Highly Stable and Ultrahigh-Rate Li Metal Anode Enabled by Fluorinated Carbon Fibers.

The advanced energy storage of an Li metal substituted for graphite anode can provide a significant enhancement in a battery's energy density. Nevertheless, the practical implementation of metallic Li has seriously been fettered by the notorious Li dendrite growth and the huge volumetric variation of Li metal inducing poor cycling performance and safety concerns. In this regard, constructing a robust SEI layer combined with a 3D host to stabilize the Li metal is strongly in demand. Herein, a highly stable hosted Li with an LiF dominated SEI has successfully been achieved through metal-free fluorinated carbon fibers (FCF) with strong lithiophilicity. The metal-free design is cost-effective and can retain the energy density of the Li metal, minimizing the unnecessary energy sacrifice from the extra high gravimetric density lithiophilic sites. The FCF hosted Li delivers a promoted high Coulombic efficiency, homogeneous Li deposition, and ultrahigh rate stable cycling over 1000 cycles at 20 mA cm-2 with a much lower voltage polarization (≈220 mV). Moreover, half cells coupled with LiNi0.8 Co0.1 Mn0.1 O2 , sulfur or even thick LiCoO2 cathode demonstrate superior rate performances and enhanced cycling stability even under a lean electrolyte. This work proves the feasibility of FCF hosted Li for practical usage and provides a novel approach toward cost-effective and high performance lithium metal batteries.

High-Performance Three-Dimensional Li Anode Scaffold Enabled by Homogeneous Zn Nanoclusters.

The large-scale implementation of lithium metal batteries (LMBs) has long been plagued by the uncontrollable Li deposition triggered safety issues. Herein, a lithiophilic three-dimensional Li anode scaffold, which is prepared by molten Li infusion aided by confined growth of low-cost Zn clusters, is rationally constructed for high-performance LMBs. Owing to the synergy of the carbon host and the effective regulation from the Zn nanoclusters, the large volumetric change of Li metal is well mitigated and shows a smooth and dendrite-free behavior. The Li anode scaffold can deliver much improved Coulombic efficiency, superior rate performance, and long cycle lifespan with much lower voltage polarization. Furthermore, the half cells of Li anode scaffold paired with LiFePO4 /LiCoO2 /sulfur can achieve a higher specific capacity and longer stable cycling life than those with conventional Li foil. The Li|LFP cells can achieve a stable cycling over 250 cycles at 1C with a higher capacity retention of ≈90.8%, and a higher initial discharge capacity of 924.6 mAh g-1 with a high capacity retention over 300 cycles can also be obtained in Li|S cells at 1C. This work demonstrates a cost-effective and scalable strategy for stable Li metal anode toward next-generation and high-performance LMBs.

Iodine-doped carbon nanotubes boosting the adsorption effect and conversion kinetics of lithium-sulfur batteries.

Compared with lithium-ion batteries (LIBs), lithium-sulfur batteries (LSBs), based on electrochemical reactions involving multi-step 16-electron transformations provide higher specific capacity (1672 mAh g-1) and specific energy (2600 Wh kg-1), exhibiting great potential in the field of energy storage. However, the inherent insulation of sulfur, slow electrochemical reaction kinetics and detrimental shuttle-effect of lithium polysulfides (LiPSs) restrict the development of LSBs in practical applications. Herein, the iodine-doped carbon nanotubes (I-CNTs) is firstly reported as sulfur host material to the enhance the adsorption-conversion kinetics of LSBs. Iodine doping can significantly improve the polarity of I-CNTs. Iodine atoms with lone pair electrons (Lewis base) in iodine-doped CNTs can interact with lithium cations (Lewis acidic) in LiPSs, thereby anchoring polysulfides and suppressing subsequent shuttling behavior. Moreover, the charge transfer between iodine species (electron acceptor) and CNTs (electron donor) decreases the gap band and subsequently improves the conductivity of I-CNTs. The enhanced adsorption effect and conductivity are beneficial for accelerating reaction kinetics and enhancing electrocatalytic activity. The in-situ Raman spectroscopy, quasi in-situ electrochemical impedance spectroscopy (EIS) and Li2S potentiostatic deposition current-time (i-t) curves were conducted to verify mechanism of complex sulfur reduction reaction (SRR). Owing to above advantages, the I-CNTs@S composite cathode exhibits an ultrahigh initial capacity of 1326 mAh g-1 as well as outstanding cyclicability and rate performance. Our research results provide inspirations for the design of multifunctional host material for sulfur/carbon composite cathodes in LSBs.

