Understanding the failure mechanism towards developing high-voltage single-crystal Ni-rich Co-free cathodes

Benefited from its high process feasibility and controllable costs,binary-metal layered structured LiNi_(0.8)Mn_(0.2)O_(2)(NM)can effectively alleviate the cobalt supply crisis under the surge of global electric vehicles(EVs)sales,which is considered as the most promising nextgeneration cathode material for lithium-ion batteries(LIBs).However,the lack of deep understanding on the failure mechanism of NM has seriously hindered its application,especially under the harsh condition of high-voltage without sacrifices of reversible capacity.Herein,singlecrystal LiNi_(0.8)Mn_(0.2)O_(2) is selected and compared with traditional LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM),mainly focusing on the failure mechanism of Cofree cathode and illuminating the significant effect of Co element on the Li/Ni antisite defect and dynamic characteristic.Specifically,the presence of high Li/Ni antisite defect in NM cathode easily results in the extremely dramatic H2/H3 phase transition,which exacerbates the distortion of the lattice,mechanical strain changes and exhibits poor electrochemical performance,especially under the high cutoff voltage.Furthermore,the reaction kinetic of NM is impaired due to the absence of Co element,especially at the single-crystal architecture.Whereas,the negative influence of Li/Ni antisite defect is controllable at low current densities,owing to the attenuated polarization.Notably,Co-free NM can exhibit better safety performance than that of NCM cathode.These findings are beneficial for understanding the fundamental reaction mechanism of single-crystal Ni-rich Co-free cathode materials,providing new insights and great encouragements to design and develop the next generation of LIBs with low-cost and high-safety performances.

How do high-voltage cathode and PEO electrolyte get along well?EIS analysis mechanism&potentiometric control strategy

PEO-based all-solid-state electrolytes are extensively utilized and researched owing to their exceptional safety,low-mass-density,and cost-effectiveness.However,the low oxidation potential of PEO makes the interface problem with the high-voltage cathode extremely severe.In this work,the impedance of PEO-based all-solid-state batteries with high-voltage cathode(NCM811)was studied at different potentials.The Nyquist plots displayed a gyrate arc at low-frequencies for NCM811/PEO interface.Based on the kinetic modeling,it was deduced that there is a decomposition reaction of PEO-matrix in addition to de-embedded reaction of NCM811,and the PEO intermediate product(dehydra-PEO)adsorbed on the electrode surface leading to low-frequency inductive arcs.Furthermore,the distribution of relaxation time shows the dehydra-PEO results in the kinetic tardiness of the charge transfer process in the temporal dimension.Hence,an artificial interface layer(CEI_(x))was modified on the surface of NCM811 to regulate the potential of cathode/electrolyte interface to prevent the high-voltage deterioration of PEO.NCM/CEI_(x)/PEO batteries exhibit capacity retentions of 96.0%,84.6%,and 76.8%after undergoing 100 cycles at cut-off voltages of 4.1,4.2,and 4.3 V,respectively.Therefore,here the failure mechanism of high-voltage PEO electrolyte is investigated by EIS and a proposed solving strategy is presented.

Degradation analysis and doping modification optimization for high-voltage P-type layered cathode in sodium-ion batteries

Advancing high-voltage stability of layered sodium-ion oxides represents a pivotal avenue for their progress in energy storage applications.Despite this,a comprehensive understanding of the mechanisms underpinning their structural deterioration at elevated voltages remains insufficiently explored.In this study,we unveil a layer delamination phenomenon of Na_(0.67)Ni_(0.3)Mn_(0.7)O_(2)(NNM)within the 2.0-4.3 V voltage,attributed to considerable volumetric fluctuations along the c-axis and lattice oxygen reactions induced by the simultaneous Ni^(3+)/Ni^(4+)and anion redox reactions.By introducing Mg doping to diminished Ni-O antibonding,the anion oxidation-reduction reactions are effectively mitigated,and the structural integrity of the P2 phase remains firmly intact,safeguarding active sites and precluding the formation of novel interfaces.The Na_(0.67)Mg_(0.05)Ni_(0.25)Mn_(0.7)O_(2)(NMNM-5)exhibits a specific capacity of100.7 mA h g^(-1),signifying an 83%improvement compared to the NNM material within the voltage of2.0-4.3 V.This investigation underscores the intricate interplay between high-voltage stability and structural degradation mechanisms in layered sodium-ion oxides.

