Structurally tunable characteristics of ionic liquids for optimizing lithium plating/stripping via electrolyte engineering

Electrolyte chemistry offers the opportunity to regulate the solid electrolyte interphase(SEI) and Li^(+)solvation,which is considered to be crucial to the growth of lithium crystals for safe lithium metal batteries(LMBs).Structurally tunable characteristics of ionic liquids(ILs) from anion type,cationic substituent chain length and cationic substituents,will contribute this field.Here,we explore the influence mechanism of imidazole-based ILs as electrolyte additives on Li+solvation and the formation of SEI.ILs can participate into the formation of efficient SEI,together with cathode electrolyte interphase(CEI).Moreover,ILs can also regulate the sheath structure of Li^(+)solvation,to fasten the kinetics of Li.Furthermore,the imidazole-based cations with long alkyl chain can form an electrostatic shield around newly formed Li nucleus,and suppress further Li plating at this site.Under the optimized condition,the 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide([OMIm]TFSI) additive shows the best ability to enhance the electrochemical performance,endowing the Li||Li symmetric cell with a stable life(over800 h) at 0.5 mA cm^(-2) and the Li||LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2)(NMC622) full cell with a high capacity of 141.7 mAh g^(-1) after 200 cycles at 0.5 C.

Diethyl phenylphosphonite contributing to solid electrolyte interphase and cathode electrolyte interphase for lithium metal batteries

Lithium metal batteries have obtained increasing interest due to their high specific capacity.Nonetheless,the growth of lithium dendrites brings safety risks to batteries and further deteriorates the performance.Herein,we explore diethyl phenylphosphonite(DEPP) as the electrolyte additive to alleviate this problem.DEPP can be preferentially decomposed than carbonate solvents to form the stable interface between electrolyte and lithium anode for inhibiting the dendrite growth.As expected,the symmetrical LiIILi cells could achieve a stable cycling performance with 200 h at 1 mA cm^(-2).Moreover,DEPP can be preferentially oxidized on the surface of lithium cobalt oxides(LiCoO_(2)) to form a dense cathode electrolyte interphase(CEI) film for suppressing the continuous oxidative decomposition of the electrolyte and eliminating the adverse effects of HF on the battery.This endows LiCoO_(2) IILi full battery with the enhanced cycling and rate performance.

Research progress in failure mechanisms and electrolyte modification of high-voltage nickel-rich layered oxide-based lithium metal batteries

High-voltage nickel(Ni)-rich layered oxide-based lithium metal batteries(LMBs)exhibit a great potential in advanced batteries due to the ultra-high energy density.However,it is still necessary to deal with the challenges in poor cyclic and thermal stability before realizing practical application where cycling life is considered.Among many improved strategies,mechanical and chemical stability for the electrode electrolyte interface plays a key role in addressing these challenges.Therefore,extensive effort has been made to address the challenges of electrode-electrolyte interface.In this progress,the failure mechanism of Ni-rich cathode,lithium metal anode and electrolytes are reviewed,and the latest breakthrough in stabilizing electrode-electrolyte interface is also summarized.Finally,the challenges and future research directions of Ni-rich LMBs are put forward.

电解液添加剂多因子设计原则:以金属锂电池电解液添加剂全氟烷基磺酸钾盐为例

随着便携式电子设备、电动汽车、智能电网等领域的快速发展,市场对于高能量密度储能器件的需要日益增长.以石墨为负极的传统锂离子电池能量密度有限,尤其是与电动汽车动力电池的发展目标(300~500 Wh kg-1)尚有较大差距.因此,研究开发新一代电池技术十分迫切[1].