Electronic-ionic bi-functional conduction ß-Li3PS4-coated graphene hollow spheres as a highly stable lithium metal anode skeleton.

Although Li metal is considered the most potential anode for Li based batteries, the repeatedly large volume variation and low Coulombic efficiency (CE) are still serious challenges for commercial application. Herein, the interconnect closed hollow graphene spheres with electronic-ionic bi-functional conduction network containing Li4.4Sn nanoparticles loaded internally and ß-Li3PS4 solid electrolyte layer coated externally (ß-LPS/SG/Li4.4Sn) is proposed to achieve uniform and dense Li deposition. Density functional theory (DFT) calculation and experimental results show that Li4.4Sn owns larger Li binding energy and lower nucleation overpotential than spherical graphene (SG), thus being able to guide Li traversing and depositing inside the hollow spheres. The Tafel curves, Li+ diffusion activation energy and experimental results reveal that the ß-Li3PS4 coating layer significantly improves the ionic conductivity of the negative skeleton, covers the defect sites on the SG surface, provides continuous ion transmission channels and accelerates Li+ migration rate. The synergy of both can inhibit the formation of dendritic Li and reduce side reaction between freshly deposited lithium and the organic electrolyte. It's found that Li is preferentially deposited within the SG, evenly deposited on the spherical shell surface until it's completely filled to obtain a dense lithium layer without tip effect. As a result, the ß-LPS/SG/Li4.4Sn anode exhibits a long life of up to 2800 h, an extremely low overpotential (∼13 mV) and a high CE of 99.8 % after 470 cycles. The LiFePO4-based full cell runs stably with a high capacity retention of 86.93 % after 800 cycles at 1C. It is considered that the novel structure design of Li anode skeleton with electron-ionic bi-functional conduction is a promising direction to construct long-term stable lithium metal anodes.

In Situ Trapping Strategy Enables a High-Loading Ni Single-Atom Catalyst as a Separator Modifier for a High-Performance Li-S Battery.

The poor electrochemical reaction kinetics of Li polysulfides is a key barrier that prevents the Li-S batteries from widespread applications. Ni single atoms dispersed on carbon matrixes derived from ZIF-8 are a promising type of catalyst for accelerating the conversion of active sulfur species. However, Ni favors a square-planar coordination that can only be doped on the external surface of ZIF-8, leading to a low loading amount of Ni single atoms after pyrolysis. Herein, we demonstrate an in situ trapping strategy to synthesize Ni and melamine-codoped ZIF-8 precursor (Ni-ZIF-8-MA) by simultaneously introducing melamine and Ni during the synthesis of ZIF-8, which can remarkably decrease the particle size of ZIF-8 and further anchor Ni via Ni-N6 coordination. Consequently, a novel high-loading Ni single-atom (3.3 wt %) catalyst implanted in an N-doped nanocarbon matrix (Ni@NNC) is obtained after high-temperature pyrolysis. This catalyst as a separator modifier shows a superior catalytic effect on the electrochemical transitions of Li polysulfides, which endows the corresponding Li-S batteries with a high specific capacity of 1232.4 mA h g-1 at 0.3 C and an excellent rate capability of 814.9 mA h g-1 at 3 C. Furthermore, a superior areal capacity of 4.6 mA h cm-2 with stable cycling over 160 cycles can be achieved under a critical condition with a low electrolyte/sulfur ratio (8.4 µL mg-1) and high sulfur loading (4.85 mg cm-2). The outstanding electrochemical performances can be attributed to the strong adsorption and fast conversion of Li polysulfides on the highly dense active sites of Ni@NNC. This intriguing work provides new inspirations for designing high-loading single-atom catalysts applied in Li-S batteries.

Interfacial Manipulation via In Situ Constructed Fast Ion Transport Channels toward an Ultrahigh Rate and Practical Li Metal Anode.

The successful substitution of Li metal for the conventional intercalation anode can promote a significant increase in the cell energy density. However, the practical application of the Li metal anode has long been fettered by the unstable solid electrolyte interface (SEI) layer on the Li metal surface and notorious dendritic Li growth. Herein, a stabilized SEI layer with in situ constructed fast ion transport channels has successfully been achieved by a robust In2S3-cemented poly(vinyl alcohol) coating. The modified Li metal demonstrates significantly enhanced Coulombic efficiency, high rate performance (10 mA cm-2), and ultralong life cycling stability (∼4900 cycles). The Li|LiCoO2 (LCO) cell presents an ultralong-term stable operation over 500 cycles at 1 C with an extremely low capacity decay rate (∼0.018% per cycle). And the Li|LCO full cell with the ultrahigh loading cathode (∼25 mg cm-2) and ultrathin Li foil (∼40 µm) also reveals a prolonged cycling performance under the low negative-to-positive capacity ratio of 2.2. Furthermore, the Li|LCO pouch cell with a commercial cathode and ultrathin Li foil still manifests excellent cycling performance even under the harsh conditions of limited Li metal and lean electrolyte. This work provides a cost-effective and scalable strategy toward high performance practical Li metal batteries.