High-Voltage and Fast-Charging Lithium Cobalt Oxide Cathodes: From Key Challenges and Strategies to Future Perspectives

Lithium-ion batteries(LIBs)with the“double-high”characteristics of high energy density and high power density are in urgent demand for facilitating the development of advanced portable electronics.However,the lithium ion(Li+)-storage performance of the most commercialized lithium cobalt oxide(LiCoO_(2),LCO)cathodes is still far from satisfactory in terms of high-voltage and fast-charging capabilities for reaching the double-high target.Herein,we systematically summarize and discuss high-voltage and fast-charging LCO cathodes,covering in depth the key fundamental challenges,latest advancements in modification strategies,and future perspectives in this field.Comprehensive and elaborated discussions are first presented on key fundamental challenges related to structural degradation,interfacial instability,the inhomogeneity reactions,and sluggish interfacial kinetics.We provide an instructive summary of deep insights into promising modification strategies and underlying mechanisms,categorized into element doping(Li-site,cobalt-/oxygen-site,and multi-site doping)for improved Li+diffusivity and bulkstructure stability;surface coating(dielectrics,ionic/electronic conductors,and their combination)for surface stability and conductivity;nanosizing;combinations of these strategies;and other strategies(i.e.,optimization of the electrolyte,binder,tortuosity of electrodes,charging protocols,and prelithiation methods).Finally,forward-looking perspectives and promising directions are sketched out and insightfully elucidated,providing constructive suggestions and instructions for designing and realizing high-voltage and fast-charging LCO cathodes for next-generation double-high LIBs.

Unique double-layer solid electrolyte interphase formed with fluorinated ether-based electrolytes for high-voltage lithium metal batteries

Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.

Electric field and force characteristic of dust aerosol particles on the surface of high-voltage transmission line

High-voltage transmission lines play a crucial role in facilitating the utilization of renewable energy in regions prone to desertification. The accumulation of atmospheric particles on the surface of these lines can significantly impact corona discharge and wind-induced conductor displacement. Accurately quantifying the force exerted by particles adhering to conductor surfaces is essential for evaluating fouling conditions and making informed decisions. Therefore, this study investigates the changes in electric field intensity along branched conductors caused by various fouling layers and their resulting influence on the adhesion of dust particles. The findings indicate that as individual particle size increases, the field strength at the top of the particle gradually decreases and eventually stabilizes at approximately 49.22 k V/cm, which corresponds to a field strength approximately 1.96 times higher than that of an unpolluted transmission line. Furthermore,when particle spacing exceeds 15 times the particle size, the field strength around the transmission line gradually decreases and approaches the level observed on non-adhering surface. The electric field remains relatively stable. In a triangular arrangement of three particles, the maximum field strength at the tip of the fouling layer is approximately 1.44 times higher than that of double particles and 1.5 times higher compared to single particles. These results suggest that particles adhering to the transmission line have a greater affinity for adsorbing charged particles. Additionally, relevant numerical calculations demonstrate that in dry environments, the primary adhesion forces between particles and transmission lines follow an order of electrostatic force and van der Waals force. Specifically, at the minimum field strength, these forces are approximately74.73 times and 19.43 times stronger than the gravitational force acting on the particles.

Pairing nitroxyl radical and phenazine with electron-withdrawing/-donating substituents in “water-in-ionic liquid” for high-voltage aqueous redox flow batteries

Aqueous redox-active organic materials-base electrolytes are sustainable alternatives to vanadium-based electrolyte for redoxflow batteries(RFBs)due to the advantages of high ionic conductivity,environmentally benign,safety and low cost.However,the underexplored redox properties of organic materials and the narrow thermodynamic electrolysis window of water(1.23 V)hinder their wide applications.Therefore,seeking suitable organic redox couples and aqueous electrolytes with a high output voltage is highly suggested for advancing the aqueous organic RFBs.In this work,the functionalized phenazine and nitroxyl radical with electron-donating and electron-withdrawing group exhibit redox potential of-0.88 V and 0.78 V vs.Ag,respectively,in“water-in-ionic liquid”supporting electrolytes.Raman spectra reveal that the activity of water is largely suppressed in“water-in-ionic liquid”due to the enhanced hydrogen bond interactions between ionic liquid and water,enabling an electrochemical stability window above 3 V.“Water-in-ionic liquid”supporting electrolytes help to shift redox potential of nitroxyl radical and enable the redox activity of functionalized phenazine.The assembled aqueous RFB allows a theoretical cell voltage of 1.66 V and shows a practical discharge voltage of 1.5 V in the“water-in-ionic liquid”electrolytes.Meanwhile,capacity retention of 99.91%per cycle is achieved over 500 charge/discharge cycles.A power density of 112 mW cm^(-2) is obtained at a current density of 30 mA cm^(-2).This work highlights the importance of rationally combining supporting electrolytes and organic molecules to achieve high-voltage aqueous RFBs.

