High-energy Batteries Research Articles

Safer lithium-ion batteries realized by electrolyte with thermoresponsive poly(vinylidene fluoride-co-trifluoroethylene)

The increasingly widespread use of electric vehicles has necessitated the development of high-energy batteries capable of operating under harsh conditions, e.g., at elevated temperatures and high charge/discharge rates. Hence, considerable attention has been focused on enhancing the safety of lithium-ion batteries (LIBs). Herein, a thermoresponsive polymer, poly(vinylidene fluoride-co-trifluoroethylene) with 75 mol% vinylidene fluoride and 25 mol% trifluoroethylene (TrFE-25), is employed as an electrolyte additive to enhance the thermal stability of LIBs (LiCoO2/graphite full cells). Under thermal-abuse conditions, i.e., above a certain threshold temperature, the TrFE-25-containing electrolyte turns into a gel, thereby abruptly increasing of the electrolyte viscosity and interfacial resistance. The gel layers block ion transport, suppress exothermic reactions between the electrodes and electrolyte, and hinder separator shrinkage via adhesive bonding to the anode and cathode, thus preventing internal short-circuiting and enhancing battery safety. According to the results of cycling tests, the addition of TrFE-25 to the baseline electrolyte has no negative effects under normal conditions. Therefore, the proposed methodology holds promise for improving the safety of LIBs, particularly those with flammable carbonate-based electrolytes, and paves the way for the widespread use of these batteries in electric vehicles.

A novel polymeric lithicone coating for superior lithium metal anodes

Lithium metal (Li) is commonly regarded as the “holy grail” of rechargeable batteries and can serve as anodes for constituting various high-energy lithium metal batteries (LMBs). However, it suffers from two notorious issues: (1) continuous formation of inhomogeneous solid electrolyte interphase and (2) Li dendritic growth. In this study, we developed a novel polymeric lithicone via a new molecular layer deposition (MLD) process, using lithium tert-butoxide (LTB) and hydroquinone (HQ) as precursors. We revealed that such an MLD process enabled the resultant LiHQ to grow linearly in a highly controllable and cyclic mode at a growth rate of 4 Å cycle−1. Furthermore, its low process deposition temperature of 150 °C made it possible to practice high-quality coatings over Li anodes directly. We demonstrated that, very compellingly, this LiHQ coating could protect Li anodes from corrosion and dendritic growth. As a consequence, this LiHQ coating has enabled Li||Li symmetric cells an extremely long cyclability up to 8000 Li-plating/stripping cycles without failure. More excitingly, we demonstrated that, coupled with LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes, the LiHQ-modified Li anodes could help the resultant Li||NMC811 realize a much better capacity retention and much longer cyclability. Thus, this study represents a strategic route for developing commercializeable LMBs.

Partial cationic exchange boosting sodium storage of NaVP2O7

Sodium vanadium pyrophosphate (NaVP2O7 or NVP) with KAlP2O7-type structure exhibits an elevated redox potential (3.9 V vs. Na/Na+) compared to other vanadium-based polyanion cathodes, which enhances its superiority for high-energy sodium-ion batteries (SIBs), but encounters with the low Na+ conduction. Herein, we propose a cation exchange strategy to generate a skeleton-expanded Na1-xKxVP2O7 (x ≈ 0.25, denoted as NKVP) cathode stemming from its pyrophosphate counterpart KVP2O7. Different from previous entire ion-exchange method, the partial retained K skeleton in NKVP expanded the Na-ion conduction bottleneck to facilitate the Na-ions to across, lowered the Na-ion diffusion barriers (0.33 to 0.27 eV), which directly boosted Na-ion diffusion kinetics. As a result, the NKVP exhibited much higher specific capacity than NVP (73.8 vs. 25.2 mAh g−1), and it remained 55.7 % even at 40C (4.1 A g−1), surpassing most of pyrophosphate cathode. This was also verified at high-rate NKVP//NaTi2(PO4)3 and NKVP//hard‑carbon full cells. Moreover, the expanded bottleneck also reinforced the structure stability, enabling the NKVP cycle at 10C over 2200 cycles. This research opens new avenues for the design of high-rate and long-cycling polyanionic materials.

