacitive contribution at high specific current upon cycling.

Parallel kinetic resolution of aziridines via chiral phosphoric acid-catalyzed apparent hydrolytic ring-opening.

We report a chiral phosphoric acid catalyzed apparent hydrolytic ring-opening reaction of racemic aziridines in a regiodivergent parallel kinetic resolution manner. Harnessing the acyloxy-assisted strategy, the highly stereocontrolled nucleophilic ring-opening of aziridines with water is achieved. Different kinds of aziridines are applicable in the process, giving a variety of enantioenriched aromatic or aliphatic amino alcohols with up to 99% yields and up to >99.5 : 0.5 enantiomeric ratio. Preliminary mechanistic study as well as product elaborations were inducted as well.

Stable Operation Induced by Plastic Crystal Electrolyte Used in Ni-Rich NMC811 Cathodes for Li-Ion Batteries.

The LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode material has been of significant consideration owing to its high energy density for Li-ion batteries. However, the poor cycling stability in a carbonate electrolyte limits its further development. In this work, we report the excellent electrochemical performance of the NMC811 cathode using a rational electrolyte based on organic ionic plastic crystal N-ethyl-N-methyl pyrrolidinium bis(fluorosulfonyl)imide C2mpyr[FSI], with the addition of (1:1 mol) LiFSI salt. This plastic crystal electrolyte (PC) is a thick viscous liquid with an ionic conductivity of 2.3 × 10-3 S cm-1 and a high Li+ transference number of 0.4 at ambient temperature. The NMC811@PC cathode delivers a discharge capacity of 188 mA h g-1 at a rate of 0.2 C with a capacity retention of 94.5% after 200 cycles, much higher than that of using a carbonate electrolyte (54.3%). Moreover, the NMC811@PC cathode also exhibits a superior high-rate capability with a discharge capacity of 111.0 mA h g-1 at the 10 C rate. The significantly improved cycle performance of the NMC811@PC cathode can be attributed to the high Li+ conductivity of the PC electrolyte, the stable Li+ conductive CEI film, and the maintaining of particle integrity during long-term cycling. The admirable electrochemical performance of the NMC811|C2mpyr[FSI]:[LiFSI] system exhibits a promising application of the plastic crystal electrolyte for high voltage layered oxide cathode materials in advanced lithium-ion batteries.

Prussian blue/RGO with less coordinated water as superior cathode material for sodium-ion batteries.

A micro-cubic Prussian blue (PB) with less coordinated water is first developed by electron exchange between graphene oxide and PB. The obtained reduced graphene oxide-PB composite exhibited increased redox reactions of the Fe sites and delivered ultrahigh specific capacity of 163.3 mA h g-1 (30 mA g-1) as well as excellent cycle stability as a cathode in sodium-ion batteries.

Retraction: Prussian blue without coordinated water as a superior cathode for sodium-ion batteries.

Retraction of 'Prussian blue without coordinated water as a superior cathode for sodium-ion batteries' by Dezhi Yang et al., Chem. Commun., 2015, 51, 8181-8184, https://doi.org/10.1039/C5CC01180A.

Spray-dried assembly of 3D N,P-Co-doped graphene microspheres embedded with core-shell CoP/MoP@C nanoparticles for enhanced lithium-ion storage.

The advancement of novel synthetic approaches for micro/nanostructural manipulation of transition metal phosphide (TMP) materials with precisely controlled engineering is crucial to realize their practical use in batteries. Here, we develop a novel spray-drying strategy to construct three-dimensional (3D) N,P co-doped graphene (G-NP) microspheres embedded with core-shell CoP@C and MoP@C nanoparticles (CoP@C⊂G-NP, MoP@⊂G-NP). This intentional design shows a close correlation between the microstructural G-NP and chemistry of the core-shell CoP@C/MoP@C nanoparticle system that contributes towards their anode performance in lithium-ion batteries (LIBs). The obtained structure features a conformal porous G-NP framework prepared via the co-doping of heteroatoms (N,P) that features a 3D conductive highway that allows rapid ion and electron passage and maintains the overall structural integrity of the material. The interior carbon shell can efficiently restrain volume evolution and prevent CoP/MoP nanoparticle aggregation, providing excellent mechanical stability. As a result, the CoP@C⊂G-NP and MoP@⊂G-NP composites deliver high specific capacities of 823.6 and 602.9 mA h g-1 at a current density of 0.1 A g-1 and exhibit excellent cycling stabilities of 438 and 301 mA h g-1 after 500 and 800 cycles at 1 A g-1. The present work details a novel approach to fabricate core-shell TMPs@C⊂G-NP-based electrode materials for use in next-generation LIBs and can be expanded to other potential energy storage applications.

