High-Entropy Polymer Electrolytes Derived from Multivalent Polymeric Ligands for Solid-State Lithium Metal Batteries with Accelerated Li+ Transport.

Solid-state polymer-based electrolytes (SSPEs) exhibit great possibilities in realizing high-energy-density solid-state lithium metal batteries (SSLMBs). However, current SSPEs suffer from low ionic conductivity and unsatisfactory interfacial compatibility with metallic Li because of the high crystallinity of polymers and sluggish Li+ movement in SSPEs. Herein, differing from common strategies of copolymerization, a new strategy of constructing a high-entropy SSPE from multivariant polymeric ligands is proposed. As a protocol, poly(vinylidene fluoride-co-hexafluoropropylene) (PH) chains are grafted to the demoed polyethylene imine (PEI) with abundant -NH2 groups via a click-like reaction (HE-PEIgPHE). Compared to a PH-based SSPE, our HE-PEIgPHE shows a higher modulus (6.75 vs 5.18 MPa), a higher ionic conductivity (2.14 × 10-4 vs 1.03 × 10-4 S cm-1), and a higher Li+ transference number (0.55 vs 0.42). A Li|HE-PEIgPHE|Li cell exhibits a long lifetime (1500 h), and a Li|HE-PEIgPHE|LiFePO4 cell delivers an initial capacity of 160 mAh g-1 and a capacity retention of 98.7%, demonstrating the potential of our HE-PEIgPHE for the SSLMBs.

Dead Lithium in Lithium Metal Batteries: Formation, Characterization and Strategies.

Lithium (Li) metal anode (LMA) replacing graphite anode for developing Li metal batteries (LMB) with the higher energy density has attracted much attention. However, LMA faces many issues, e.g., Li dendrites, dead Li and the side reactions, which causes the safety hazards and low coulomb efficiency (CE) of battery, therefore, LMB still cannot replace the current Li ion battery for practical use. Among those issues, dead Li is one of the decisive factors affecting the CE of LMB. To better understand dead Li, we summarize the recent work about the generation of dead Li, its impact on batteries performance, and the strategies to reuse and eliminate dead Li. Finally, the prospect of the future LMA and resultant LMB is also put forward.

Superior Li+ Kinetics by "Low-Activity-Solvent" Engineering for Stable Lithium Metal Batteries.

The structure of solvated Li+ has a significant influence on the electrolyte/electrode interphase (EEI) components and desolvation energy barrier, which are two key factors in determining the Li+ diffusion kinetics in lithium metal batteries. Herein, the "solvent activity" concept is proposed to quantitatively describe the correlation between the electrolyte elements and the structure of solvated Li+. Through fitting the correlation of the electrode potential and solvent concentration, we suggest a "low-activity-solvent" electrolyte (LASE) system for deriving a stable inorganic-rich EEI. Nano LiF particles, as a model, were used to capture free solvent molecules for the formation of a LASE system. This advanced LASE not only exhibits outstanding antidendrite growth behavior but also delivers an impressive performance in Li/LiNi0.8Co0.1Mn0.1O2 cells (a capacity of 169 mAh g-1 after 250 cycles at 0.5 C).

Interfacial Modulation of a Self-Sacrificial Synthesized SnO2@Sn Core-Shell Heterostructure Anode toward High-Capacity Reversible Li+ Storage.