Initiating cationic-anionic chemistry with stepwise surface-to-inner conversion in copper selenide superstructures for high-energy rechargeable magnesium batteries

Copper selenides are viewed as the most capable cathode materials for rechargeable magnesium batteries, yet suffer from unsatisfactory energy density due to their low operating voltage plateau (∼0.9 V vs. Mg/Mg2+) and insufficient reversible capacity. Herein, a stepwise conversion from surface cationic-anionic redox to inside electrochemical displacement reaction is realized in copper selenide (Cu2-xSe) superstructure cathodes. A highly reversible high-voltage platform at ∼1.6 V is discovered during discharge process. Ex-situ spectroscopy and microscopy results demonstrate that the high-voltage plateau is contributed by surface Cu2+ charge-carrier transformation and anionic Se2– redox reaction while sufficient inner Cu-Mg replacement conversion at low-voltage region. Following the favorable mechanism, the Cu2-xSe superstructure cathodes can present high specific capacity of 385.4 mAh g–1 at 0.1 A g–1 and outstanding energy density of 426.3 Wh kg–1. Moreover, the Cu2-xSe superstructure cathodes also maintain a reversible capacity of 223.6 mAh g–1 over 700 cycles with 0.0147 % capacity degradation per cycle at 1.0 A g–1 and long-term charge-discharge lifetime for 3000 cycles at 5.0 A g–1. This research reports a new Mg2+ storage mechanism for copper selenide cathodes and provides novel route to develop high-energy-density rechargeable magnesium batteries.

The high-fluorinated bi-molecular combination enables high-energy lithium batteries under challenging environment

The drawbacks of temperature sensitivity, high voltage intolerance, and flammability of lithium batteries are gradually brought to light in conventional carbonate electrolytes. To solve these problems, a localized high concentration electrolyte (LHCE) employing highly fluorinated ethyl trifluoroacetate (TFAE) and 2,2,3,3-tetrafluoro-1-(1,1,2,2-tetrafluoroethoxy) propane (TFEP) is designed. When applied in high-energy lithium batteries, the discharge specific capacity of Li||NMC811 battery can maintain 143.6 mAh/g after 500 cycles at 4.6 V and 1C, and the capacity retention of Li||LNMO battery retains as high as 89.99 % after 500 cycles at 5 V. In addition, this LHCE also possesses the ability to operate the battery under challenging conditions including low temperature, fast charge, safety risks, etc. The LHCE based on TFAE and TFEP has unique solvated structures to generate a moderate LiF-rich interfacial layer, ensuring the fast Li+ migration. This work will provide strong guidance for future electrolyte industrial design of high-energy lithium battery.

Borate modified Co-free LiNi0.5Mn1.5O4 cathode material: A pathway to superior interface and cycling stability in LNMO/graphite full-cells

Cobalt-free LiNi0.5Mn1.5O4 (LNMO) holds great promise as a next-generation cathode material for high-energy and high-power density lithium-ion batteries (LIBs), making it a key contender for large-scale energy storage systems (ESS) and transportation applications. Despite its potential, the commercial utilization of LNMO has been impeded by its rapid capacity deterioration attributed to an unstable LNMO/electrolyte interface caused by the intrinsically high operating voltage of LNMO. Here, we present a pragmatic and scalable strategy to improve the LNMO/electrolyte interface through borate-based surface coating of the LNMO. Optimizing the coating process yielded high-rate capability and stable LNMO/electrolyte interface analyzed by extended float tests. Borate-LNMO materials show superior cycling stability at 25 °C and 45 °C, attributed to a robust cathode electrolyte interphase (CEI) formation. The bare LNMO and 0.25-B2O3-LNMO demostrated a cycling stability of around 41.20 % and 62.50 % respectively after 1000 cycles in LNMO/graphite full-cells. Post-mortem X-ray photoelectron spectroscopy (XPS) analysis revealed fewer side reaction products on borate-LNMO cathodes compared to bare LNMO. Additionally, scanning electron microscopy (SEM) revealed a thicker and denser solid-electrolyte interphase (SEI) on cycled graphite anodes from bare LNMO cells, while a thin and robust SEI was observed on graphite from borate-LNMO cells. Finally, we have conclusively demonstrated that the primary aging mechanism in LNMO/graphite full cells stems from the instability at the LNMO/electrolyte or/and graphite/electrolyte interface, rather than material-related degradation phenomenon. These compelling outcomes underscore the potential of cathode material surface coating in general and especially of borate coating on LNMO as a promising and cost-effective enabler for the use of LNMO in next-generation LIBs.

