Loosely coordinating diluted highly concentrated electrolyte toward -60℃ Li metal batteries

Lithium metal batteries(LMBs) promise energy density over 400 Wh kg^(-1).However,they suffer severe electrochemical performance deterioration at sub-zero temperatures.Such failure behavior highly correlates to inferior lithium metal anode(LMA) compatibility and sluggish Li^(+) desolvation.Here,we demonstrate that cyclopentylmethyl ether(CPME) based diluted high-concentration electrolyte(DHCE)enables-60℃ LMBs operation.By leveraging the loose coordination between Li^(+) and CPME,such developed electrolyte boosts the formation of ion clusters to derive anion-dominant interfacial chemistry for enhancing LMA compatibility and greatly accelerates Li^(+) desolvation kinetics.The resulting electrolyte demonstrates high Coulombic efficiencies(CE),providing over 99.5%,99.1%,98.5% and 95% at 25,-20,-40,and-60℃respectively.The assembled Li-S battery exhibits remarkable cyclic stability in-20,and-40℃ at 0.2 C charging and 0.5 C discharging.Even at-60℃,Li-S cell with this designed electrolyte retains> 70% of the initial capacity over 170 cycles.Besides,lithium metal coin cell and pouch cell with10 mg cm^(-2) high S cathode loading exhibit cycling stability at-20℃.This work offers an opportunity for rational designing electrolytes toward low temperature LMBs.

A Comparative Investigation of Single Crystal and Polycrystalline Ni-Rich NCMs as Cathodes for Lithium-Ion Batteries

Nickel-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM,1-x-y≥0.6)is known as a promising cathode material for lithium-ion batteries since its superiority of high voltage and large capacity.However,polycrystalline Ni-rich NCMs suffer from poor cycle stability,limiting its further application.Herein,single crystal and polycrystalline LiNi_(0.84)Co_(0.07)Mn_(0.09)O_(2)cathode materials are compared to figure out the relation of the morphology and the electrochemical storage performance.According to the Li^(+)diffusion coefficient,the lower capacity of single crystal samples is mainly ascribed to the limited Li+diffusion in the large bulk.In situ XRD illustrates that the polycrystalline and single crystal NCMs show a virtually identical manner and magnitude in lattice contraction and expansion during cycling.Also,the electrochemically active surface area(ECSA)measurement is employed in lithium-ion battery study for the first time,and these two cathodes show huge discrepancy in the ECSA after the initial cycle.These results suggest that the single crystal sample exhibits reduced cracking,surface side reaction,and Ni/Li mixing but suffers the lower Li^(+)diffusion kinetics.This work offers a view of how the morphology of Ni-rich NCM effects the electrochemical performance,which is instructive for developing a promising strategy to achieve good rate performance and excellent cycling stability.

Rational design of metal selenides nanomaterials for alkali metal ion(Li^(+)/Na^(+)/K^(+))batteries:current status and perspectives

Recently,metal selenides have obtained widespread attention as electrode materials for alkali(Li^(+)/Na^(+)/K^(+))batteries due to their promising theoretical capacity and mechanism.Nevertheless,metal selenides,similar to metal oxides and sulfides,also suffer from severe volume explosion during repeated charge/discharge processes,which results in the structure collapse and the following pulverization of electrode materials.Hence,it leads to poor cycle stability and influencing their further application.In order to solve these issues,some special strategies,including elemental doping,coupling with carbon materials,synthesis of the bimetal selenides with heterostructure,etc.,have been gradually applied to design novel electrode materials with outstanding electrochemical performance.Herein,the recent research progress on metal selenides as anodes for alkali ion batteries is summarized,including the regulation of crystal structure,synthesis strategies,modification methods,and electrochemical mechanisms and kinetics.Besides,the challenges of metal selenides and the perspective for future electrode material design are proposed.It is hoped to pave a way for the development of metal selenide electrode materials for the potential applications for alkali metal ion(Li^(+)/Na^(+)/K^(+))batteries.