Sn-based anodes are promising high-capacity anode materials for low-cost lithium ion batteries. Unfortunately, their development is generally restricted by rapid capacity fading resulting from large volume expansion and the corresponding structural failure of the solid electrolyte interphase (SEI) during the lithiation/delithiation process. Herein, heterostructural core-shell SnO2-layer-wrapped Sn nanoparticles embedded in a porous conductive nitrogen-doped carbon (SOWSH@PCNC) are proposed. In this design, the self-sacrificial Zn template from the precursors is used as the pore former, and the LiF-Li3N-rich SEI modulation layer is motivated to average uniform Li+ flux against local excessive lithiation. Meanwhile, both the chemically active nitrogen sites and the heterojunction interfaces within SnO2@Sn are implanted as electronic/ionic promoters to facilitate fast reaction kinetics. Consequently, the as-converted SOWSH@PCNC electrodes demonstrate a significantly boosted Li+ capacity of 961 mA h g-1 at 200 mA g-1 and excellent cycling stability with a low capacity decaying rate of 0.071% after 400 cycles at 500 mA g-1, suggesting their great promise as an anode material in high-performance lithium ion batteries.

Anion Receptor Enhanced Li Ion Transportation for High-Performance Lithium Metal Batteries.

High-potential lithium metal batteries (LMBs) are still facing many challenges, such as the growth of lithium (Li) dendrites and resultant safety hazards, low-rate capabilities, etc. To this end, electrolyte engineering is believed to be a feasible strategy and interests many researchers. In this work, a novel gel polymer electrolyte membrane, which is composed of polyethyleneimine (PEI)/poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) cross-linked membrane and electrolyte (PPCM GPE), is prepared successfully. Due to the fact that the amine groups on PEI molecular chains can provide the rich anion receptors and strongly pin the anions of electrolytes and thus confine the movement of anions, our designed PPCM GPE owns a high Li+ transference number (0.70) and finally contributes to the uniform Li+ deposition and inhibits the growth of Li dendrites. In addition, the cells with PPCM GPE as a separator behave the impressive electrochemical performances, i.e., a low overpotential and an ultralong and stable cycling performance in Li∥Li cells, a low overvoltage of about 34 mV after a stable cycling for 400 h even at a high current density of 5 mA/cm2, and, in Li∥LFP full batteries, a specific capacity of 78 mAh/g after 250 cycles at a 5 C rate. These excellent results suggest a potential application of our PPCM GPE in developing high-energy-density LMBs.

A Polar and Ordered-Channel Composite Separator Enables Antidendrite and Long-Cycle Lithium Metal Batteries.

Lithium (Li) metal as an anode replacing the traditional graphite could largely enhance the specific energy density of Li batteries. However, the repeated formation of solid electrolyte interfaces on the surface of Li metal upon plating/stripping leads to a low Coulombic efficiency, and the growth of Li dendrites upon cycling probably causes the short circuit or even explosion of the batteries, both of which block the commercial application of Li metal in lithium metal batteries (LMBs). Herein, we report an antidendrite AAO@PVDF-HFP composite separator fabricated by a two-step method, which features the ordered pore channels and the polar groups in the channels. This novel composite separator has a good wettability to the electrolyte, high mechanical properties, and high ionic conductivity. Expectedly, the assembled batteries based on our novel composite separator show many impressive performances. In Li-Li cells, the cycling life up to 1600 h at an areal current density of 2 mA/cm2 can be realized; in Li-Cu cells, the cycling life of more than 1000 h with a high Coulombic efficiency of 99.9% at 1 mA/cm2 can be achieved. More interestingly, the Li/LiFePO4 full batteries constructed by the novel AAO@PVDF-HFP composite separators show a high discharge capacity of 140 mAh/g and weak capacity decays even after 360 cycles. The novel design of the separator with ordered channels and polar groups presents an effective route for developing the next-generation LMBs.

Tuning Two Interfaces with Fluoroethylene Carbonate Electrolytes for High-Performance Li/LCO Batteries.

