A Polymer‐Reinforced SEI Layer Induced by a Cyclic Carbonate‐Based Polymer Electrolyte Boosting 4.45 V LiCoO2/Li Metal Batteries

Lithium (Li) metal batteries (LMBs) are enjoying a renaissance due to the high energy densities. However, they still suffer from the problem of uncontrollable Li dendrite and pulverization caused by continuous cracking of solid electrolyte interphase (SEI) layers. To address these issues, developing spontaneously built robust polymer‐reinforced SEI layers during electrochemical conditioning can be a simple yet effective solution. Herein, a robust homopolymer of cyclic carbonate urethane methacrylate is presented as the polymer matrix through an in situ polymerization method, in which cyclic carbonate units can participate in building a stable polymer‐integrated SEI layer during cycling. The as‐investigated gel polymer electrolyte (GPE) assembled LiCoO₂/Li metal batteries exhibit a fantastic cyclability with a capacity retention of 92% after 200 cycles at 0.5 C (1 C = 180 mAh g^?1), evidently exceeding that of the counterpart using liquid electrolytes. It is noted that the anionic ring‐opening polymerization of the cyclic carbonate units on the polymer close to the Li metal anodes enables a mechanically reinforced SEI layer, thus rendering excellent compatibility with Li anodes. The in situ formed polymer‐reinforced SEI layers afford a splendid strategy for developing high voltage resistant GPEs compatible with Li metal anodes toward high energy LMBs.     

An In Situ Cross‐Linked Nonaqueous Polymer Electrolyte for Zinc‐Metal Polymer Batteries and Hybrid Supercapacitors

This work reports the facile synthesis of nonaqueous zinc‐ion conducting polymer electrolyte (ZIP) membranes using an ultraviolet (UV)‐light‐induced photopolymerization technique, with room temperature (RT) ionic conductivity values in the order of 10^?3 S cm^?1. The ZIP membranes demonstrate excellent physicochemical and electrochemical properties, including an electrochemical stability window of >2.4 V versus Zn|Zn²⁺ and dendrite‐free plating/stripping processes in symmetric Zn||Zn cells. Besides, a UV‐polymerization‐assisted in situ process is developed to produce ZIP (abbreviated i‐ZIP), which is adopted for the first time to fabricate a nonaqueous zinc‐metal polymer battery (ZMPB; VOPO₄|i‐ZIP|Zn) and zinc‐metal hybrid polymer supercapacitor (ZMPS; activated carbon|i‐ZIP|Zn) cells. The VOPO₄ cathode employed in ZMPB possesses a layered morphology, exhibiting a high average operating voltage of ≈1.2 V. As compared to the conventional polymer cell assembling approach using the ex situ process, the in situ process is simple and it enhances the overall electrochemical performance, which enables the widespread intrusion of ZMPBs and ZMPSs into the application domain. Indeed, considering the promising aspects of the proposed ZIP and its easy processability, this work opens up a new direction for the emergence of the zinc‐based energy storage technologies.     

Additive‐Assisted Novel Dual‐Salt Electrolyte Addresses Wide Temperature Operation of Lithium–Metal Batteries

In this study, self‐synthesized lithium trifluoro(perfluoro‐tert‐butyloxyl)borate (LiTFPFB) is combined with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to formulate a novel 1 m dual‐salt electrolyte, which contains lithium difluorophosphate (LiPO₂F₂) additive and dominant carbonate solvents with low melting point and high boiling point. The addition of LiPO₂F₂ into this novel dual‐salt electrolyte dramatically improves cycleability and rate capability of a LiNi_0.5Mn_0.3Co_0.2O₂/Li (NMC/Li) battery, ranging from ?40 to 90 °C. The NMC/Li batteries adopt a Li–metal anode with low thickness of 100 µm (even 50 µm) and a moderately high cathode mass loading level of 10 mg cm^?2. For the first time, this paper provides valuable perspectives for developing practical lithium–metal batteries over a wide temperature range.     