Electrochemical Studies of Lithium Intercalation into Graphite Film Electrode for Li^+-ion Batteries

To study the electrochemical kinetic properties of the Li/Graphite system, cycle voltammerty (CV), ac-impedance and chro- noamperometry (CA) techniques have been used. The results showed that the diffusion of lithium ions in Li_xC_6 is the rate-determining step. The chemical diffusion coefficients of lithium (D_Li) have been estimated for different x values. As for the same material, the value of D_Li was calculated in order to compare the differences among the three techniques.

High-performance magnesium/sodium hybrid ion battery based on sodium vanadate oxide for reversible storage of Na^(+)and Mg^(2+)

Magnesium ion batteries(MIBs)are a potential field for the energy storage of the future but are restricted by insufficient rate capability and rapid capacity degradation.Magnesium-sodium hybrid ion batteries(MSHBs)are an effective way to address these problems.Here,we report a new type of MSHBs that use layered sodium vanadate((Na,Mn)V_(8)O_(20)·5H_(2)O,Mn-NVO)cathodes coupled with an organic 3,4,9,10-perylenetetracarboxylic diimide(PTCDI)anode in Mg^(2+)/Na^(+)hybrid electrolytes.During electrochemical cycling,Mg^(2+)and Na^(+)co-participate in the cathode reactions,and the introduction of Na^(+)promotes the structural stability of the Mn-NVO cathode,as cleared by several ex-situ characterizations.Consequently,the Mn-NVO cathode presents great specific capacity(249.9 mA h g^(−1)at 300 mA g^(−1))and cycling(1500 cycles at 1500 mA g^(−1))in the Mg^(2+)/Na^(+)hybrid electrolytes.Besides,full battery displays long lifespan with 10,000 cycles at 1000 mA g^(−1).The rate performance and cycling stability of MSHBs have been improved by an economical and scalable method,and the mechanism for these improvements is discussed.

离子色谱法同时测定样品中的Li^+、Na^+、NH_4^+、K^+、Mg^(2+)、Ca^(2+)离子

本文采用离子色谱法同时测定水样及烫发剂、脱毛膏、牙膏样品中的阳离子Ｌｉ＋、Ｎａ＋、ＮＨ＋４、Ｋ＋、Ｍｇ２＋、Ｃａ２＋，选用甲烷磺酸作淋洗液，测定方法的相关性好（ｒ＞０．９９９０），线性范围广，精密度高（ＲＳＤ％＜１．６），准确度好（ＲＳＤ％＜２．０），样品加标回收率为９２．２％～１０８．２％，检出限高。采用《饮用天然矿泉水标准检验方法》（ＧＢ８５３８）的方法作对比测定，测定位无明显差别。同时对酸度、共存非测定离子、相邻离子等干扰因素进行研究，确保测定的准确性，结果令人满意。

熔盐对Li^+/Na^+离子交换及折射率分布的影响

研究发现利用Li+ /Na+ 离子交换制取径向梯度折射率 (GRIN)棒透镜时 ,在NaNO3熔盐中 ,添加NaCl,会影响Li+ /Na+ 离子交换反应平衡 ,最终改变径向GRIN棒透镜的折射率分布、折射率差值及像差 并着重分析和讨论了在本实验中NaNO3+NaCl混合熔盐对径向GRIN棒透镜中折射率分布。

红细胞Na^+-Li^+反转运速率测定方法的改进

目的 建立适合临床方便快速进行Na+ Li+ 反转运速率测定 (Na+ Li+ countertransport,Na+ Li+ CT)方法。方法 将定量负荷过Li+ 的红细胞置于Na+ 介质中 ,单位时间以原子吸收发射法测定Na+ 介质中Li+ 浓度 ,即可计算出红细胞Na+ Li+ 反转运速率。结果 标本用 6mL全血在 4℃和室温时 ,须在 1h内测定。批内误差为高速率组 (1.45± 0 .15)mmol·h- 1·kg- 1Hb(CV =10 .3 % ) ,低速率组 (0 .62 1± 0 .0 72 )mmol·h- 1·kg- 1Hb (CV =11.6% )。结论 减少标本用量 ,缩短保温时间可行 。

