Rechargeable Li Metal Batteries Research Articles

The Progress of Polymer Composites Protecting Safe Li Metal Batteries: Solid-/Quasi-Solid Electrolytes and Electrolyte Additives.

The impressive theoretical capacity and low electrode potential render Li metal anodes the most promising candidate for next-generation Li-based batteries. However, uncontrolled growth of Li dendrites and associated parasitic reactions have impeded their cycling stability and raised safety concerns regarding future commercialization. The uncontrolled growth of Li dendrites and associated parasitic reactions, however, pose challenges to the cycling stability and safety concerns for future commercialization. To tackle these challenges and enhance safety, a range of polymers have demonstrated promising potential owing to their distinctive electrochemical, physical, and mechanical properties. This review provides a comprehensive discussion on the utilization of polymers in rechargeable Li-metal batteries, encompassing solid polymer electrolytes, quasi-solid electrolytes, and electrolyte polymer additives. Furthermore, it conducts an analysis of the benefits and challenges associated with employing polymers in various applications. Lastly, this review puts forward future development directions and proposes potential strategies for integrating polymers into Li metal anodes.

Accelerated Selective Li+ Transports Assisted by Microcrack-Free Anionic Network Polymer Membranes for Long Cyclable Lithium Metal Batteries.

Rechargeable Li metal batteries have the potential to meet the demands of high-energy density batteries for electric vehicles and grid-energy storage system applications. Achieving this goal, however, requires resolving not only safety concerns and a shortened battery cycle life arising from a combination of undesirable lithium dendrite and solid-electrolyte interphase formations. Here, a series of microcrack-free anionic network polymer membranes formed by a facile one-step click reaction are reported, displaying a high cation conductivity of 3.1 × 10-5 S cm-1 at high temperature, a wide electrochemical stability window up to 5V, a remarkable resistance to dendrite growth, and outstanding non-flammability. These enhanced properties are attributed to the presence of tethered borate anions in microcrack-free membranes, which benefits the acceleration of selective Li+ cations transport as well as suppression of dendrite growth. Ultimately, the microcrack-free anionic network polymer membranes render Li metal batteries a safe and long-cyclable energy storage device at high temperatures with a capacity retention of 92.7% and an average coulombic efficiency of 99.867% at 450 cycles.

Recovery of isolated lithium through discharged state calendar ageing.

Rechargeable Li-metal batteries have the potential to more than double the specific energy of the state-of-the-art rechargeable Li-ion batteries, making Li-metal batteries a prime candidate for next-generation high-energy battery technology1-3. However, current Li-metal batteries suffer from fast cycle degradation compared with their Li-ion battery counterparts2,3, preventing their practical adoption. A main contributor to capacity degradation is the disconnection of Li from the electrochemical circuit, forming isolated Li4-8. Calendar ageing studies have shown that resting in the charged state promotes further reaction of active Li with the surrounding electrolyte9-12. Here we discover that calendar ageing in the discharged state improves capacity retention through isolated Li recovery, which is in contrast with the well-known phenomenon of capacity degradation observed during the charged state calendar ageing. Inactive capacity recovery is verified through observation of Coulombic efficiency greater than 100% on both Li||Cu half-cells and anode-free cells using a hybrid continuous-resting cycling protocol and with titration gas chromatography. An operando optical setup further confirms excess isolated Li reactivation as the predominant contributor to the increased capacity recovery. These insights into a previously unknown pathway for capacity recovery through discharged state resting emphasize the marked impact of cycling strategies on Li-metal battery performance.

Artificial Li3N SEI-Enforced Stable Cycling of Li Powder Composite Anode in Carbonate Electrolytes

Lithium metal is considered one of the most attractive anode materials for next-generation batteries. However, the practical application of rechargeable Li-metal batteries has been hindered by the uncontrollable growth of Li dendrites and large volume changes during electrochemical cycling, leading to low Coulombic efficiency and safety concerns. This study reports a facile process of printing copper nitride nanowires (Cu3N NWs) onto Li metal powder (LMP) composite anode surface via a roll-pressing technique. Cu3N readily reacts with Li to form lithium nitride (Li3N), which is regarded as an excellent component for the interfacial layer on Li metal. The Li3N layer possesses a high ionic conductivity and ensures a homogeneous Li-ion flux, resulting in the suppression of dendrites. As a result, Li/Li symmetric cells assembled with the Li3N-LMP electrode exhibited lower overpotentials and superior cycling performance. Furthermore, NCM622/Li3N-LMP full cells demonstrated better capacity retention behavior (over 90% after 250 cycles) and higher discharge capacities during rate capability tests compared to the bare LMP cell. This study highlights the importance of a rational design of interfacial layers on LMP anodes for stable and long-term cycling.