In Situ Construction of Efficient Interface Layer with Lithiophilic Nanoseeds toward Dendrite-Free and Low N/P Ratio Li Metal Batteries.

Li metal is considered as one of the most promising candidates for constructing advanced high-energy energy storage due to its ultrahigh theoretical capacity and lowest electrochemical potential. However, its practical commercialization is seriously hindered by the challenges of Li dendrite growth, low Coulombic efficiency, and huge volumetric variation. Herein, an efficient in situ generated Li2 S-rich interface layer joint with preplanted Sb nano active sites in hosted Li metal anode is easily achieved with the nanosized Sb2 S3 decorated carbonaceous network. The yielded CC@Sb2 S3 @Li anode demonstrates uniform Li deposition, high Coulombic efficiency, and alleviated volumetric variation. Therefore, the Li symmetric cells show ultralong lifespan stable cycling over 3200 cycles with a very low voltage hysteresis (≈18 mV) at 5 mA cm-2 . Impressively, the Li|LiFePO4 full cell delivers an exceptionally prolonged cycling over 180 cycles with a superior capacity retention as high as ≈90% even under the harsh condition of an extremely low negative to positive capacity ratio of ≈0.44 with lean electrolyte (4.4 µL mAh-1 ). Moreover, the Li|LiNi0.5 Co0.2 Mn0.3 O2 full cell also maintains an excellent cycling performance under the more realistic harsh conditions. This work provides a new avenue and significant step paving the Li metal toward the practical application.

Uniform and Anisotropic Solid Electrolyte Membrane Enables Superior Solid-State Li Metal Batteries.

Rational structure design is a successful approach to develop high-performance composite solid electrolytes (CSEs) for solid-state Li metal batteries. Herein, a novel CSE membrane is proposed, that consists of interwoven garnet/polyethylene oxide-Li bis(trifluoromethylsulphonyl)imide (LLZO/PEO-LiTFSI) microfibers. This CSE exhibits high Li-ion conductivity and exceptional Li dendrite suppression capability, which can be attributed to the uniform LLZO dispersion in PEO-LiTFSI and the vertical/horizontal anisotropic Li-ion conduction in the CSE. The uniform LLZO particles can generate large interaction regions between LLZO and PEO-LiTFSI, which thus form continuous Li-ion transfer pathways, retard the interfacial side reactions and strengthen the deformation resistance. More importantly, the anisotropic Li-ion conduction, that is, Li-ion transfers much faster along the microfibers than across the microfibers, can effectively homogenize the electric field distribution in the CSE during cycling, which thus prevents the excessive concentration of Li-ion flux. Finally, solid-state Li||LiFePO4 cells based on this CSE show excellent electrochemical performances. This work enriches the structure design strategy of high-performance CSEs and may be helpful for further pushing the solid-state Li metal batteries towards practical applications.

Highly Lithiophilic Copper-Reinforced Scaffold Enables Stable Li Metal Anode.

Lithium (Li) metal is regarded as one of the most prospective electrodes for next-generation rechargeable batteries. However, its widespread usage has been fettered by low coulombic efficiency (CE), poor cycling stability, and serious safety concerns, mainly arising from huge volumetric variation, inhomogeneous Li deposition, and dendrite growth during repeated Li plating/stripping cycles. Herein, we propose a facile one-pot electrospinning-derived highly lithiophilic nanocopper-reinforced three-dimensional-structured carbon nanofiber (Cu-CNF) as functional scaffold to stabilize the Li metal. The Cu-CNF scaffolded Li metal demonstrates homogeneous nanoplate-like Li deposition, enhanced CE, and ultrastable long lifespan cycling. As coupled with LiNi0.8Co0.1Mn0.1O2 (NCM811), the cell possesses a remarkably stable high capacity retention of 93% over 300 cycles at 0.2 C. Furthermore, the cells paired with a thick LiFePO4 (LFP) electrode (∼12 mg cm-2) still can deliver a superior cycling performance even under the harsh conditions of an extremely low negative/positive electrode capacity (N/P) ratio (∼1.5) and lean electrolyte. Density functional theory calculations are performed to disclose the mechanism of the enhanced electrochemical performance of Cu-CNF scaffolded Li. This work provides a handy and cost-effective method to design superior performance Li metal anodes for practical applications.