Li^+、Na^+和Eu^(3+)共掺Lu_2O_3的制备及发光特性研究

用高温固相法合成了不同掺杂浓度的Li^+、Na^+和Eu^(3+)共掺Lu2O3闪烁体发光材料,使用XRD进行结构表征,用扫描电镜观察了样品形貌,测量了激发光谱、发射光谱,分析了Li+、Na+和Eu3+的掺杂浓度以及温度对合成样品发光强度的影响。结果显示,Li^+、Na^+掺杂摩尔分数分别为2.5%和1%,在800℃空气中煅烧2 h制备的Lu2O3∶5%Eu~ (3+)样品的发光最强。在同样条件下,比单掺2.5%Na+的样品发光强度提高1.89倍,比单掺2.5%Li+的样品发光强度提高3.97倍,比不掺Li+和Na+的样品发光强度提高6.43倍。

沉淀法制备Li^+、Na^+掺杂Gd_2O_3:Eu^(3+)荧光粉及发光特性研究

用沉淀法制备Li^+、Na^+和Eu^(3+)共掺Gd_2O_3荧光粉,并与微波-固相法制备的样品进行了比较。通过测量该粉体的XRD、激发光谱和发射光谱,比较了样品的微观结构和讨论了不同合成条件对Gd_2O_3:Eu^(3+)荧光粉发光特性的影响。结果显示在相同的条件下,对于未掺入Li^+的Gd_2O_3:Eu^(3+)样品比较,沉淀法制备样品的发光强度是微波-固相法制备样品的1.68倍;掺入Li^+的Gd_2O_3:Eu^(3+)样品比较,沉淀法制备样品的发光强度是微波—固相法制备样品的1.82倍。当使用草酸作为沉淀剂,掺杂浓度为Li^+(4.5 mol%)、Na^+(4.5mol%)、Eu^(3+)(4.5mol%),在800℃煅烧2h后获得样品的发光强度,是Gd_2O_3:Eu^(3+)荧光粉的5.91倍。

Insights into the enhanced structure stability and electrochemical performance of Ti^(4+)/F^(-) co-doped P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2) cathodes for sodium ion batteries at high voltage

P2-Na_(0.67)N_(i0.33)Mn_(0.67)O_(2)is considered as a promising cathode material for sodium-ion battery (SIBs)because of its high capacity and discharge potential.However,its practical use is limited by Na^(+)/vacancy ordering and P2-O2 phase transition.Herein,a Ti^(4+)/F^(-) co-doping strategy is developed to address these issues.The optimal P2-Na_(0.67)Ni_(0.33)Mn_(0.37)Ti_(0.3)O_(1.9)F_(0.1) exhibits much enhanced sodium storage performance in the high voltage range of 2.0–4.4 V,including a cycling stability of 77.2%over 300cycles at a rate of 2 C and a high-rate capability of 87.7 m Ah g^(-1) at 6 C.Moreover,the P2-Na_(0.67)Ni_(0.33)Mn_(0.37)Ti_(0.3)O_(1.9)F_(0.1) delivers reversible capacities of 82.7 and 128.1 m Ah g^(-1) at-10 and 50℃ at a rate of 2 C,respectively.The capacity retentions over 200 cycles at-10℃ is 94.2%,implying more opportunity for practical application.In-situ X-ray diffraction analysis reveals that both P2-O2 phase transitions and Na^(+)/vacancy ordering is suppressed by Ti^(4+)/F^(-) co-doping,which resulting in fast Na^(+) diffusion and stable phase structure.The hard carbon//P2-Na_(0.67)Ni_(0.33)Mn_(0.37)Ti_(0.3)O_(1.9)F_(0.1) full cell exhibits a high energy density of 310.2 Wh kg^(-1) and remarkable cyclability with 82.1%retention after 300 cycles at 1 C in the voltage range of 1.5–4.2 V.These results demonstrate that the co-doping Ti^(4+)/F^(-) is a promising strategy to improve the electrochemical properties of P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2),providing a facile tactic to develop high performance cathode materials for SIBs.