Multiple uniform lithium-ion transport channels in Li6.4La3Zr1.4Ta0.6O12/Ce(OH)3 modified polypropylene composite separator for high-performance lithium metal batteries

Lithium (Li) metal anodes (LMAs) are regarded as leading technology for advanced-generation batteries due to their high theoretical capacity and favorable redox potential. However, the practical integration of LMAs into high-energy rechargeable batteries is hindered by the challenge of Li dendrite growth. In this work, nanoparticles of Li6.4La3Zr1.4Ta0.6O12 (LLZTO) loaded with Ce(OH)3 (LLZTCO) were designed and synthesized by a hydrothermal method. A functional composite separator was crafted by coating one side of a polypropylene (PP) separator with a composite electrolyte comprised of polyvinylidene fluoride (PVDF) and LLZTCO. The synergistic interactions between PVDF and LLZTCO provide numerous rapid lithium-ion (Li+) channels, facilitating the efficient redistribution of disparate Li+ flux originating from the insulated PP separator. The composite separator demonstrated an ionic conductivity (σ) of 3.68 × 10–3 S cm−1, substantial Li+ transference number (t+) of 0.73, and a high electrochemical window of 4.8 V at 25℃. Furthermore, the Li/LLZTCO@PP/Li symmetric cells demonstrated stable cycling for over 2000 h without significant dendrite formation. The Li/LiFePO4 (LFP) cells assembled with LLZTCO@PP separators exhibited a capacity retention of 91.6 % after 400 cycles at 1C. This study offers a practical approach to fabricating composite separators with enhanced safety and superior electrochemical performance.

Unlocking iron metal as a cathode for sustainable Li-ion batteries by an anion solid solution.

Traditional cathode chemistry of Li-ion batteries relies on the transport of Li-ions within the solid structures, with the transition metal ions and anions acting as the static components. Here, we demonstrate that a solid solution of F- and PO43- facilitates the reversible conversion of a fine mixture of iron powder, LiF, and Li3PO4 into iron salts. Notably, in its fully lithiated state, we use commercial iron metal powder in this cathode, departing from electrodes that begin with iron salts, such as FeF3. Our results show that Fe-cations and anions of F- and PO43- act as charge carriers in addition to Li-ions during the conversion from iron metal to a solid solution of iron salts. This composite electrode delivers a reversible capacity of up to 368 mAh/g and a specific energy of 940 Wh/kg. Our study underscores the potential of amorphous composites comprising lithium salts as high-energy battery electrodes.

Exploring relaxation behaviors in Hydrogen-Bond networks within binary mixtures of propylene carbonate and primary alcohols through broadband dielectric spectroscopy and molecular dynamic simulation

This work investigates the dielectric properties and the relaxation behaviors of propylene carbonate (PC) and its binary mixtures with methanol and ethanol. A coaxial-circular cutoff waveguide junction was employed to characterize broadband dielectric spectra ranging from 0.1 GHz to 18 GHz, and a two-group Debye model was used to extract relaxation parameters. Excess thermodynamic parameters, Kirkwood orientational correlation factors, and Bruggeman factors for PC-alcohol mixtures were also analyzed and presented. These data provide insights into microscopic dynamic processes as the PC concentration in the mixtures gradually increases. These processes include the continuous disassociation of the alcohols’ hydrogen-bond (H-bond) networks, the formation of new PC-alcohol H-bond networks, the parallel alignment of heterogeneous dipoles, and a significant enhancement of the dielectric effect. Furthermore, a series of molecular dynamics (MD) simulations using the TraPPE-UA forcefield were conducted, and the obtained thermodynamic and electromagnetic parameters demonstrated good agreement with experimental results. Based on radial distribution functions, dipole–dipole spatial orientational correlations, and H-bond life times extracted from the MD simulations, we observed the gradual formation of PC-cage and alcohol-cluster microstructures in PC-rich mixtures. The data and physical insights provided in this work are expected to have practical implications in high-energy battery applications and the pharmaceutical industry.