Recent Progress on Nanomodification Applied in Anodes of Rechargeable Li Metal Batteries

Recent Progress on Nanomodification Applied in Anodes of Rechargeable Li Metal Batteries

Revealing the Mechanism Behind Sudden Capacity Loss in Lithium Metal Batteries

Rechargeable Li-metal batteries (LMBs) are attractive energy storage candidates for electric vehicles (EVs) because they offer higher energy density than batteries built with intercalation electrodes. However, one of the main barriers to the commercial deployment of LMBs has been their relatively short cycle life. Re-designing the electrolyte system shows promise in achieving acceptable cycle life, but even so, the resulting cells display a challenging end-of-life (EOL) behavior: a sudden capacity loss. Herein, we report a new method for analyzing voltage profiles during cycling to distinguish between the capacity loss originating from the loss of cathode capacity vs growth in cell resistance. This analysis reveals that sudden capacity loss was preceded by acceleration in the rate of growth of cell resistance, and cycling of multiple cells showed that this phenomenon is sensitive to the initial quantity of electrolyte in the cells. In contrast, the cathode capacity degraded at a constant rate independent of the electrolyte quantity. Combining this evidence with post-analysis of harvested electrolyte and electrodes, we conclude that neither the loss of active lithium nor the loss of active cathode material was the primary source of sudden capacity loss; instead, consumption and decomposition of electrolyte causes the drastic capacity loss at EOL.

A highly stable Li metal anode enabled by -SO3− group modification for high energy rechargeable Li metal batteries

A highly stable Li metal anode enabled by -SO3− group modification for high energy rechargeable Li metal batteries

(Invited) Dendrite Formation in Lithium Electrodeposition – Insights from Experiments and Modeling

High-energy density batteries are essential for powering future electric vehicles and electric aircrafts. The Li-metal anode offers the highest theoretical specific energy among practically available anode materials; however, a major hurdle in the progress towards rechargeable Li-metal batteries is the dendritic electrodeposition of Li metal during the battery charging process. The physicochemical mechanisms behind Li dendrite formation have been a topic of rich and fervent research, but many questions remain presently unanswered. Among these, a key question of significance to battery charging is: at what time instant is Li dendritic growth initiated? In the present talk, this question will be addressed through a combination of experiments and modeling. Chronopotentiometry during galvanostatic Li electrodeposition coupled with in situ optical microscopy reveals that the first emergence of Li dendrites corresponds to the time instant when the surface overpotential reaches a maximum.1 Electrochemical impedance spectroscopy shows that the increase in the surface overpotential preceding this maximum is due to gradual growth of the solid electrolyte interphase (SEI). This SEI layer growth induces Li+ concentration depletion at the electrode-SEI interface, promoting amplification of surface asperities and thus dendrites that rupture the SEI. A transport model incorporating Li+ diffusion across a growing SEI layer is developed, and shown to predict Li dendrite onset times that are in good agreement with experimental observations over a wide range of current densities, temperature, and initial SEI thicknesses.2 A key conclusion of our work is that liquid-phase mass transport limitations, often characterized by the Sand’s equation, do not reliably predict the onset of Li dendrites.3 Rather, transport characteristics and associated instabilities within solid-phase surface films on Li are predominantly responsible for dendrite formation. Our work provides clues for how dendrite formation could be arrested for enabling rechargeable Li-metal anodes for use in next-generation batteries.