Li^(+)Solvation Mediated Interfacial Kinetic of Alloying Matrix for Stable Li Anodes

Severe lithium(Li)dendrite growth caused by the uneven overpotential deposition is a formidable challenge for high energy density Li metal batteries(LMBs).Herein,we investigate a synergetic interfacial kinetic to regulate Li deposition behavior and stabilize Li metal anode.Through constructing Li alloying matrix with a bi-functional silver(Ag)-Li_(3)N blended interface,fast Li^(+)conductivity and high Li affinity can be achieved simultaneously,resulting in both decreased Li nucleation and mass transfercontrolled overpotentials.Beyond these properties,a more important feature is demonstrated herein;that is,the inward diffusion depth of the Li adatoms inside of the Ag site can be restricted by the Li^(+)solvation structure in a highly coordinating environment.The latter feature can ensure the durability of the operational Ag sites,thereby elongating the Li protection ability of the Ag-Li_(3)N interface greatly.This work provides a deep insight into the synergetic effect of functional alloying structure and Li^(+)solvation mediated interfacial kinetic on Li metal protection.

Characteristics,materials,and performance of Ru-containing oxide cathode materials for rechargeable batteries

Li-rich Mn-based cathode materials have attracted extensive attention due to their remarkable energy density contributed by additional anionic redox.However,they always suffer from some undesired problems impeding their further commercialization such as irreversible oxygen loss,transition metal migration,sluggish kinetics and so on.Fortunately,the above issues can be relieved effectively when 3d metal Mn is replaced by 4d metal Ru.We focus on the recent progress of Ru-containing cathode materials and make a detailed summary in this review.At first,we attempt to combine and elucidate the relationship between oxygen and Ru redox.Subsequently,the up-to-date materials of Ru-based cathode materials for Li^(+)/Na^(+)batteries are concluded systematically.Afterward,the effects of Ru are discussed in depth including enhancing the reversibility of anionic redox and structural stability,modulating the ratio between cationic and anionic redox,improving the kinetics of Li^(+)/Na^(+),inhibiting the transition metal migration and so on.More importantly,the future designs of Ru-containing cathode materials are also proposed enlighteningly.We hope this review could offer some new perspectives to comprehend the layered oxides involving anionic redox and provide useful guidelines to achieve better Li^(+)/Na^(+)rechargeable batteries.

Suppressing dendritic metallic Li formation on graphite anode under battery fast charging

Lithium-ion batteries(LIBs)with fast-charging capability are essential for enhancing consumer experience and accelerating the global market adoption of electric vehicles.However,achieving fast-charging capability without compromising energy density,cycling lifespan,and safety of LIBs remains a significant challenge due to the formation of dendritic Li metal on graphite anode under fast charging condition.In view of this,the fundamentals for the dendritic metallic Li formation and the strategies for suppressing metallic Li plating based on analyzing the entire Li^(+)transport pathway at the anode including electrolyte,pore structure of electrode,and surface and bulk of materials are summarized and discussed in this review.Besides,we highlight the importance of designing thick electrodes with fast Li^(+)transport kinetics and comprehensively understanding the interaction between solid electrolyte interphase(SEI)and Li^(+)migration in order to avoid the formation of dendritic Li metal in practical fast-charging batteries.Finally,the regulation of Li metal plating with plane morphology,instead of dendritic structure,on the surface of graphite electrode under fast-charging condition is analyzed as a future direction to achieve higher energy density of batteries without safety concerns.