Elements gradient doping in Mn-based Li-rich layered oxides for long-life lithium-ion batteries

The cobalt-free Mn-based Li-rich layered oxide material has the advantages of low cost, high energy density, and good performance at low temperatures, and is the promising choice for energy storage batteries. However, the long-cycling stability of batteries needs to be improved. Herein, the Mn-based Li-rich cathode materials with small amounts of Li2MnO3 crystal domains and gradient doping of Al and Ti elements from the surface to the bulk have been developed to improve the structure and interface stability. Then the batteries with a high energy density of 600 Wh kg−1, excellent capacity retention of 99.7 % with low voltage decay of 0.03 mV cycle−1 after 800 cycles, and good rates performances can be achieved. Therefore, the structure and cycling stability of low voltage Mn-based Li-rich cathode materials can be significantly improved by the bulk structure design and interface regulation, and this work has paved the way for developing low-cost and high-energy Mn-based energy storage batteries with long lifetime.

Engineering High-Performance Li Metal Batteries through Dual-Gradient Porous Cu-CuZn Host.

Porous copper (Cu) current collectors show promise in stabilizing Li metal anodes (LMAs). However, insufficient lithiophilicity of pure Cu and limited porosity in three-dimensional (3D) porous Cu structures led to an inefficient Li-Cu composite preparation and poor electrochemical performance of Li-Cu composite anodes. Herein, we propose a porous Cu-CuZn (DG-CCZ) host for Li composite anodes to tackle these issues. This architecture features a pore size distribution and lithiophilic-lithiophobic characteristics designed in a gradient distribution from the inside to the outside of the anode structure. This dual-gradient porous Cu-CuZn exhibits exceptional capillary wettability to molten Li and provides a high porosity of up to 66.05%. This design promotes preferential Li deposition in the interior of the porous structure during battery operation, effectively inhibiting Li dendrite formation. Consequently, all cell systems achieve significantly improved cycling stability, including Li half-cells, Li-Li symmetric cells, and Li-LFP full cells. When paired synergistically with the double-coated LiFePO4 cathode, the pouch cell configured with multiple electrodes demonstrates an impressive discharge capacity of 159.3 mAh g-1 at 1C. We believe this study can inspire the design of future 3D Li anodes with enhanced Li utilization efficiency and facilitate the development of future high-energy Li metal batteries.

Self-Limiting Phase Transition Enabling Reversible Overstoichiometric Li Storage in Ni-Rich Cathodes.

Ni-rich cathodes are some of the most promising candidates for advanced lithium-ion batteries, but their available capacities have been stagnant due to the intrinsic Li+ storage sites. Extending the voltage window down can induce the phase transition from O3 to 1T of LiNiO2-derived cathodes to accommodate excess Li+ and dramatically increase the capacity. By setting the discharge cutoff voltage of LiNi0.6Co0.2Mn0.2O2 to 1.4 V, we can reach an extremely high capacity of 393 mAh g-1 and an energy density of 1070 Wh kg-1 here. However, the phase transition causes fast capacity decay and related structural evolution is rarely understood, hindering the utilization of this feature. We find that the overlithiated phase transition is self-limiting, which will transform into solid-solution reaction with cycling and make the cathode degradation slow down. This is attributed to the migration of abundant transition metal ions into lithium layers induced by the overlithiation, allowing the intercalation of overstoichiometric Li+ into the crystal without the O3 framework change. Based on this, the wide-potential cycling stability is further improved via a facile charge-discharge protocol. This work provides deep insight into the overstoichiometric Li+ storage behaviors in conventional layered cathodes and opens a new avenue toward high-energy batteries.

In Situ Integration of a Flame Retardant Quasisolid Gel Polymer Electrolyte with a Si-Based Anode for High-Energy Li-Ion Batteries.