Various electrolytes have been reported to enhance the reversibility of Li-metal electrodes. However, for these electrolytes, concurrent and balanced control of Li-metal and positive electrode interfaces is a critical step toward fabrication of high-performance Li-metal batteries. Here, we report the tuning of Li-metal and lithium cobalt oxide (LCO) interfaces with fluoroethylene carbonate (FEC)-containing electrolytes to achieve high cycling stability of Li/LCO batteries. Reversibility of the Li-metal electrode is considerably enhanced for electrolytes with high FEC contents, confirming the positive effect of FEC on the stabilization of the Li-metal electrode. However, for FEC contents of 50 wt % and above, the discharge capacity is significantly reduced because of the formation of a passivation layer on the LCO cathodes. Using balanced tuning of the two interfaces, stable cycling over 350 cycles at 1.5 mA cm-2 is achieved for a Li/LCO cell with the 1 M LiPF6 FEC/DEC = 30/70 electrolyte. The enhanced reversibility of the Li-metal electrode is associated with the formation of LiF and polycarbonate in the FEC-derived solid electrolyte interface (SEI) layer. In addition, electrolytes with high FEC contents lead to lateral Li deposition on the sides of Li deposits and larger dimensions of rodlike Li deposits, suggesting the elastic and ion-conductive nature of the FEC-derived SEI layer.

An Ultrahigh Capacity Graphite/Li2S Battery with Holey-Li2S Nanoarchitectures.

The pairing of high-capacity Li2S cathode (1166 mAh g-1) and lithium-free anode (LFA) provides an unparalleled potential in developing safe and energy-dense next-generation secondary batteries. However, the low utilization of the Li2S cathode and the lack of electrolytes compatible to both electrodes are impeding the development. Here, a novel graphite/Li2S battery system, which features a self-assembled, holey-Li2S nanoarchitecture and a stable solid electrolyte interface (SEI) on the graphite electrode, is reported. The holey structure on Li2S is beneficial in decomposing Li2S at the first charging process due to the enhanced Li ion extraction and transfer from the Li2S to the electrolyte. In addition, the concentrated dioxolane (DOL)-rich electrolyte designed lowers the irreversible capacity loss for SEI formation. By using the combined strategies, the graphite/holey-Li2S battery delivers an ultrahigh discharge capacity of 810 mAh g-1 at 0.1 C (based on the mass of Li2S) and of 714 mAh g-1 at 0.2 C. Moreover, it exhibits a reversible capacity of 300 mAh g-1 after a record lifecycle of 600 cycles at 1 C. These results suggest the great potential of the designed LFA/holey-Li2S batteries for practical use.

In Situ Electrochemically Derived Amorphous-Li2 S for High Performance Li2 S/Graphite Full Cell.

High-capacity Li2 S cathode (1166 mAh g-1 ) is regarded as a promising candidate for the next-generation lithium ion batteries. However, its high potential barrier upon the initial activation process leads to a low utilization of Li2 S. In this work, a Li2 S/graphite full cell with the zero activation potential barrier is achieved through an in situ electrochemical conversion of Li2 S8 catholyte into the amorphous Li2 S. Theoretical calculations indicate that the zero activation potential for amorphous Li2 S can be ascribed to its lower Li extraction energy than that of the crystalline Li2 S. The constructed Li2 S/graphite full cell delivers a high discharge capacity of 1006 mAh g-1 , indicating a high utilization of the amorphous Li2 S as a cathode. Moreover, a long cycle life with 500 cycles for this Li2 S/graphite full cell is realized. This in situ electrochemical conversion strategy designed here is inspired for developing high energy Li2 S-based full cells in future.

Liquid-Phase Electrochemical Scanning Electron Microscopy for In Situ Investigation of Lithium Dendrite Growth and Dissolution.

An in situ electrochemical scanning electronic microscopy method is developed to systematically study the lithium plating/stripping processes in liquid electrolytes. The results demonstrate that the lithium dendrite growth speed and mechanism is greatly affected by the additives in the ether-based electrolyte.

Synthesis, Crystal Structure, and Electrochemical Properties of a Simple Magnesium Electrolyte for Magnesium/Sulfur Batteries.