Quantifying Capacity Loss Mechanisms of Li Metal Anodes Beyond Inactive Li0

Lithium metal anodes are promising alternatives to graphite for use in next-generation lithium-ion batteries due to their higher capacity (3,860 mAh/g vs. 372 mAh/g). However, Li anodes still display excessive capacity loss over cycling, leading to underwhelming Coulombic efficiency (CE, <99.9%) compared to graphite (>99.95%).1 These losses can derive from: (1) the formation of electronically isolated Li0 (often referred to as ‘dead’ or inactive’); and (2) the parasitic reactions between Li and the electrolyte that form the solid electrolyte interphase (SEI). Characterization of the Li anode has historically relied on surface characterization techniques such as XPS and FTIR, which cannot quantitatively reveal the total amounts of specific SEI phases. More precise quantification has recently become possible due to advances in chemical titration, which notably revealed that inactive Li0 is the dominant loss mechanism at low-to-moderate CE (<90%).2 At high CE (>90%), SEI losses are increasingly dominant and become the loss mode to minimize. Despite its importance, titration of SEI losses have thus far largely focused on LiH,3-5 with precise quantification of other accompanying phases still lacking.To bridge this gap, here we apply quantitative titration based on GC, ICP-AES and NMR to track an extended array of key SEI phases: semicarbonates (ROCO2Li), lithium carbide (Li2C2), olefins (RLi), LiF, P-containing phases, and total Li loss with, which teach new insights beyond inactive Li0. In 1 M LiPF6 EC/DEC, we demonstrate chemical resolution up to 71% of Li loss and 33% of SEI loss inventory. The analysis was also expanded to additional carbonate electrolytes of varying CEs (from <10% to >96%). Soluble SEI phases were particularly important at ultra-low CE (<10%), and their formation was suppressed higher CEs. Among the quantifiable SEI phases, ROCO2Li was consistently the major phase, but its proportions were invariant with CE. Instead, Li2C2, a minor phase, exhibited clear inverse correlation with CE. These results add further nuance beyond inactive Li0 to the current understanding of capacity loss, and demonstrate that, while minor phases often receive less focus and are harder to characterize, they can play governing roles in SEI function, particularly at high CE when formation of inactive Li0 is minimized. Hobold, G. M.; Lopez, J.; Guo, R.; Minafra, N.; Banerjee, A.; Shirley Meng, Y.; Shao-Horn, Y.; Gallant, B. M., Moving Beyond 99.9% Coulombic Efficiency for Lithium Anodes in Liquid Electrolytes. Nat. Energy 2021, 6 (10), 951-960. Fang, C.; Li, J.; Zhang, M.; Zhang, Y.; Yang, F.; Lee, J. Z.; Lee, M. H.; Alvarado, J.; Schroeder, M. A.; Yang, Y.; Lu, B.; Williams, N.; Ceja, M.; Yang, L.; Cai, M.; Gu, J.; Xu, K.; Wang, X.; Meng, Y. S., Quantifying Inactive Lithium in Lithium Metal Batteries. Nature 2019, 572 (7770), 511-515. Tao, M.; Xiang, Y.; Zhao, D.; Shan, P.; Sun, Y.; Yang, Y., Quantifying the Evolution of Inactive Li/Lithium Hydride and Their Correlations in Rechargeable Anode-Free Li Batteries. Nano Lett. 2022. Xu, G.; Li, J.; Wang, C.; Du, X.; Lu, D.; Xie, B.; Wang, X.; Lu, C.; Liu, H.; Dong, S.; Cui, G.; Chen, L., The Formation/Decomposition Equilibrium of LiH and Its Contribution on Anode Failure in Practical Lithium Metal Batteries. Angew. Chem. Int. Ed. Engl. 2021, 60 (14), 7770-7776. Xiang, Y.; Tao, M.; Zhong, G.; Liang, Z.; Zheng, G.; Huang, X.; Liu, X.; Jin, Y.; Xu, N.; Armand, M.; Zhang, J. G.; Xu, K.; Fu, R.; Yang, Y., Quantitatively Analyzing the Failure Processes of Rechargeable Li Metal Batteries. Sci. Adv. 2021, 7 (46), eabj3423.

Highly lithiophilic and structurally stable Cu–Zn alloy skeleton for high-performance Li-rich ternary anodes

Lithium (Li)-rich ternary alloy, comprising a multi-alloy phase as the built-in three-dimensional (3D) framework and a Li metal phase as a reversible Li reservoir, is a promising high-energy–density anode for rechargeable Li metal batteries. The introduction of metal/metalloid components to the alloy can effectively regulate Li deposition and maintain the dimensional integrity of the Li anode. Herein, the lithium–copper–zinc (Li–Cu–Zn) ternary alloy, as a new type of alloy anode, is synthesized via a facile thermal melting method. The fully delithiated 3D scaffold comprised two Cu–Zn alloy phases named CuZn and CuZn5. These alloy phases exhibit higher lithiophilicity and structural stability than Li–Zn and Li–Cu alloys. Moreover, the CuZn phase is electrochemically inert, ensuring the geometric stability of the anode, while the CuZn5 phase can readily undergo alloying reaction with Li to form the LiZn phase, thereby facilitating uniform Li nucleation and deposition. The hybridized multiphase alloy structure and specific energy storage mechanism of the Cu–Zn based alloy scaffold in the ternary alloy anode facilitate dendrite-free Li deposition and prolonged cycle lifetime. The Li metal full battery based on lithium iron phosphate (LiFePO4) cathode exhibits high cycling stability with high-capacity retention of 95.4% after 1000 cycles at 1C.