A Flexible Ceramic/Polymer Hybrid Solid Electrolyte for Solid-State Lithium Metal Batteries

Ceramic/polymer hybrid solid electrolytes (HSEs) have attracted worldwide attentions because they can overcome defects by combining the advantages of ceramic electrolytes (CEs) and solid polymer electrolytes (SPEs). However, the interface compatibility of CEs and SPEs in HSE limits their full function to a great extent. Herein, a flexible ceramic/polymer HSE is prepared via in situ coupling reaction. Ceramic and polymer are closely combined by strong chemical bonds, thus the problem of interface compatibility is resolved and the ions can transport rapidly by an expressway. The as-prepared membrane demonstrates an ionic conductivity of 9.83 × 10⁻⁴ S cm⁻¹ at room temperature and a high Li⁺ transference numbers of 0.68. This in situ coupling reaction method provides an effective way to resolve the problem of interface compatibility.     

The Synergetic Effect of Lithium Bisoxalatodifluorophosphate and Fluoroethylene Carbonate on Dendrite Suppression for Fast Charging Lithium Metal Batteries

Fluorinated solid‐electrolyte interphase (SEI) derived from fluoroethylene carbonate (FEC) is particularly favored for dendrite suppression in lithium metal batteries because of the high Young's modulus (≈64.9 Gpa) and low electronic conductivity (10^?31 S cm^?1) of LiF. However, the transportation ability of Li⁺ in this fluorinated SEI under high current densities is limited by the low ionic conductivity of LiF (≈10^?12 S cm^?1). Herein, by rational design, 0.1 m lithium bisoxalatodifluorophosphate (LiDFBOP) is adopted to modify fluorinated SEI in FEC based electrolyte for fast charging lithium metal batteries. Benefiting from the synergetic effect of LiDFBOP and FEC, a fluorinated SEI rich in LiF and Li_xPO_yF_z species can be yielded, which can further improve the stability and ionic conductivity of SEI for fast Li⁺ transportation. Meanwhile, the average coulombic efficiency for Li plating/stripping is improved from 92.0% to 96.7%, thus promoting stable cycling of Li||Li symmetrical batteries with dendrite free morphologies, even at high current densities (3.0 mA cm^?2) and high plating/stripping capacities (3.0 mAh cm^?2). More attractively, in practical Li||LiNi_0.6Co_0.2Mn_0.2O₂ batteries, the cycling life at 1C and rate capacities at 6C are also significantly improved. Therefore, the synergetic effect of LiDFBOP and FEC provides great potential for achieving advanced lithium metal batteries with fast charging ability.     

锂离子电池正极材料LiNi-x-yCoxMnyO2的研究现状

正极材料对锂离子电池的性能和价格具有决定性的作用，对正极材料的研究一直是锂离子电池研究中的热点。主要对一类新型正极材料LiNi-x-yCoxMnyO2的国内外研究现状进行了综述，并比较了不同合成方法对其电化学性能的影响，最后对这类正极材料的研究给予了展望。     

In Situ Formation of Polysulfonamide Supported Poly(ethylene glycol) Divinyl Ether Based Polymer Electrolyte toward Monolithic Sodium Ion Batteries

Sodium ion battery is one of the promising rechargeable batteries due to the low‐cost and abundant sodium sources. In this work, a monolithic sodium ion battery based on a Na₃V₂(PO₄)₃ cathode, MoS₂ layered anode, and polyether‐based polymer electrolyte is reported. In addition, a new kind of polysulfonamide‐supported poly(ethylene glycol) divinyl ether based polymer electrolyte is also demonstrated for monolithic sodium ion battery via in situ preparation. The resultant polymer electrolyte exhibits relatively high ionic conductivity (1.2 mS cm^?1) at ambient temperature, wide electrochemical window (4.7 V), and favorable mechanical strength (25 MPa). Moreover, such a monolithic Na₃V₂(PO₄)₃/MoS₂ sodium ion battery using this polymer electrolyte delivers outstanding rate capability (up to 10 C) and superior cyclic stability (84%) after 1000 cycles at 0.5 C. What is more essential, such a polymer electrolyte based soft‐package monolithic sodium ion cell can still power a red light emitting diode lamp and run finite times without suffering from any internal short‐circuit failures, even in the case of a bended and wrinkled state. Considering these aspects, this work no doubt provides a new approach for the design of a high‐performance polymer electrolyte toward monolithic sodium ion battery with exceptional rate capability and high safety.     