Synergistic antibacterial effect of graphene-coated titanium loaded with levofloxacin.

In this study, graphene coating was introduced to the modified titanium surface to prevent bacterial infection in oral implants. We modified the titanium surface through SLA and silanization treatment and then coated the surface with graphene. The structure and surface properties were characterized by XPS and SEM. Graphene-coated titanium sheet was incubated with bacteria to test the antibacterial property, which was enhanced by adsorption and release of levofloxacin. We further implanted the graphene-coated titanium sheet loaded with levofloxacin into rabbits to test the antibacterial properties in vivo. The graphene coating exhibited inherent antibacterial properties through membrane stress and the generation of reactive oxygen species (ROS). When loaded with levofloxacin, the graphene coating exhibited a synergistic antibacterial effect and effectively prevented bacterial infections following the implantation. The graphene coating is promising to improve the antibacterial functions of oral implant surfaces to prevent bacterial infection.

Structural Tuning of a Flexible and Porous Polypyrrole Film by a Template-Assisted Method for Enhanced Capacitance for Supercapacitor Applications.

Constructing a rational electrode structure for supercapacitors is critical to accelerate the electrochemical kinetics process and thus promote the capacitance. Focusing on the flexible supercapacitor electrode, we synthesized a three-dimensional (3D) porous polypyrrole (PPy) film using a modified vapor phase polymerization method with the use of a porous template (CaCO3). The porous design provided the PPy film with an improved surface area and pore volume. The porous PPy film electrode was studied as a binder-free electrode for supercapacitors. It was found that the abundant interpenetrated pores created by the CaCO3 templates within the 3D framework are beneficial to overcoming the diffusion-controlled limit in the overall electrochemical process. It was revealed by electrochemical investigation that a more pseudocapacitive contribution than diffusion-controlled process contribution was observed in the total charge in the redox reaction. The galvanostatic charge/discharge (GCD) measurements showed that the optimized 3D porous PPy film electrode delivered a high capacitance of 313.6 F g-1 and an areal capacitance of 98.0 mF cm-2 at 1.0 A g-1 in a three-electrode configuration, which is nearly three times that of the dense counterpart electrode synthesized in the absence of the CaCO3 template. A specific capacitance of 62.5 F g-1 at 0.5 A g-1 and 31.1 F g-1 at 10 A g-1 was obtained in a symmetric capacitor device. In addition, the porous structure provided the PPy film with the attractive capability of accommodating the volume change during the doping/dedoping process. This is essential for the PPy film to maintain a long cycling life in a practical operation for a supercapacitor. It turned out that a high capacitance retention up to 81.3% after 10,000 GCD cycles was obtained for the symmetric supercapacitor device with the 3D porous PPy electrode (57.1% capacitive retention was observed for the dense PPy electrode). The strategy and the insight analysis are expected to provide valuable guidance for the design and the synthesis of flexible and wearable film electrodes with high performance.

Surface Tuning to Promote the Electrocatalysis for Oxygen Evolution Reaction: From Metal-Free to Cobalt-Based Carbon Electrocatalysts.

Heterogeneous electrocatalytic reactions only occur at the interface between the electrocatalyst and reactant. Therefore, the active sites are only necessary to be distributed on the surface of the electrocatalyst. Based on this motivation, here, we demonstrate a systematic study on surface tuning for a carbon-based electrocatalyst from metal-free (with the heteroatoms N and S, NS/C) to metal-containing surfaces (with Co, N, and S, CoNS/C). The CoNS/C electrocatalyst was obtained by pyrolyzing the Co precoordinated and p-toluenesulfonate-doped polypyrrole (PPy). It was found that the coordination of Co on the PPy ring tuned the final carbon electrocatalyst into a catalyst with a CoNx moiety-rich surface. In addition, the as-synthesized CoNS/C was determined to have a very high loading of cobalt up to 2.02 wt %. The pyrolysis of the cobalt-containing precursor tends to proceed toward a characteristic of a higher sp2 carbon content, a higher surface area, and more nitrogen as well as active nitrogen sites than its metal-free counterpart. The most distinguished feature for such a catalyst is that the truly most active component is only distributed on the surface, in contrast with that of the conventional metal-N-based catalyst present throughout the bulky structure. Especially, the electrocatalytic activity toward oxygen evolution reaction (OER) has been investigated experimentally and theoretically. The results showed that the OER performance of the carbon-based electrocatalyst was remarkably boosted after the introduction of Co with an overpotential decrease from 678 to 345 mV at 10 mA cm-2. Furthermore, CoNS/C displayed an excellent durability upon a long-term measurement. The apparent activation energy measurements revealed that the metal-rich surface contributed to overcome the energy barrier for OER. In addition, density functional theory calculations have been conducted to explain the correlated OER mechanism. This study is expected to provide an effective strategy for the design and the synthesis of highly active metal-nitrogen-type electrocatalysts with a high metal loading for various electrocatalytic reactions.