Morphology evolution of electrodeposited lithium on metal substrates

Lithium (Li) metal is deemed to be the high-energy-density anode material for next generation batteries, but its practical application is impeded by the uneven electrodeposition during charge of battery, which leads to the low Coulombic efficiency and potential safety issue. Here, multiscale modeling is fabricated to understand the morphology evolution of Li during electrodeposition process, from the self-diffusion of Li adatoms on electrode surface, to the nucleation process, and to the formation of Li microstructures, revealing the correlation between final morphology and deposition substrates. Energy batteries and self-diffusion of Li adatom on various substrates (lithium, copper, nickel, magnesium, and silver) result in the different nucleation size, which is calculated by kinetic Monte Carlo simulation based on classical nucleation theory. Formation of Li substructures that are grown from Li nuclei, is revealed by phase field modeling coupled with cellular automaton method. Our results show that larger Li nuclei is obtained under faster self-diffusion of Li adatom, leading to the low aspect ratio of Li substructures and the subsequent morphology evolution of electrodeposited Li. Furthermore, the electrodeposition of Li is strongly regulated by the selection of substrates, giving the practical guideline of anode design in rechargeable Li metal batteries. It is worthy to mention that this method to investigate the electro-crystallization process involving nucleation and growth can be transplanted to the other metallic anode, such as sodium, potassium, zinc, magnesium, calcium and the like.

Enabling Long Cycling with Excellent Structure Stability for High-Nickel Layered Cathodes in Lithium Metal Batteries

Rechargeable Li metal batteries (LMBs) constructed from Li metal and high-Ni NMCs have attracted much attention because of their high energy density in electrical vehicles. The choice of electrolyte plays a crucial role in determining the performance of Li||high-Ni NMC LMBs. In this work, we investigated the electrochemical performance and microstructure change of Li||0.7Nb-NMC 9055 LMBs using ether-based electrolyte (LiFSI–1.2DME–3TTE) and carbonate electrolyte (1 M LiPF6 in EC/DMC). The results show that ether-based electrolyte can significantly enhance the cycling life of Li||0.7Nb-NMC 9055 battery, providing a capacity of 203 mAh/g vs 179 mAh/g (carbonate electrolyte) for 150 cycles without voltage decay at C/5 charge and C/2 discharge rates. The excellent electrochemical performance (capacity and voltage) originates from the perfect structural stability confirmed by the dQ/dV versus V curves, which was further supported by electrochemical impedance spectroscopy test, showing nearly no surface charge transfer resistance increase in ether-based electrolyte, versus continuous growth in carbonate electrolyte.

Prefabrication of a Lithium Fluoride Interfacial Layer to Enable Dendrite-Free Lithium Deposition

Lithium metal is one of the most attractive anode materials for rechargeable batteries. However, its high reactivity with electrolytes, huge volume change, and dendrite growth upon charge or discharge lead to a low CE and the cycle instability of batteries. Due to the low surface diffusion resistance, LiF is conducive to guiding Li+ deposition rapidly and is an ideal component for the surface coating of lithium metal. In the current study, a fluorinated layer was prepared on a lithium metal anode surface by means of chemical vapor deposition (CVD). In the carbonate-based electrolyte, smooth Li deposits were observed for these LiF-coated lithium anodes after cycling, providing excellent electrochemical stability for the lithium metal anode in the liquid organic electrolyte. The CE of Li|Cu batteries increases from 83% for pristine Li to 92% for LiF-coated ones. Moreover, LiF-Li|LFP exhibits a decent rate and cycling performance. After 120 cycles, the capacity retention of 99% at 1C is obtained, and the specific capacity is maintained above 149 mAh/g. Our investigation provides a simple and low-cost method to improve the performance of rechargeable Li-metal batteries.