1,3,5-Trifluorobenzene endorsed EC-free electrolyte for high-voltage and wide-temperature lithium-ion batteries

Ethylene carbonate(EC)is susceptible to the aggressive chemistry of nickel-rich cathodes,making it undesirable for high-voltage lithium-ion batteries(LIBs).The arbitrary elimination of EC leads to better oxidative tolerance but always incurs interfacial degradation and electrolyte decomposition.Herein,an EC-free electrolyte is deliberately developed based on gradient solvation by pairing solvation-protection agent(1,3,5-trifluorobenzene,F_(3)B)with propylene carbonate(PC)/methyl ethyl carbonate(EMC)formulation.F_(3)B keeps out of inner coordination shell but decomposes preferentially to construct robust interphase,inhibiting solvent decomposition and electrode corrosion.Thereby,the optimized electrolyte(1.1 M)with wide liquid range(-70–77℃)conveys decent interfacial compatibility and high-voltage stability(4.6 V for LiNi_(0.6)Mn_(0.2)Co_(0.2)O_(2),NCM622),qualifying reliable operation of practical NCM/graphite pouch cell(81.1%capacity retention over 600 cycles at 0.5 C).The solvation preservation and interface protection from F_(3)B blaze a new avenue for developing high-voltage electrolytes in next-generation LIBs.

Towards extreme fast charging of 4.6 V LiCoO_(2) via mitigating high-voltage kinetic hindrance

High-voltage LiCoO_(2)(LCO) is an attractive cathode for ultra-high energy density lithium-ion batteries(LIBs) in the 3 C markets.However,the sluggish lithium-ion diffusion at high voltage significantly hampers its rate capability.Herein,combining experiments with density functional theory(DFT) calculations,we demonstrate that the kinetic limitations can be mitigated by a facial Mg^(2+)+Gd^(3+)co-doping method.The as-prepared LCO shows significantly enhanced Li-ion diffusion mobility at high voltage,making more homogenous Li-ion de/intercalation at a high-rate charge/discharge process.The homogeneity enables the structural stability of LCO at a high-rate current density,inhibiting stress accumulation and irreversible phase transition.When used in combination with a Li metal anode,the doped LCO shows an extreme fast charging(XFC) capability,with a superior high capacity of 193.1 mAh g^(-1)even at the current density of 20 C and high-rate capacity retention of 91.3% after 100 cycles at 5 C.This work provides a new insight to prepare XFC high-voltage LCO cathode materials.

Lithium plating-free 1 Ah-level high-voltage lithium-ion pouch battery via ambi-functional pentaerythritol disulfate

Elevating the charge cut-off voltage beyond traditional 4.2 V is a commonly accepted technology to increase the energy density of Li-ion batteries(LIBs) but the risk of Li-dendrites and fire hazard increases as well. The use of ambi-functional additive, which forms stable solid electrolyte interphase(SEI) simultaneously at both cathode and anode, is a key to enabling a dendrites-free and well-working high-voltage LIB. Herein, a novel ambi-functional additive, pentaerythritol disulfate(PEDS), at 1 wt% without any other additive is demonstrated. We show the feasibility and high impacts of PEDS in forming lithium sulfateincorporated robust SEI layers at NCM523 cathode and graphite anode in 1 Ah-level pouch cell under4.4 V, 25 °C and 0.1 C rate, which mitigates the high-voltage instability, metal-dissolution and cracks on NCM523 particles, and prevents Li-dendrites at graphite anode. Improved capacity retention of 83%after 300 cycles is thereby achieved, with respect to 69% with base electrolyte, offering a promising path toward the design of practical high-energy LIBs.

Stress wave analysis of high-voltage pulse discharge rock fragmentation based on plasma channel impedance model

High-voltage pulse discharge(HVPD)rock fragmentation controls a plasma channel forming inside the rock by adjusting the electrical parameters,electrode type,etc.In this work,an HVPD rock fragmentation test platform was built and the test waveforms were measured.Considering the effects of temperature,channel expansion and electromagnetic radiation,the impedance model of the plasma channel in the rock was established.The parameters and initial values of the model were determined by an iterative computational process.The model calculation results can reasonably characterize the development of the plasma channel in the rock and estimate the shock wave characteristics.Based on the plasma channel impedance model,the temporal and spatial distribution characteristics of the radial stress and tangential stress in the rock were calculated,and the rock fragmentation effect of the HVPD was analyzed.