Improved Cycling Performance of P2-Na0.67Ni0.33Mn0.67O2 Based on Sn Substitution Combined with Polypyrrole Coating.

P2-Na0.67Ni0.33Mn0.67O2 presents high working voltage with a theoretical capacity of 173 mAh g-1. However, the lattice oxygen on the particle surface participates in the redox reactions when the material is charged over 4.22 V. The resulting oxidized oxygen aggravates the electrolyte decomposition and transition metal dissolution, which cause severe capacity decay. The commonly reported cation substitution methods enhance the cycle stability by suppressing the high voltage plateau but lead to lower average working voltage and reduced capacity. Herein, we stabilized the lattice oxygen by a small amount of Sn substitution based on the strong Sn-O bond without sacrificing the high voltage performance and further protected the particle surface by polypyrrole (PPy) coating. The obtained Na0.67Ni0.33Mn0.63Sn0.04O2@PPy (3.3 wt %) composite showed excellent cycling stability with a reversible capacity of 137.6 (10) and 120.0 mAh g-1 (100 mA g-1) with a capacity retention of 95% (10 mA g-1, 50 cycles) and 82.5% (100 mA g-1, 100 cycles), respectively. The present work indicates that slight Sn substitution combined with PPy coating could be an effective approach to achieving superior cycling stability for high-voltage layered transition metal oxides.

MXene Frameworks Promote the Growth and Stability of LiF-Rich Solid-Electrolyte Interphases on Silicon Nanoparticle Bundles.

Silicon-based materials are the desirable anodes for next-generation lithium-ion batteries; however, the large volume change of Si during the charging/discharging process causes electrode fracture and an unstable solid-electrolyte interphase (SEI) layer, which severely impair their stability and Coulombic efficiency. Herein, a bundle of silicon nanoparticles is encapsulated in robust micrometer-sized MXene frameworks, in which the MXene nanosheets are precrumpled by capillary compression force to effectively buffer the stress induced by the volume change, and the abundant covalent bonds (Ti-O-Ti) between adjacent nanosheets formed through a facile thermal self-cross-linking reaction further guarantee the robustness of the MXene architecture. Both factors stabilize the electrode structure. Moreover, the abundant fluorine terminations on MXene nanosheets contribute to an in situ formation of a highly compact, durable, and mechanically robust LiF-rich SEI layer outside the frameworks upon cycling, which not only shuts down the parasitic reaction between Si and an organic electrolyte but also enhances the structural stability of MXene frameworks. Benefiting from these merits, the as-prepared anodes deliver a high specific capacity of 1797 mA h g-1 at 0.2 A g-1 and a high capacity retention of 86.7% after 500 cycles at 2 A g-1 with an average Coulombic efficiency of 99.6%. Significantly, this work paves the way for other high-capacity electrode materials with a strong volume effect.

Cobalt phosphide embedded in a graphene nanosheet network as a high-performance anode for Li-ion batteries.

Cobalt phosphide (CoP) is a potential alternative to Li-ion battery (LIB) anodes due to its high specific capacity. However, there remain challenges, including low rate capability and rapid capacity degradation, because of its structural pulverization and poor electrical conductivity. Here, we demonstrate an effective strategy to enhance CoP-based anodes by developing a CoP/graphene nanocomposite. Such a nanocomposite can be achieved by embedding nanostructured CoP in a reduced graphene oxide (rGO) nanosheet network through a versatile method including the low-temperature formation of metal oxide nanoparticles, freeze-drying, and a subsequent phosphidation process. Benefiting from its favorable nanoarchitecture, the CoP/rGO nanocomposite is found to possess enhanced conductivity, porosity and structural stability. As a result, the nanocomposite shows a high specific capacity up to 1154 mA h g-1 at a current density of 100 mA g-1 and a remarkable rate capability (840 mA h g-1 at 2 A g-1). Moreover, a high capacity of 808 mA h g-1 is achieved even after 2000 cycles. These promising features indicate that our strategy could open the door to the further applications of CoP-based anodes in LIBs.

Coaxial Carbon Nanotube Supported TiO2@MoO2@Carbon Core-Shell Anode for Ultrafast and High-Capacity Sodium Ion Storage.