Silicon (Si) stands out as a promising high-capacity anode material for high-energy Li-ion batteries. However, a drastic volume change of Si during cycling leads to the electrode structure collapse and interfacial stability degradation. Herein, a multifunctional quasisolid gel polymer electrolyte (QSGPE) is designed, which is synthesized through the in situ polymerization of methylene bis(acrylamide) with silica-nanoresin composed of nanosilica and a trifunctional cross-linker in cells, leading to the creation of a "breathing" three-dimensional elastic Li-ion conducting framework that seamlessly integrates an electrode, a binder, and an electrolyte. The silicon particles within the anode are encapsulated by buffering the QSGPE after cross-linking polymerization, which synergistically interacts with the existing PAA binder to reinforce the electrode structure and stabilize the interface. In addition, the formation of the LiF- and Li3N-rich SEI layer further improves the interfacial property. The QSGPE demonstrates a wide electrochemical window until 5.5 V, good flame retardancy, high ionic conductivity (1.13 × 10-3 S cm-1), and a Li+ transference number of 0.649. The advanced QSGPE and cell design endow both nano- and submicrosized silicon (smSi) anodes with high initial Coulombic efficiencies over 88.0% and impressive cycling stability up to 600 cycles at 1 A g-1. Furthermore, the NCM811//Si cell achieves capacity retention of ca. 82% after 100 cycles at 0.5 A g-1. This work provides an effective strategy for extending the cycling life of the Si anode and constructing an integrated cell structure by in situ polymerization of the quasisolid gel polymer electrolyte.

Understanding the limitations of thick electrodes on the rate capability of high-energy density lithium-ion batteries

As a core component of transportation electrification, lithium-ion batteries need to address two critical challenges: achieving high energy density and enabling fast charging. However, changes in electrode thickness could result in a trade-off between these two characteristics. Herein, the impact of electrode thickness on the electrochemical performance, thermal behavior, as well as energy and power density of LiNi0.8Co0.1Mn0.1O2(NCM)/graphite batteries are investigated through mathematical modeling. Underutilization of active materials of the thick electrode is identified as the primary limitation on rate capability, which can be attributed to the slow solid-state diffusion and poor electrolyte transport within the electrode, especially the enlarged concentration gradients in the solid phase and the lithium depletion in the electrolyte phase during high-rate charging. Evolutions of local current density and heat generation rate along the electrode thickness are compared, identifying the underlying mechanism of inducing uneven reaction kinetics inside the battery. The trade-off between the energy and power density as a function of electrode thickness is investigated based on the limitations of charge transfer and mass transport. Furthermore, the rate-limiting factors under various application requirements are elucidated. This study will provide guidance for the electrode design of high-energy-density batteries with fast-charging capabilities.

From Bulk to Interface: Solvent Exchange Dynamics and Their Role in Ion Transport and the Interfacial Model of Rechargeable Magnesium Batteries.

Multivalent battery chemistries have been explored in response to the increasing demand for high-energy rechargeable batteries utilizing sustainable resources. Solvation structures of working cations have been recognized as a key component in the design of electrolytes; however, most structure-property correlations of metal ions in organic electrolytes usually build upon favorable static solvation structures, often overlooking solvent exchange dynamics. We here report the ion solvation structures and solvent exchange rates of magnesium electrolytes in various solvents by using multimodal nuclear magnetic resonance (NMR) analysis and molecular dynamics/density functional theory (MD/DFT) calculations. These magnesium solvation structures and solvent exchange dynamics are correlated to the combined effects of several physicochemical properties of the solvents. Moreover, Mg2+ transport and interfacial charge transfer efficiency are found to be closely correlated to the solvent exchange rate in the binary electrolytes where the solvent exchange is tunable by the fraction of diluent solvents. Our primary findings are (1) most battery-related solvents undergo ultraslow solvent exchange coordinating to Mg2+ (with time scales ranging from 0.5 μs to 5 ms), (2) the cation transport mechanism is a mixture of vehicular and structural diffusion even at the ultraslow exchange limit (with faster solvent exchange leading to faster cation transport), and (3) an interfacial model wherein organic-rich regions facilitate desolvation and inorganic regions promote Mg2+ transport is consistent with our NMR, electrochemistry, and cryogenic X-ray photoelectron spectroscopy (cryo-XPS) results. This observed ultraslow solvent exchange and its importance for ion transport and interfacial properties necessitate the judicious selection of solvents and informed design of electrolyte blends for multivalent electrolytes.