In Situ Construction of a LiF-Enriched Interface for Stable All-Solid-State Batteries and its Origin Revealed by Cryo-TEM

The application of solid polymer electrolytes (SPEs) is still inherently limited by the unstable lithium (Li)/electrolyte interface, despite the advantages of security, flexibility, and workability of SPEs. Herein, the Li/electrolyte interface is modified by introducing Li₂S additive to harvest stable all-solid-state lithium metal batteries (LMBs). Cryo-transmission electron microscopy (cryo-TEM) results demonstrate a mosaic interface between poly(ethylene oxide) (PEO) electrolytes and Li metal anodes, in which abundant crystalline grains of Li, Li₂O, LiOH, and Li₂CO₃ are randomly distributed. Besides, cryo-TEM visualization, combined with molecular dynamics simulations, reveals that the introduction of Li₂S accelerates the decomposition of N(CF₃SO₂)₂⁻ and consequently promotes the formation of abundant LiF nanocrystals in the Li/PEO interface. The generated LiF is further verified to inhibit the breakage of C O bonds in the polymer chains and prevents the continuous interface reaction between Li and PEO. Therefore, the all-solid-state LMBs with the LiF-enriched interface exhibit improved cycling capability and stability in a cell configuration with an ultralong lifespan over 1800 h. This work is believed to open up a new avenue for rational design of high-performance all-solid-state LMBs.     

LiNi3/8Co2/8Mn3/8O2正极材料氟掺杂改性研究

以共沉淀氢氧化物为前驱体制备了F-掺杂化合物LiNi_3/8Co_2/8Mn_3/8O_2-yF_y(y:0,0.05,0.10,0.20),采用XRD、XPS、SEM、循环伏安(CV)、充放电测试、DSC等表征了其结构与性能.结果表明,F^-掺杂置换部分O^2-生成固溶体,不改变样品中过渡金属离子的价态. F^-掺杂量y为0.05、0.10时,比容量不受影响,但在充放电过程中c_h方向膨胀率由未掺杂样的2.06％分别下降至1.017％、1.018％,改善了其结构稳定性与循环寿命,30周后容量保持率分别达97.5％、96.2％;而y增至0.20时,离子混乱度升高,且颗粒间烧结过于严重,内阻增加,使容量与循环特性再度恶化.F^-掺杂还促进材料烧结,使该材料粒径通过粉碎分级控制成为可能,有利于该材料电极的制备.另外,F^-掺杂也使LiNi_3/8Co_2/8Mn_3/8O₂热稳定性得到一定程度改善.     

锂硫电池硫/导电聚合物正极材料的研究进展

综述了锂硫电池硫/导电聚合物正极材料的研究进展。重点探讨了导电聚合物在硫基正极材料改性中的制备方法、结构设计,并对其中存在的问题进行了分析。最后对硫/导电聚合物正极材料的进一步发展及商业化应用进行了展望。     

In Situ Electrochemically Derived Amorphous‐Li2S for High Performance Li2S/Graphite Full Cell

High‐capacity Li₂S 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 Li₂S. In this work, a Li₂S/graphite full cell with the zero activation potential barrier is achieved through an in situ electrochemical conversion of Li₂S₈ catholyte into the amorphous Li₂S. Theoretical calculations indicate that the zero activation potential for amorphous Li₂S can be ascribed to its lower Li extraction energy than that of the crystalline Li₂S. The constructed Li₂S/graphite full cell delivers a high discharge capacity of 1006 mAh g^?1, indicating a high utilization of the amorphous Li₂S as a cathode. Moreover, a long cycle life with 500 cycles for this Li₂S/graphite full cell is realized. This in situ electrochemical conversion strategy designed here is inspired for developing high energy Li₂S‐based full cells in future.     