Electrolytes enriched by potassium perfluorinated sulfonates for lithium metal batteries

Lithium(Li) metal is widely considered as a promising anode for next-generation lithium metal batteries(LMBs) due to its high theoretical capacity and lowest electrochemical potential. However, the uncontrollable formation of Li dendrites has prevented its practical application. Herein, we propose a kind of multifunctional electrolyte additives(potassium perfluorinated sulfonates) from the multi-factor principle for electrolyte additive molecular design(EDMD) view to suppress the Li dendrite growth. The effects of these additives are revealed through experimental results, molecular dynamics simulations and firstprinciples calculations. Firstly, K^(+)can form an electrostatic shield on the surface of Li anode to prevent the growth of Li dendrites. Secondly, potassium perfluorinated sulfonates can improve the activity of electrolytes as co-conductive salts, and lower the electro-potential of Li nucleation. Thirdly, perfluorinated sulfonate anions not only can change the Li^(+)solvation sheath structure to decrease the desolvation energy barrier and increase the ion migration rate, but also can be partly decomposed to form the superior solid electrolyte interphase(SEI). Benefited from the synergistic effects, an outstanding cycle life over250 h at 1 m A cm^(-2) is achieved in symmetric Li||Li cells. In particular, potassium perfluorinated sulfonate additives(e.g., potassium perfluorohexyl sulfonate, denoted as K+PFHS) can also contribute to the formation of high-quality cathode electrolyte interphase(CEI). As a result, Li||LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2) full cells exhibit significantly enhanced cycling stability. This multi-factor principle for EDMD offers a unique insight on understanding the electrochemical behavior of ion-type electrolyte additives on both the Li metal anode and high-voltage cathode.

Cotton-derived oxygen/sulfur co-doped hard carbon as advanced anode material for potassium-ion batteries

Hard carbon is regarded as promising anode materials for potassium-ion batteries(KIBs)owing to their low price and easy availability.However,the limited rate capability still needs to be improved.Herein,we demonstrate the fabrication of oxygen/sulfur co-doped hard carbon through a facile hydrolyzationsulfuration process of skimmed cotton.The simultaneous dopants significantly improve potassium ion diffusion rate.When served as the anode for KIBs,this hydrolyzed hard carbon delivered a high reversible capacity(409 mAh/g at 0.1 A/g),superior rate capability(135 mAh/g at 2 A/g)and excellent cyclability(about 120 mAh/g overt 500 cycles at 2 A/g).This work provides a facile strategy to prepare low-cost doped-hard carbon with superior potassium storage property.

宽温域锂电池电解液研究进展

锂电池因具有高能量密度、长循环寿命、无记忆效应等优点,在储能设备市场领域取得了巨大的成功.应用场景的拓展是锂离子电池发展的方向之一,航天、军事装备、极地探索等新型应用场景的不断增加,要求锂离子电池应具有更宽的工作温度区间,因此,开发宽温域锂电池技术迫在眉睫.然而过低的工作温度会带来电解液黏度增大、电池内阻增大、电池可逆容量下降、电化学反应路径改变等问题;过高的工作温度则会对电解液/电极界面、电极材料稳定性带来挑战,带来副反应增多的问题.开发适用于宽温域锂电池的电解液体系是解决上述问题的关键.基于此,本文将从极端温度对于电池运行机理的影响、高温以及低温电解液等方面,探讨近年来宽温域锂电池电解液的研究进展,并针对领域内需要解决的问题和未来发展方向进行展望.

Electrolyte chemistry for lithium metal batteries

Li metal batteries(LMBs) are considered as the next-generation energy storage systems because of their high energy density.However,due to the high reactivity of Li metal with the electrolyte,the unwanted safety concerns inhibit the practical application of LMBs.To overcome these drawbacks,exploring suitable electrolytes is considered to be urgent.Great effort has been made to modify electrolytes to achieve the stability of LMBs.In this review,different kinds of LMBs are firstly introduced.Then,the regulation of electrode–electrolyte interphase is discussed.Next,recent advances on the functional electrolytes for LMBs are overviewed,including fireproof electrolytes,extreme-temperature electrolytes and high-voltage electrolytes.Finally,the perspective on the development of future electrolytes is provided.

Porous surfur-doped hard carbon for excellent potassium storage

Hard carbon is promising anode for potassium-ion batteries(PIBs),however,the poor rate capability hinders its development as potential anode.To address this question,we design a sulfur-doped porous hard carbon(S-HC)for PIBs through the combination of structural design and composition adjustment.The as-designed S-HC exhibits a long cycling life with^191 mAh/g after 300 cycles at 1 A/g,and an excellent rate capability with^100 mAh/g at 5 A/g,which was attributed to its structural characteristics and compositions.The S-HC demonstrates to be promising anode in the future.