Heterogeneous engineering of MnSe@NC@ReS_(2) core-shell nanowires for advanced sodium-/potassium-ion batteries

Sodium-ion batteries(SIBs) and potassium-ion batteries(PIBs) have been attracting great attentions and widely been exploited due to the abundant sodium/potassium resources.Hence,the preparation of high-powered anode materials for SIBs/PIBs plays a decisive role for the commercial applications of SIBs/PIBs in the future.Manganese selenides are a class of potential anode materials for SIBs/PIBs because of their small band gap and high electrical conductivity.In this work,MnSe and ReS_(2) core-shell nanowires connecting by polydopamine derived carbon nanotube(MnSe@NC@ReS_(2)) have been successfully synthesized from growing ReS_(2) nanosheets array on the surface of MnSe@NC nano wires,which present excellent Na^(+)/K^(+) storage performance.While applied as SIBs anode,the specific capacity of 300 mAh·g^(-1) was maintwined after 400 cycles at the current density of 1.0 A·g^(-1).Besides,it could also keep 120 mAh·g^(-1) specific capacity after 900 cycles at 1.0 A·g^(-1) for the anode of PIBs.These heterogeneous engineering and one-dimensional-two-dimensional(1D-2D) hybrid strategies could provide an ideal strategy for the synthesis of new hetero-structured anode materials with outstanding battery performance for SIBs and PIBs.

Lithium-ion and solvent co-intercalation enhancing the energy density of fluorinated graphene cathode

Fluorinated carbons CF_xhold the highest theoretical energy density(e.g.,2180 W h kg^(-1)when x=1)among all cathode materials of lithium primary batteries.However,the low conductivity and severe polarization limit it to achieve its theory.In this study,we design a new electrolyte,namely 1 M LiBF_(4)DMSO:DOL(1:9 vol.),achieving a high energy density in Li/CF_xprimary cells.The DMSO with a small molecular size and high donor number successfully solvates Li^(+)into a defined Li^(+)-solvation structure.Such solvated Li^(+)can intercalate into the large-spacing carbon layers and achieve an improved capacity.Consequently,when discharged to 1.0 V,the CF_(1.12)cathode demonstrates a specific capacity of 1944 m A h g^(-1)with a specific energy density of 3793 W h kg^(-1).This strategy demonstrates that designing the electrolyte is powerful in improving the electrochemical performance of CF_(x) cathode.

Boosting rate performance of layered lithium-rich cathode materials by oxygen vacancy induced surface multicomponent integration

The rapid development of electric vehicles and portable energy storage systems demands improvements in the energy density and cost-effectiveness of lithium-ion batteries,a domain in which Lithium-rich layered cathode(LLO)materials inherently excel.However,these materials face practical challenges,such as low initial Coulombic efficiency,inferior cycle/rate performance,and voltage decline during cycling,which limit practical application.Our study introduces a surface multi-component integration strategy that incorporates oxygen vacancies into the pristine LLO material Li1.2Mn_(0.6)Ni_(0.2)O_(2).This process involves a brief citric acid treatment followed by calcination,aiming to explore rate-dependent degradation behavior.The induced surface oxygen vacancies can reduce surface oxygen partial pressure and diminish the generation of O_(2)and other highly reactive oxygen species on the surface,thereby facilitating the activation of Li ions trapped in tetrahedral sites while overcoming transport barriers.Additionally,the formation of a spinel-like phase with 3D Li+diffusion channels significantly improves Li^(+)diffusion kinetics and stabilizes the surface structure.The optimally modified sample boasts a discharge capacity of 299.5 mA h g^(-1)at a 0.1 C and 251.6 mA h g^(-1)at a 1 C during the initial activation cycle,with an impressive capacity of 222.1 mA h g^(-1)at a 5 C.Most notably,it retained nearly 70%of its capacity after 300 cycles at this elevated rate.This straightforward,effective,and highly viable modification strategy provides a crucial resolution for overcoming challenges associated with LLO materials,making them more suitable for practical application.