Most simple magnesium salts tend to passivate the Mg metal surface too quickly to function as electrolytes for Mg batteries. In the present work, an electroactive salt [Mg(THF)6 ][AlCl4 ]2 was synthesized and structurally characterized. The Mg electrolyte based on this simple mononuclear salt showed a high Mg cycling efficiency, good anodic stability (2.5 V vs. Mg), and high ionic conductivity (8.5 mS cm(-1) ). Magnesium/sulfur cells employing the as-prepared electrolyte exhibited good cycling performance over 20 cycles in the range of 0.3-2.6 V, thus indicating an electrochemically reversible conversion of S to MgS without severe passivation of the Mg metal electrode surface.

Prelithiation of Nanostructured Sulfur Cathode by an "On-Sheet" Solid-State Reaction.

A novel "on-sheet" solid-state chemical reaction method is designed to fabricate a nanostructured Li2 S-reduced graphene oxide (rGO) cathode using a semi-sacrificial sulfur-graphene oxide template. The as-fabricated Li2 S-rGO nanocomposite shows a superior electrochemical performance, e.g., high utilization of Li2 S active materials (86.3 wt%), long cell life (1000 cycles), and excellent rate ability.

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.

Fabrication of mesoporous Li2S-C nanofibers for high performance Li/Li2S cell cathodes.

A Li2S electrode is a very promising cathode for Li-ion batteries. However, the high voltage needed to activate Li/Li2S cells represents a challenging problem. Here, we report for the first time a mesoporous Li2S-C nanofiber composite with 72 wt% Li2S. The assembled Li/Li2S cells showed a low and stable voltage plateau of 2.51 V for the first charge and can deliver a high initial discharge capacity of ∼800 mA h g(-1).

High-rate, ultralong cycle-life lithium/sulfur batteries enabled by nitrogen-doped graphene.

Nitrogen-doped graphene (NG) is a promising conductive matrix material for fabricating high-performance Li/S batteries. Here we report a simple, low-cost, and scalable method to prepare an additive-free nanocomposite cathode in which sulfur nanoparticles are wrapped inside the NG sheets (S@NG). We show that the Li/S@NG can deliver high specific discharge capacities at high rates, that is, ∼ 1167 mAh g(-1) at 0.2 C, ∼ 1058 mAh g(-1) at 0.5 C, ∼ 971 mAh g(-1) at 1 C, ∼ 802 mAh g(-1) at 2 C, and ∼ 606 mAh g(-1) at 5 C. The cells also demonstrate an ultralong cycle life exceeding 2000 cycles and an extremely low capacity-decay rate (0.028% per cycle), which is among the best performance demonstrated so far for Li/S cells. Furthermore, the S@NG cathode can be cycled with an excellent Coulombic efficiency of above 97% after 2000 cycles. With a high active S content (60%) in the total electrode weight, the S@NG cathode could provide a specific energy that is competitive to the state-of-the-art Li-ion cells even after 2000 cycles. The X-ray spectroscopic analysis and ab initio calculation results indicate that the excellent performance can be attributed to the well-restored C-C lattice and the unique lithium polysulfide binding capability of the N functional groups in the NG sheets. The results indicate that the S@NG nanocomposite based Li/S cells have a great potential to replace the current Li-ion batteries.

Facile and rapid synthesis of RGO-In2S3 composites with enhanced cyclability and high capacity for lithium storage.

A sheet-on-sheet reduced graphene oxide-ß-In(2)S(3) (RGO-In(2)S(3)) composite, was successfully synthesized via a one-step mild method. This fresh composite used as an anode material exhibits enhanced cyclability and specific capacity for lithium storage. These results are linked with the intrinsic layered structure of ß-In(2)S(3) sheets and the effective combination of ß-In(2)S(3) and RGO sheets. This results in a high specific surface area and good conductivity of RGO-In(2)S(3) composites, with higher transport rates of electrolyte ions and electrons, and a more effective electrochemical reaction of the active material. This facile and rapid synthesis method is a promising route for a large-scale production of graphene-based metal sulfides, which could be used as electrode materials for Li-ion batteries.