Solid electrolyte interphase-ization of Mg2+-blocking layers for lithium ions in anode-free rechargeable lithium metal batteries

A novel concept of solid electrolyte interphase (SEI)-ization of Mg2+-blocking layers for Li+ ions and its effect on their deposition in anode-free rechargeable Li-metal batteries (AFLMBs) has been introduced. The deposition quality of Li on Cu current collectors (CCs) has been improved by the addition of a moderate amount of Mg(N(CF3SO2)2)2 co-salt in Li+-containing carbonate-based electrolytes (Li–Mg electrolytes). Additional analyses revealed that thin, dense, and stable surface layers exhibiting permeability for Li+ and impermeability for Mg2+ ions were formed in Li–Mg electrolytes, significantly suppressing the Li dendrite growth and enhancing the deposited Li metal/Cu CC surface binding. As a result, the Mg2+-blocking layers acted as effective SEI layers from the perspective of Li+ ions, positively influencing the electrochemical performance of the AFLMB full cells.

3D Free‐Standing Carbon Nanofibers Modified by Lithiophilic Metals Enabling Dendrite‐Free Anodes for Li Metal Batteries

Li metal with high‐energy density is considered as the most promising anode for the next‐generation rechargeable Li metal batteries; however, the growth of Li dendrites seriously hinders its practical application. Herein, 3D free‐standing carbon nanofibers modified by lithiophilic metal particles (CNF/Me, Me=Sn, Fe, Co) are obtained in situ by the electrospinning method. Benefiting from the lithophilicity, the CNF/Me composite may effectively prevent the formation of Li dendrites in the Li metal batteries. The optimized CNF/Sn–Li composite electrode exhibits a stable cycle life of over 2350 h during Li plating/stripping. When matched with typical commercial LiFePO4 (LFP) cathode, the LFP//CNF/Sn–Li full cell presents a high initial discharge specific capacity of 139 mAh g−1 at 1 C, which remains at 146 mAh g−1 after 400 cycles. When another state‐of‐the‐art commercial LiNi0.8Co0.1Mn0.1O2 (NCM(811)) cathode is used, the assembled NCM//CNF/Sn–Li full cell shows a large initial specific discharge capacity of 206 mAh g−1 at substantially enhanced 10 C, which keeps at the good capacity of 99 mAh g−1 after 300 cycles. These results are greatly superior to the counterparts with Li as the anodes, indicating the great potential for practical utilization of the advanced CNF/Sn–Li electrode.

1,3,2-Dioxathiolane 2,2-Dioxide as a Bifunctional Electrolyte Additive to Enhance the Stability of Lithium Metal Anodes

Rechargeable Li-metal batteries (LMBs) are regarded as the future generation of prospective high-energy rechargeable battery systems. However, the strong reactivity of the Li metal is highly likely to cause side reactions with electrolytes, resulting in low coulombic efficiency (CE), and Li dendrite growth is the culprit of safety concerns. In this work, we report on a new approach utilizing 1,3,2-dioxathiolane 2,2-dioxide (DTD) additives in electrolytes to enhance the performance of LMBs. The mechanisms of the DTD molecule were investigated in detail using mass spectral titration, molecular dynamics simulations, and in situ optical microscopy. In general, the DTD molecule not only changes the Li-ion solvation structure but also optimizes the SEI component, which decreases the energy barrier for Li deposition and reduces the generation of “dead Li”. As a result, the deposition morphology of Li was totally changed, and the growth of Li dendrites was effectively suppressed. Electrochemical tests showed that the average CE of the Li||Cu half-cells was improved from 71.0% for 60 cycles to 95.8% for 275 cycles after the introduction of 5.0 wt % DTD in the carbonate electrolyte. Moreover, the Li||Li symmetric cell and the Li||NCM811 full cell exhibited significantly enhanced cycling stability.