Bifunctional Fluorinated Separator Enabling Polysulfide Trapping and Li Deposition for Lithium-Sulfur Batteries.

Lithium-sulfur batteries (LSBs) are deemed as one of the most promising next generation energy storage system substitutes for conventional lithium ion batteries due to their high energy density, low cost, and environmental friendliness. The practical application of LSBs has long been blocked by the serious lithium polysulfide (LiPS) shuttle effect and notorious Li dendrite growth, inducing fast capacity decay and limited cycling lifespan. Herein, fluorinated carbon prepared via a safe and scalable strategy has rationally been coated on a separator affording bifunctional fluorinated Celgard (F-Celgard) for LSB construction. The F-Celgard shows superior Li+ flux modulation and LiPS trapping capability, which has been verified by the density function theory calculations. The Li symmetric cells demonstrate long and stable Li plating/stripping with much smaller polarization voltage and dendrite-free Li deposition. In addition, LSBs show superior rate performances with higher discharge capacities and long-time stable cycling over 1000 cycles at 1 C with a low decay rate of ∼0.038% per cycle. With a high sulfur loading (∼5.2 mg cm-2), a high initial areal capacity of ∼4.2 mAh cm-2 can be obtained with a superior capacity retention of ∼91.8% at 0.2 C. This work demonstrates a facile, cost-effective, and scalable strategy toward highly stable LSBs for practical usage.

Unravelling the room-temperature atomic structure and growth kinetics of lithium metal.

Alkali metals are widely studied in various fields such as medicine and battery. However, limited by the chemical reactivity and electron/ion beam sensitivity, the intrinsic atomic structure of alkali metals and its fundamental properties are difficult to be revealed. Here, a simple and versatile method is proposed to form the alkali metals in situ inside the transmission electron microscope. Taking alkali salts as the starting materials and electron beam as the trigger, alkali metals can be obtained directly. With this method, atomic resolution imaging of lithium and sodium metal is achieved at room temperature, and the growth of alkali metals is visualized at atomic-scale with millisecond temporal resolution. Furthermore, our observations unravel the ambiguities in lithium metal growth on garnet-type solid electrolytes for lithium-metal batteries. Finally, our method enables a direct study of physical contact property of lithium metal as well as its surface passivation oxide layer, which may contribute to better understanding of lithium dendrite and solid electrolyte interphase issues in lithium ion batteries.

High-Rate and Large-Capacity Lithium Metal Anode Enabled by Volume Conformal and Self-Healable Composite Polymer Electrolyte.

The widespread implementation of lithium-metal batteries (LMBs) with Li metal anodes of high energy density has long been prevented due to the safety concern of dendrite-related failure. Here a solid-liquid hybrid electrolyte consisting of composite polymer electrolyte (CPE) soaked with liquid electrolyte is reported. The CPE membrane composes of self-healing polymer and Li+-conducting nanoparticles. The electrodeposited lithium metal in a uniform, smooth, and dense behavior is achieved using a hybrid electrolyte, rather than dendritic and pulverized structure for a conventional separator. The Li foil symmetric cells can deliver remarkable cycling performance at ultrahigh current density up to 20 mA cm-2 with an extremely low voltage hysteresis over 1500 cycles. A large areal capacity of 10 mAh cm-2 at 10 mA cm-2 could also be obtained. Furthermore, the Li|Li4Ti5O12 cells based on the hybrid electrolyte achieve a higher specific capacity and longer cycling life than those using conventional separators. The superior performances are mainly attributed to strong adhesion, volume conformity, and self-healing functionality of CPE, providing a novel approach and a significant step toward cost-effective and large-scalable LMBs.

Catalytic production of 1,2-propanediol from glycerol in bio-ethanol solvent.

Production of 1,2-propanediol (1,2-PDO) from glycerol hydrogenolysis was carried out in bio-ethanol solvent over small amount of Rh-promoted Cu/solid-base catalysts prepared via layered double hydroxide precursors. It was found that glycerol hydrogenolysis proceeded easily on Rh-Cu/solid-base catalysts than separated Rh and Cu/solid-base. The conversion of glycerol and selectivity to 1,2-PDO over Rh(0.02)Cu(0.4)/Mg(5.6)Al(1.98)O(8.57) reached 91.0% and 98.7%, respectively, at 2.0 MPa H(2), 180 °C. And this catalyst was stable in five consecutive hydrogenolysis tests in ethanol.