Strategies to enhance Li^(+) transference number in liquid electrolytes for better lithium batteries

Growing market demand from portable electronics to electric automobiles boosts the development of lithium-ion batteries(LIBs)with high energy density and rate performance.However,strong solvation effect between lithium ions(Li^(+))and solvent molecules in common electrolytes limits the mobility of Li^(+)ions in electrolytes.Consequently,anions dominate the charge conduction in electrolytes,and in most cases,the value of Li^(+)transference number(T_(+))is between 0.2 and 0.4.A low T_(+)will aggravate concentration polarization in the process of charging and discharging,especially at high rate,which not only increases the overpotential but also intensifies side reactions,along with uneven deposition of lithium(Li)and the growth of lithium dendrites when lithium metal is used as anode.In this review,promising strategies to improve T_(+)in liquid electrolytes would be summarized.The migration of Li^(+)ions is affected directly by the types and concentration of lithium salts,solvents,and additives in bulk electrolytes.Besides,Li^(+)ions will pass through the separator and solid electrolyte interphase(SEI)when transferring between anodes and cathodes.With this in mind,we will classify and summarize threads of enhancing T_(+)from five aspects:lithium salts,solvents,additives,separators,and SEI based on different mechanisms,including covalently bonding,desolvation effect,Lewis acid-base interaction,electrostatic interaction,pore sieving,and supramolecular interaction.We believe this review will present a systematic understanding and summary on T_(+)and point out some feasible threads to enhance battery performance by enhancing T_(+).

Mitigating kinetic hindrance of single-crystal Ni-rich cathodes through morphology modulation,nickel reduction,and lithium vacancy generation achieved by terbium doping

Single crystallization has proven to be effective in enhancing the capacity and stability of Ni-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(SNCM)cathode materials,particularly at high cut-off voltages.Nevertheless,the synthesis of high-quality single-crystal particles remains challenging because of severe particle agglomeration and irregular morphologies.Moreover,the limited kinetics of solid-phase Li^(+)diffusion pose a significant concern because of the extended diffusion path in large single-crystal particles.To address these challenges,we developed a Tb-doped single-crystal LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(SNCM-Tb)cathode material using a straightforward mixed molten salt sintering process.The Tb-doped Ni-rich single crystals presented a quasi-spherical morphology,which is markedly different from those reported in previous studies.Tb^(4+)oping significantly enhanced the dynamic transport of Li^(+)ions in the layered oxide phase by reducing the Ni valence state and creating Li vacancies.A SNCM-Tb material with 1 at%Tb doping shows a Li^(+)diffusion coefficient up to more than 9 times higher than pristine SNCM in the non-diluted state.In situ X-ray diffraction analysis demonstrated a significantly facilitated H1-H2-H3 phase transition in the SNCM-Tb materials,thereby enhancing their rate capacity and structural stability.SNCM-Tb exhibited a reversible capacity of 186.9 mA h g^(-1)at 5 C,retaining 94.6%capacity after 100 cycles at 0.5 C under a 4,5 V cut-off.Our study elucidates the Tb^(4+)doping mechanisms and proposes a scalable method for enhancing the performance of single-crystal Ni-rich NCM materials.

A water-stable high-voltage P3-type cathode for sodium-ion batteries

The Na-deficient P3-type layered oxide cathode material usually experience complex in-plane Na^(+)/vacancy ordering rearrangement and undesirable P3-O3 phase transitions in the high-voltage region,leading to inferior cycling performance.Additionally,they exhibit unsatisfactory stability when exposed to water for extended periods.To address these challenges,we propose a Cu/Ti co-doped P3-type cathode material(Na_(0.67)Ni_(0.3)Cu_(0.03)Mn_(0.6)Ti_(0.07)O_(2)),which effectively mitigates Na^(+)/vacancy ordering and suppresses P3-O3 phase transitions at high voltages.As a result,the as-prepared sample exhibited outstanding cyclic performance,with 81.9%retention after 500 cycles within 2.5–4.15 V,and 75.7%retention after300 cycles within 2.5–4.25 V.Meanwhile,it demonstrates enhanced Na^(+)transport kinetics during desodiation/sodiation and reduced growth of charge transfer impedance(R_(ct))after various cycles.Furthermore,the sample showed superb stability against water,exhibiting no discernible degradation in structure,morphology,or electrochemical performance.This co-doping strategy provides new insights for innovative and prospective cathode materials.