Cu-CNTs current collector fabricated by deformation-driven metallurgy for anode-free Li metal batteries

Rechargeable anode-free Li metal batteries (AFLMBs) with improved energy density and reduced cost are beneficial for emission peak and carbon neutralization. Herein, multi-walled carbon nanotubes reinforced Cu matrix composite (Cu-CNTs) enabled by deformation-driven metallurgy (DDM) technology is proposed to retrieve the lithiophilicity of current collectors (CCs) in AFLMBs. Fine-grained Cu-CNTs with a large number of grain boundaries and homogenous distribution of broken CNTs are achieved based on the severe plastic deformation principle since the CNTs inhibit slide of dislocations and migration of grain boundaries. Grain boundaries in fine-grained Cu-CNTs with low-size distribution gradients provide desirable nucleation sites due to their higher disorder and active state. Excellent lithiophilicity of the broken CNTs is exhibited where its layered structure for Li ion insertion contributes to uniform Li deposition. Half cells assembled by Cu-CNTs CC with 2 vol% CNTs display advanced cycling stability with an average coulombic efficiency of 97.8% after 500 cycles at 1.0 mA‧cm−2. Full cells with LiFePO4 cathode possess excellent capacity retention of 69.4% after 100 cycles at 0.5 C. This work provides a novel strategy for fabricating CCs to achieve superior electrochemical performances for future applications of AFLMBs.

Tension-Induced Cavitation in Li-Metal Stripping.

Designing stable Li metal and supporting solid structures (SSS) is of fundamental importance in rechargeable Li-metal batteries. Yet, the stripping kinetics of Li metal and its mechanical effect on the supporting solids (including solid electrolyte interface) remain mysterious to date. Here, through nanoscale in situ observations of a solid-state Li-metal battery in an electron microscope, two distinct cavitation-mediated Li stripping modes controlled by the ratio of the SSS thickness (t) to the Li deposit's radius (r) are discovered. A quantitative criterion is established to understand the damage tolerance of SSS on the Li-metal stripping pathways. For mechanically unstable SSS (t/r< 0.21), the stripping proceeds via tension-induced multisite cavitation accompanied by severe SSS buckling and necking, ultimately leading to Li "trapping" or "dead Li" formation; for mechanically stable SSS (t/r> 0.21), the Li metal undergoes nearly planar stripping from the root via single cavitation, showing negligible buckling. This work proves the existence of an electronically conductive precursor film coated on the interior of solid electrolytes that however can be mechanically damaged, and it is of potential importance to the design of delicate Li-metal supporting structures to high-performance solid-state Li-metal batteries.

Introducing KI as a functional electrolyte additive to stabilize Li metal anode

A lithium metal battery (LMBs) is an excellent battery system for advanced electrochemical energy storage. However, the growth of lithium dendrites, the accumulation of inactive lithium, and the side reactions between lithium metal and electrolytes limit the cycling stability of LMBs. Herein, we introduce KI additive into lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)/ether-based electrolyte and lithium hexafluorophosphate (LiPF6)/ester-based electrolyte for cycling stability improvement of LMBs. Cu-mesh@Ag||Li half-cell with 0.01 M KI additive exhibits a Coulombic efficiency as high as 98.8 % over 200 cycles. The improved performance due to the electrostatic shielding effect formed by K+ at low concentration and the rapid recovery of inactive lithium by iodine redox. The corresponding Li||Li symmetrical cell shows an outstanding lifespan of 1400 h at 1.0 mA cm−2 with 1.0 mAh cm−2. Meanwhile, in the 1 M LiTFSI + 0.01 M KI electrolyte, the Cu-mesh@Ag-Li||LiFePO4 (LFP) full cell holds capacity retention of 91.7 % over 800cycles at 2.0 C, the Li||LiNi0.8Co0.1Mn0.1O2 (NCM811) full cell possesses much better capacity retention of 54 % after 500 cycles at 1.0 C. This work offers a cost-effective proposal to improve application potential with the electrolyte engineering of rechargeable Li metal batteries.

(Invited) Electrolyte Design for Wide-Temperature Li-Ion and Li-Metal Batteries

Improving the wide temperature operation of rechargeable batteries is vital to the operation of electronics in extreme environments, where systems capable of higher energy, high-rate discharge and long cycling are in short supply. In this talk, we will show electrolyte designs to achieve high-energy density and stable cycling performance in wide temperature range for both lithium-ion and lithium metal batteries. We will show how to circumvent the sluggish ion desolvation process found in typical lithium-ion batteries during discharge. These batteries are enabled by a novel ester electrolyte, which simultaneously provided high electrochemical stability and ionic conductivity at low temperature. Then we will extend the fundamental understanding developed from these system to other high-capacity, high-rate electrodes, leading to further improved energy density and stability for both high and extremely low temperatures, demonstrated by rechargeable Li metal batteries using both high-Ni oxide and sulfur cathodes.