The sluggish kinetic in electrode materials is one of the critical challenges in achieving high-power sodium ion storage. We report a coaxial core-shell nanostructure composed of carbon nanotube (CNT) as the core and TiO2@MoO2@C as shells for a hierarchically nanoarchitectured anode for improved electrode kinetics. The 1D tubular nanostructure can effectively reduce ion diffusion path, increase electrical conductivity, accommodate the stress due to volume change upon cycling, and provide additional interfacial active sites for enhanced charge storage and transport properties. Significantly, a synergistic effect between TiO2 and MoO2 nanostructures is investigated through ex situ solid-state nuclear magnetic resonance. The electrode exhibits a good rate capability (150 mAh g-1 at 20 A g-1) and superior cycling stability with a reversibly capacity of 175 mAh g-1 at 10 A g-1 for over 8000 cycles.

Rational Design of the Robust Janus Shell on Silicon Anodes for High-Performance Lithium-Ion Batteries.

The high-capacity silicon anode is regarded as a promising electrode material for next-generation lithium-ion batteries. Unfortunately, its practical application is still severely hindered by electrode fracture and unstable solid electrolyte interphase during cycling. Herein, we design a structure of encapsulating silicon in a robust "janus shell", in which an internal graphene shell with sufficient void space is used to absorb the mechanical stress induced by volume expansion, and the conformal carbon outer shell is introduced to strongly bond the loosely stacked graphene shell and simultaneously seal the nanopores on the surface. With the ultrastable janus carbon shell, the excellent structural integrity of the electrode and stable solid electrolyte interphase layer could be effectively preserved, resulting in an impressive cycling behavior. Indeed, the as-synthesized anodes demonstrate superior cycle stability and excellent rate performance, delivering a high reversible capacity of 1416 mA h g-1 at a current density of 0.2 A g-1 and 852 mA h g-1 at a high current density of 5 A g-1. Remarkably, the superior capacity retention of 88.5% could be achieved even after 400 cycles at a high current density of 2 A g-1. More importantly, this work opens up a novel avenue to address high-capacity anodes with a large volume change.

A nitrogen-containing carbon film derived from vapor phase polymerized polypyrrole as a fast charging/discharging capability anode for lithium-ion batteries.

A nitrogen-containing carbon (N-C) film was synthesized by pyrolysis of vapor phase polymerized polypyrrole (PPy). This carbon film exhibits excellent rate capability and cyclability as a lithium-ion battery anode. The reversible capacities are 908.4, 825.7, 664.0, 531.6, 415.5 and 325.9 mA h g(-1) at 1C, 2C, 5C, 10C, 20C and 40C, respectively.

Carbon coated SnO2 nanoparticles anchored on CNT as a superior anode material for lithium-ion batteries.

Hierarchically structured carbon coated SnO2 nanoparticles well-anchored on the surface of a CNT (C-SnO2/CNT) material were synthesized by a facile hydrothermal process and subsequent carbonization. The as-obtained C-SnO2/CNT hybrid, when applied as an anode material for lithium ion batteries (LIBs), showed a high reversible capacity up to 1572 mA h g(-1) at 200 mA g(-1) with a superior rate capability (685 mA h g(-1) at 4000 mA g(-1)). Even after 100 charge/discharge cycles at 1000 mA g(-1), a specific capacity of 1100 mA h g(-1) can still be maintained. Such impressive electrochemical performance can be mainly attributed to the hierarchical sandwiched structure and strong synergistic effects of the ultrafine SnO2 nanoparticles and the carbon coating, and thus presents this material a promising anode material for LIBs.

A dual-spatially-confined reservoir by packing micropores within dense graphene for long-life lithium/sulfur batteries.

In lithium/sulfur batteries, micropores could bring about strong interactions with polysulfides, but could not alleviate the partial polysulfide overflowing outside because of the volume expansion of the lithiated sulfur. A dual-spatially-confined reservoir for sulfur by wrapping microporous carbon with dense graphene, micro@meso-porous DSC (dual-spatial carbon), is synthesized to solve this issue. Such a structure is prepared through two distinctive methods: graphene promoted in situ hydrothermal carbonization of organics to grow micropores on itself, and liquid mediated drying of graphene hydrogel to form mesoporous graphene frameworks. In contrast to previously reported hierarchical carbon/S, the inner micropores are mainly responsible for loading sulfur, which could help confine its particle size, thus increasing the electrical/ionic conductivity and the utilization of sulfur, and restrain lithium polysulfide dissolution because of strong interaction with pore walls; while the outer mesopores act as another reservoir to stabilize the overflowed polysulfide and to enhance the Li(+) transport. The S-micro@meso-porous DSC cathode exhibits better discharge capacity and cycling performance than S-microporous AC and S-micro@macro-porous DSC, i.e., 59% and 37% higher capacity remaining at 0.5 C than the latter two, respectively.