Recent Advances in Electrolytes for High-Voltage Cathodes of Lithium-Ion Batteries

With the increasing scale of energy storage,it is urgently demanding for further advancements on battery technologies in terms of energy density,cost,cycle life and safety.The development of lithium-ion batteries(LIBs)not only relies on electrodes,but also the functional electrolyte systems to achieve controllable formation of solid electrolyte interphase and high ionic conductivity.In order to satisfy the needs of higher energy density,high-voltage(>4.3 V)cathodes such as Li-rich layered compounds,olivine LiNiPO_(4),spinel LiNi_(0.5)Mn_(1.5)O_(4) have been extensively studied.However,high-voltage cathodebased LIBs fade rapidly mainly owing to the anodic decomposition of electrolytes,gradually thickening of interfacial passivation layer and vast irreversible capacity loss,hence encountering huge obstacle toward practical applications.To tackle this roadblock,substantial progress has been made toward oxidation-resistant electrolytes to block its side reaction with high-voltage cathodes.In this review,we discuss degradation mechanisms of electrolytes at electrolyte/cathode interface and ideal requirements of electrolytes for high-voltage cathode,as well as summarize recent advances of oxidation-resistant electrolyte optimization mainly from solvents and additives.With these insights,it is anticipated that development of liquid electrolyte tolerable to high-voltage cathode will boost the large-scale practical applications of high-voltage cathode-based LIBs.

A Tip-Inhibitor Interphase Embedded with Soluble Polysulfides for High-Voltage Li Metal Batteries

The high-voltage battery has now become a goal in order to meet the demands for high energy density.However,the severe side reactions between Li metal and carbonate-based electrolytes in this system result in unstable interphase,leading to non-uniform Li-ion flux and thus aggravating the dendrite growth of Li.The protect interphase,traditional solid electrolyte interface(SEI),is a loose solid layer consisted of many components,which generally does not possess the function of preventing the lithium budding.Herein,based on polysulfide solubility in ester,we proposed a strategy to eliminate the dendrite by constructing a unique SEI in which the dynamic polysulfides were in situ formed and encapsuled.For this purpose,a 2-fluorophenylsulfur pentafluoride(2-FSPF)was employed as an additive in carbonate-based electrolyte that can be decomposed electrochemically during battery operation to form such a polysulfide-rich interphase.These polysulfides with certain fluidity can adhere to dynamically the budding tip of Li metal,as a so-called tip-inhibitor,when the local current density of the tip rising,thus to hinder Li^(+)diffusion toward the tip,resulting in inhibiting the further growth of Li dendrites and leveling the Li deposition.At the current density of 1 mA cm^(-2),the average Coulombic efficiency of Li//Cu cells is as high as 98.39%during 600 cycles,and the stable cycling of Li//Li symmetric cell reaches 3500 h.Furthermore,due to the high anodic stability,the Li//high-voltage LiCoO_(2)(LCO)full cells and Li–O_(2)battery achieve excellent cycle performance with lean electrolyte.

Rationalizing Na-ion solvation structure by weakening carbonate solvent coordination ability for high-voltage sodium metal batteries

Commercial carbonate-based electrolytes feature highly reactive activities with alkali metals,yielding low Coulombic efficiencies and poor cycle life in lithium metal batteries,which possess much higher chemical activity in the rising star sodium metal batteries.To be motivated,we have proposed that decreasing the solvent solvation ability in carbonate-based electrolytes stepwise could enable longterm stable cycling of high-voltage sodium metal batteries.As the solvation capacity reduces,more anions are enticed into the solvation sheath of Na^(+),resulting in the formation of the more desirable interphase layers on the surface of the anode and the cathode.The inorganic-dominated interphases allow highly efficient Na^(+)deposition/stripping processes with a lower rate of dead sodium generation,as well as maintain a stable structure of the high-voltage cathode material.Specifically,the assembled Na||Na_(3)V_(2)(PO_(4))_(2)F_(3)battery exhibits an accelerated ion diffusion kinetics and achieves a higher capacity retention of 85.9%with during the consecutive 200 cycles under the high voltage of 4.5 V.It is anticipated that the tactics we have proposed could be applicable in other secondary metal battery systems as well.