锂离子电池正极材料LiNiO2存在的问题与解决办法

锂离子电池正极材料LiNiO2存在合成困难、循环性能差和热稳定性差等问题．这些问题都与LiNiO2本身的晶体结构有关．本文从LiNiO2晶体结构入手，分析了产生这些问题的原因，并对解决这些问题的办法进行了简要的综述．现有研究资料表明，仅仅通过优化合成条件只能在一定程度上改善LiNiO2的循环性能，要从根本解决LiNiO2的存在问题，关键是通过掺杂改性稳定其晶体结构．     

锂离子电池正极材料LiMn2O4的研究进展

具有尖晶石相的LiMn2O4因价格低、无毒、无环境污染、制备简单、研究较成熟,因此有着很好的应用前景,被看作最有可能成为新一代商用锂离子二次电池正极材料.由于LiMn2O4电化学循环稳定性能不好,表现在可逆容量衰减较大,尤其在高温下(>55℃)使用衰减更严重,从而限制了它的商业化应用.经过近十几年的研究,人们对其衰减机理有了比较清晰的了解,提出了造成容量衰减的几种可能原因如Jahn-Teller畸变效应、Mn2+在电解质中的溶解、出现稳定性较差的四方相以及电解质的分解等.通过掺杂、表面包覆、制备工艺的改进,人们已能制得循环稳定性能较好的尖晶相材料.本文结合我们研究小组的最新研究成果对锂离子二次电池正极材料LiMn2O4的最新研究进展进行综述和评论.     

Carbon Nanotube–CoF2 Multifunctional Cathode for Lithium Ion Batteries: Effect of Electrolyte on Cycle Stability

Transition metal fluorides (MF_x) offer remarkably high theoretical energy density. However, the low cycling stability, low electrical and ionic conductivity of metal fluorides have severely limited their applications as conversion‐type cathode materials for lithium ion batteries. Here, a scalable and low‐cost strategy is reported on the fabrication of multifunctional cobalt fluoride/carbon nanotube nonwoven fabric nanocomposite, which demonstrates a combination of high capacity (near‐theoretical, ) and excellent mechanical properties. Its strength and modulus of toughness exceed that of many aluminum alloys, cast iron, and other structural materials, fulfilling the use of MF_x‐based materials in batteries with load‐bearing capabilities. In the course of this study, cathode dissolution in conventional electrolytes has been discovered as the main reason that leads to the rapid growth of the solid electrolyte interphase layer and attributes to rapid cell degradation. And such largely overlooked degradation mechanism is overcome by utilizing electrolyte comprising a fluorinated solvent, which forms a protective ionically conductive layer on the cathode and anode surfaces. With this approach, 93% capacity retention is achieved after 200 cycles at the current density of 100 mA g⁻¹ and over 50% after 10 000 cycles at the current density of 1000 mA g⁻¹.     

有机-无机杂化材料PANI/V2O5的制备及其电化性能

利用V2O5凝胶前驱体和苯胺单体在溶液中原位氧化聚合制备了V2O 5和聚苯胺(PANI)的有机-无机PANI/V2O5杂化材料,分别利用X-射线衍射(XRD)、热分析(TG-DTA)、扫描电镜(SEM)、红外光谱(FT-IR)技术对杂化材料进行了表征.用PANI/V2O5作为二次锂电池的正极材料,利用恒电流充放电技术对其进行电化学性能研究,实验表明该杂化材料具有较高的首次插锂容量,在0.1C放电倍率和1.50～4.0V的电压范围内具有288 mA·h·g-1的首次放电容量,在0.3C的放电倍率下循环30次后保持180mA·h·g-1的放电容量.