A comparison between physics-based Li-ion battery models

Physics-based electrochemical battery models, such as the Doyle-Fuller-Newman (DFN) model, are valuable tools for simulating Li-ion battery behavior and understanding internal battery processes. However, the complexity and computational demands of such models limit their applicability for battery management systems and long-term aging simulations. Reduced-order models (ROMs), such as the Extended Single Particle Model (ESPM), Single Particle Model (SPM) and Polynomial and Padé approximations, here all referred to as simplifications, lead to faster computational speeds. Choosing the appropriate simplification method for a specific cell type and operating condition is a challenge. This study investigates the simulation accuracy and calculation speed of various simplifications for high-energy (HE) and high-power (HP) batteries at different current loading conditions and compares those to the full-order DFN model. The results indicate that among the ROMs, the ESPM consistently offers the best combination of high computational speed and relatively good accuracy in most conditions in comparison to the full-order DFN model. Among the approximations, higher-order polynomial approximation, third and fourth-order Padé approximation perform the best in terms of accuracy. The higher-order polynomial approximation shows an advantage in terms of computing speed, while the fourth-order Padé approximation achieves the highest overall accuracy among the different approximations.

High-energy and durable aqueous Zn batteries enabled by multi-electron transfer reactions

Aqueous Zn batteries (AZBs) have emerged as a highly promising technology for large-scale energy storage systems due to their eco-friendly, safe, and cost-effective characteristics. The current requirements for high-energy AZBs attract extensive attention to reasonably designed cathode materials with multi-electron transfer mechanisms. This review systematically overviews the development and challenges of typical cathode hosts capable of multiple electron transfer reactions for high-performance Zn batteries. Moreover, we also summarize how to trigger the multi-electron transfer chemistry of cathodes, including transition metal oxides, halogens, and organics, to further boost the energy storage capability of AZBs. Finally, perspectives on critical issues and future directions of the multi-electron transfer battery systems offer novel insights for advanced Zn batteries.

Ion Dynamics at the Intermediate Charging State of the Sodium Vanadium Fluorophosphate Cathode.

Na super ionic conductor (NASICON)-type polyanionic vanadium fluorophosphate Na3V2O2(PO4)2F (NVOPF) is a promising cathode material for high-energy sodium-ion batteries. The dynamic diffusion and exchange of sodium ions in the lattice of NVOPF are crucial for its electrochemical performance. However, standard characterizations are mostly focused on the as-synthesized material without cycling, which is different from the actual battery operation conditions. In this work, we investigated the hopping processes of sodium in NVOPF at the intermediate charging state with 23Na solid-state nuclear magnetic resonance (ssNMR) and density functional theory (DFT) calculations. Our experimental characterizations revealed six distinct sodium coordination sites in the intermediate structure and determined the exchange rates among these sites at variable temperatures. The theoretical calculations showed that these dynamic processes correspond to different ion transport pathways in the crystalline lattice. Our combined experimental and theoretical study uncovered the underlying mechanisms of the ion transport in cycled NVOPF and these understandings may help the optimization of cathode materials for sodium-ion batteries.

A 3D dual layer host with enhanced sodiophilicity as stable anode for high-energy sodium metal batteries

A 3D dual layer host with enhanced sodiophilicity as stable anode for high-energy sodium metal batteries

Interphase Engineering via Solvent Molecule Chemistry for Stable Lithium Metal Batteries.

Lithium metal battery has been regarded as promising next-generation battery system aiming for higher energy density. However, the lithium metal anode suffers severe side-reaction and dendrite issues. Its electrochemical performance is significantly dependant on the electrolyte components and solvation structure. Herein, a series of fluorinated ethers are synthesized with weak-solvation ability owing to the duple steric effect derived from the designed longer carbon chain and methine group. The electrolyte solvation structure rich in AGGs (97.96 %) enables remarkable CE of 99.71 % (25 °C) as well as high CE of 98.56 % even at -20 °C. Moreover, the lithium-sulfur battery exhibits excellent performance in a wide temperature range (-20 to 50 °C) ascribed to the modified interphase rich in LiF/LiO2. Furthermore, the pouch cell delivers superior energy density of 344.4 Wh kg-1 and maintains 80 % capacity retention after 50 cycles. The novel solvent design via molecule chemistry provides alternative strategy to adjust solvation structure and thus favors high-energy density lithium metal batteries.