The influence of pore characteristics on rock fragmentation mechanism by high-voltage electric pulse

High-voltage electric pulse(HVEP)is an innovative low-energy and high-efficiency technique.However,the underlying physics of the electrical breakdown within the rock,and the coupling mechanism between the various physical fields involved in HVEP still need to be further understood.In this study,we establish a 2D numerical model of multi-physical field coupling of the electrical breakdown of porous rock with randomly distributed pores to investigate the effect of pore characteristics(porosity,pore media composition)on the partial electrical breakdown of rock(i.e.the generation of a plasma channel inside the rock).Our findings indicate that the generation of a plasma channel is directionally selective and extends in the direction of a weak electrical breakdown intensity.As the porosity of the rock increases,so does the intensity of the electric field in the‘electrical damage’region—the greater the porosity,the greater the effectiveness of rock-breaking.As the fraction of pore fluid(S_(water)/S_(air))gradually declines,the generation time of the plasma channel decreases,and the efficacy of rock-breaking by HVEP increases.In addition,in this study,we conducted an indoor experiment utilizing an electric pulse drill to break down the rock in order to recreate the growth mode of the plasma channel in the rock.Moreover,the experimental results are consistent with the simulation results.In addition,the development of this type of partial electrical breakdown is confirmed to be related to electrode polarity and pore characteristics via the experiment of the symmetrical needle-needle electrode arrangement,which further demonstrates the mechanism of partial electrical breakdown.This research is significant for comprehending the process of electric impulse rock-breaking and gives theoretical guidance and technological support for advancing electric impulse drilling technology.

External-to-internal synergistic strategy to enable multi-scale stabilization of LiCoO_(2)at high-voltage

High-voltage LiCoO_(2)(LCO)offers a prelude to breaking the bottleneck of the energy density of lithium-ion batteries,however,LiCoO_(2)is subject to serious structural and interfacial degradation above voltages>4.55 V(vs.Li/Li^(+)).Herein,an in-situ Li_(6.25)La_(3)Zr_(2)A_(l0.25)O_(12)(LLZAO)layer is constructed on the LCO surface to achieve operating voltage at 4.6 V.The detailed characterizations(ex-situ XRD,ex-situ Raman,DFT,etc.)reveal that the LLZAO layer greatly enhances Li+conductivity attributed to the ionconducting layer on the surface/interface,and closely combines with LiCoO_(2)particle to ensure stable cathode/electrolyte interface,thus suppressing the highly reactive Co^(4+)and O^(-)triggered surface side reactions at high-voltage.Moreover,the introduction of La^(3+)/Zr^(4+)/Al^(3+)with a larger ionic radius(La^(3+)/Zr^(4+)are larger than Co^(3+))and weaker electronegativity(La/Zr/Al are weaker than Co)into Co^(3+)sites readjusts the electron cloud density between Co–O–Li,which reinforces the Co–O bond and widens the band-center gap of Co 3d and O 2p,thus restraining the detrimental phase transition(from H3 to H1-3 phase)and the formation of Co_(3)O_(4)spinel phase(attributed to lattice oxygen release),subsequently alleviating the particle cracking and structural collapse during repeated Li^(+)de/intercalation.Therefore,after 100 cycles at 3.0–4.6 V,LCO@1.0LLZAO exhibits a superior discharge capacity of 188.5 m A h g^(-1),with a capacity retention of 85.1%.The above research has brought about meaningful guidance for the evolution of cathode materials with high voltage.

A dilute fluorine-free electrolyte design for high-voltage hybrid aqueous batteries

Fluorinated salts and/or high salt concentrations are usually necessary to produce protective films on the electrodes for high-voltage aqueous batteries,yet these approaches increase the cost,toxicity and reaction resistances of battery.Herein,we report a dilute fluorine-free electrolyte design to overcome this dilemma.By using the LiClO_(4) salt and polyethylene glycol dimethyl ether(PED)solvent and optimizing the LiClO_(4)/PED/H_(2)O molar ratio,we formulate a 1 mol kg^(-1)3 V-class hybrid aqueous electrolyte that enables reversible charge/discharge of 2.5 V LiMn_(2)O_(4)|Li_(4)Ti_(5)O_(12) full cell at both low(0.5C,92.4%capacity retention in 300 cycles)and high(5C,80.4%capacity retention in 2000 cycles)rates.This excellent performance is reached even without the generation of protective film on either anode or cathode as identified by in/ex situ characterizations.The selection of appropriate ingredients that have both high stability and strong interactions with water is critical to widen the potential window of electrolyte while suppressing parasitic reactions on the electrodes.This work suggests that expensive and toxic fluorinate salts are no longer necessary for 3 V-class aqueous electrolytes,boosting the development of low-cost,environmentally-friendly,high-power and high-energy-density aqueous batteries.