Stabilizing the cycling stability of rechargeable lithium metal batteries with tris(hexafluoroisopropyl)phosphate additive

The application of rechargeable lithium metal batteries(LMBs)has been hindered by the fast growth of lithium dendrites during charge and the limited cycling life because of the decomposition of the electrolyte at the interface.Here,we have developed a non-flammable triethyl phosphate(TEP)-based electrolyte with tris(hexafluoroisopropyl)phosphate(THFP)as an additive.The polar nature of the C–F bonding and the rich CF3 groups in THFP lowers its LUMO energy and HOMO energy to help form a stable,Li F-rich solid electrolyte interphase(SEI)layer through the reduction of THFP and increases the binding ability of the PF6-anions,which significantly suppresses lithium dendrite growth and reduces the electrolyte decomposition.Moreover,THFP participates in the formation of a thin,C–F rich electrolyte interphase(CEI)layer to provide the stable cycling of the cathode at a high voltage.The symmetric Li||Li and full Li/NCM622 cells with THFP additive have small polarization and long cycling life,which demonstrates the importance of the additive to the application of the LMBs.

2020 roadmap on two-dimensional materials for energy storage and conversion

Energy storage and conversion have attained significant intere st owing to its important applications that reduce CO2 emission through employing green energy.Some promising technologies are included metalair batteries,metal-sulfur batteries,metal-ion batteries,electrochemical capacitors,etc.Here,metal elements are involved with lithium,sodium,and magnesium.For these devices,electrode materials are of importance to obtain high performance.Two-dimensional(2 D) materials are a large kind of layered structured materials with promising future as energy storage materials,which include graphene,black phosporu s,MXenes,covalent organic frameworks(COFs),2 D oxides,2 D chalcogenides,and others.Great progress has been achieved to go ahead for 2 D materials in energy storage and conversion.More researchers will join in this research field.Under the background,it has motivated us to contribute with a roadmap on ’two-dimensional materials for energy storage and conversion.

Pseudo-concentrated electrolytes for lithium metal batteries

Lithium metal batteries suffer from short lifespans and low Coulombic efficiency (CE) due to the high reactivity of Li and the poor stability of the solid electrolyte interphase (SEI). Herein, we propose the concept of a pseudo-concentrated electrolyte (PCE) induced by an electron-deficient additive (4-pyridylboronic acid;4-PBA) to form a robust, LiF-rich SEI, thus addressing the above issues. Molecular dynamics simulations confirm that 4-PBA can increase the coordination number of PF6^(-) anions in the Li+ solvation sheath to achieve pseudo-concentrated LiPF6 in the electrolyte. Moreover, the 4-PBA can scavenge harmful PF5 decomposed from LiPF6 to stabilize the LiF-rich SEI. The resulting robust LiF-rich SEI promotes Li growth along the SEI/Li interface and represses the growth of Li dendrites. Thus, excellent performance is achieved, with a high CE of 97.1% for a Li||Cu cell at 1.0 ​mA ​cm^(−2), and over 950 cycles at 0.5 ​mA ​cm^(−2) for Li||Li symmetric cells with 1.0 ​wt% 4-PBA electrolyte. Meanwhile, the resulting stable boron-containing cathode electrolyte interphase enables Li||LiNi0·6Co0·2Mn0·2O_(2) (NCM622) cells to achieve excellent stability, with a capacity retention of 86.9% after 200 cycles.

Breakthrough on understanding the solid electrolyte interphase

Solid electrolyte interphase(SEI)is derived from electrolyte decomposition,and considered as extremely crucial interface,which has a huge influence on the reversible operation of lithium-ion batteries(LIBs)and lithium metal batteries(LMBs)[1-3],e.g.,the irreversible capacity,internal resistance,Coulombic efficiency,and cycling life of batteries[4-10].However,our knowledge on SEI components and structures is still limited although SEI has been studied for several decades.