Hybrid solid electrolyte interphases formed in conventional carbonate electrolyte enable high-voltage and ultra-stable magnesium metal batteries

Magnesium metal batteries are considered as viable alternatives of lithium-ion batteries for their low cost and high capacity of magnesium.Nevertheless,the practical application of magnesium metal batteries is extremely challenging due to a lack of suitable electrolyte that can stabilize magnesium metal anode and high-voltage cathode simultaneously.Herein,we found that in-situ formed lithium/magnesium hybrid electrolyte interphases in conventional LiPF6-containing carbonate-based electrolyte can not only prevent the production of passivation layer on the magnesium metal anode,but also inhibit the oxidation of the electrolyte under high voltage.The symmetric magnesium‖magnesium battery can achieve reversible stripping/plating for 1600 and 600 h at 0.02 and 0.1 mA cm^(-2),respectively.In addition,when coupled with a carbon fiber cathode,the magnesium metal battery exhibited a capacity retention rate of 96.3% for 1000 cycles at a current density of 500 mA g^(-1)and presented a working voltage of ~3.1 V.This research paves a new and promising path to the commercialization process of rechargeable magnesium metal batteries.

Anion-Regulated Weakly Solvating Electrolytes for High-Voltage Lithium Metal Batteries

Development of advanced high-voltage electrolytes is key to achieving high-energy-density lithium metal batteries(LMBs).Weakly solvating electrolytes(WSE)can produce unique anion-driven interphasial chemistry via altering the solvating power of the solvent,but it is difficult to dissolve the majority of Li salts and fail to cycle at a cut-off voltage above 4.5 V.Herein,we present a new-type WSE that is regulated by the anion rather than the solvent,and the first realize stable cycling of dimethoxyethane(DME)at 4.6 V without the use of the“solvent-in-salt”strategy.The relationships between the degree of dissociation of salts,the solvation structure of electrolytes,and the electrochemical performance of LMBs were systematically investigated.We found that LiBF_(4),which has the lowest degree of dissociation,can construct an anion-rich inner solvation shell,resulting in anion-derived anode/cathode interphases.Thanks to such unusual solvation structure and interphasial chemistry,the Li-LiCoO_(2)full cell with LiBF_(4)-based WSE could deliver excellent rate performance(115 mAh g^(-1)at 10 C)and outstanding cycling stability even under practical conditions,including high loading(10.7 mg cm^(-2)),thin Li(50μm),and limited electrolyte(1.2μL mg^(-1)).

Easily Obtaining Excellent Performance High-voltage LiCoO_(2)via Pr_(6)O_(11)Modification

Developing an effective method to synthesize high-performance high-voltage LiCoO_(2) is essential for its industrialization in lithium batteries(LIBs).This work proposes a simple mass-produced strategy for the first time,that is,negative temperature coefficient thermosensitive Pr_(6)O_(11) nanoparticles are uniformly modified on LiCoO_(2) to prepare LiCoO_(2)@Pr_(6)O_(11)(LCO@PrO)via a liquid-phase mixing combined with annealing method.Tested at 274 mA g−1,the modified LCO@PrO electrodes deliver excellent 4.5 V high-voltage cycling performance with capacity retention ratios of 90.8%and 80.5%at 25 and 60℃,being much larger than those of 22.8%and 63.2%for bare LCO electrodes.Several effective strategies were used to clearly unveil the performance enhancement mechanism induced by Pr_(6)O_(11) modification.It is discovered that Pr_(6)O_(11) can improve interface compatibility,exhibit improved conductivity at elevated temperature,thus enhance the Li^(+)diffusion kinetics,and suppress the phase transformation of LCO and its resulting mechanical stresses.The 450 mAh LCO@PrO‖graphite pouch cells show excellent LIB performance and improved thermal safety characteristics.Importantly,the energy density of such pouch cell was increased even by~42%at 5 C.This extremely convenient technology is feasible for producing high-energy density LIBs with negligible cost increase,undoubtedly providing important academic inspiration for industrialization.