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At least 91 records · Page 5

A Single‐Ion Conducting Borate Network Polymer as a Viable Quasi‐Solid Electrolyte for Lithium Metal Batteries

Abstract Lithium‐ion batteries have remained a state‐of‐the‐art electrochemical energy storage technology for decades now, but their energy densities are limited by electrode materials and conventional liquid electrolytes can pose significant safety concerns. Lithium metal batteries featuring Li metal anodes, solid polymer electrolytes, and high‐voltage cathodes represent promising candidates for next‐generation devices exhibiting improved power and safety, but such solid polymer electrolytes generally do not exhibit the required excellent electrochemical properties and thermal stability in tandem. Here, an interpenetrating network polymer with weakly coordinating anion nodes that functions as a high‐performing single‐ion conducting electrolyte in the presence of minimal plasticizer, with a wide electrochemical stability window, a high room‐temperature conductivity of 1.5 × 10 −4 S cm −1 , and exceptional selectivity for Li‐ion conduction ( t Li+ = 0.95) is reported. Importantly, this material is also flame retardant and highly stable in contact with lithium metal. Significantly, a lithium metal battery prototype containing this quasi‐solid electrolyte is shown to outperform a conventional battery featuring a polymer electrolyte.

Shin, Dong‐Myeong↗

Design of High-Voltage Stable Hybrid Electrolyte with an Ultrahigh Li Transference Number

Considering the high energy consumption during processing, and the low compliance and adhesion of ceramic electrolytes, the integration of polymer into ceramic electrolytes provides a way to mitigate the interfacial issues. However, the severe ion concentration gradient, low ionic conductivity, and instability toward Li metal and high-voltage cathodes become the major concerns in applying hybrid electrolytes. In this work, we report a single-ionconducting hybrid electrolyte (SIE-LLZO) with 64 wt % Li 7 La 3 Zr 2 O 12 (LLZO) particles embedded in a fluoroboron-centered Li-conductive polymer framework (LiBFSIE). The SIE-LLZO electrolyte exhibited a high Li transference number of 0.94 and electrochemical stability up to 5.6 V vs Li/Li + . Promising averaged Coulombic efficiencies of 99.97% and 99.91% were achieved in cells with LiNi 0.8 Co 0.15 Al 0.05 O 2 and LiNi 0.6 Mn 0.2 Co 0.2 O2 cathodes for 400 and 200 cycles, respectively. Finally, the Li-conducting pathway in the hybrid electrolyte was further investigated by a 6 Li-to- 7 Li isotope replacement method, indicating that Li transport mainly relies on the LLZO and interface between LiBFSIE and LLZO.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries

Electrolyte engineering is critical for developing Li metal batteries. While recent works improved Li metal cyclability, a methodology for rational electrolyte design remains lacking. In this study, we propose a design strategy for electrolytes that enable anode-free Li metal batteries with single-solvent single-salt formations at standard concentrations. Rational incorporation of –CF 2 – units yields fluorinated 1,4-dimethoxylbutane as the electrolyte solvent. Paired with 1 M lithium bis(fluorosulfonyl)imide, this electrolyte possesses unique Li–F binding and high anion/solvent ratio in the solvation sheath, leading to excellent compatibility with both Li metal anodes (Coulombic efficiency ~ 99.52% and fast activation within five cycles) and high-voltage cathodes (~6 V stability). Fifty-μm-thick Li|NMC batteries retain 90% capacity after 420 cycles with an average Coulombic efficiency of 99.98%. Industrial anode-free pouch cells achieve ~325 Wh kg –1 single-cell energy density and 80% capacity retention after 100 cycles. Our design concept for electrolytes provides a promising path to high-energy, long-cycling Li metal batteries.

25 ENERGY STORAGE↗

Understanding the complexities of Li metal for solid-state Li-metal batteries

Li-metal anodes are a key enabling technology for next-generation high-energy batteries, including Li–S, Li-air, and high-voltage cathodes. While most research enabling Li metal focuses on electrolyte design, especially in the solid state, the nature of the Li metal itself has a significant impact on the performance of both solid- and liquid-based batteries. This has historically been understudied, but recent work has highlighted the importance of tailoring the Li metal to optimize high-performance batteries. This article focuses on the key aspects of Li metal that impact performance, including the method of synthesis, microstructure, surfaces, impurities, mechanics, and alloying strategies to optimize Li anode performance. Finally, the article will also briefly look at the impact of long-term cycling on the evolution of Li-metal anodes in solid-state batteries and highlight key areas of needed research.

25 ENERGY STORAGE↗

Amorphous ZrCl 4 -Based Superionic Conductor as a Cost-Effective Solid Electrolyte for Batteries

Developing highly conductive and cost-effective solid electrolytes is essential for the commercialization of all-solid-state batteries (ASSBs). Zr-based halide electrolytes hold great promise due to their low estimated cost and high oxidation stability. However, the ionic conductivities of most of them are not high enough to enable moderate- and high-rate cycling of ASSBs. Here, fast ion transport is achieved in a group of cost-effective ZrCl 4 -based electrolytes via a design strategy to create highly disordered amorphous structures. Amorphous Li 0.8 ZrCl 4 (SO 4 ) 0.4 , with a low estimated cost of $21 kg –1 , achieves an ionic conductivity of 1.86 mS cm –1 at 25 °C. It also shows a high oxidation limit of 4.5 V vs Li/Li + and good compatibility with high-voltage cathodes, as demonstrated by the stable cycling of ASSBs (73.7% capacity retention after 1000 cycles at 1 C). Synchrotron X-ray diffraction, pair distribution function analysis, and electrochemical impedance spectroscopy reveal that the outstanding conductivity of these amorphous electrolytes is closely related to their short-range and medium-range ordering, revealing new insights for designing high-performance, cost-effective solid electrolytes.

Zhang, Guangxing [Georgia Institute of Technology,↗

High areal capacity, long cycle life 4 V ceramic all-solid-state Li-ion batteries enabled by chloride solid electrolytes

All-solid-state Li batteries (ASSBs) employing inorganic solid electrolytes offer improved safety and are exciting candidates for next-generation energy storage. Herein, we report a family of lithium mixed-metal chlorospinels, Li 2 In x Sc 0.666-x Cl 4 (0 ≤ x ≤ 0.666), with high ionic conductivity (up to 2.0 mS cm -1 ) owing to a highly disordered Li-ion distribution, and low electronic conductivity (4.7 × 10-10 S cm -1 ), which are implemented for high-performance ASSBs. Owing to the excellent interfacial stability of the SE against uncoated high-voltage cathode materials, ASSBs utilizing LiCoO 2 or LiNi 0.85 Co 0.1 Mn 0.05 O 2 exhibit superior rate capability and long-term cycling (up to 4.8 V versus Li+/Li) compared to state-of-the-art ASSBs. In particular, the ASSB with LiNi 0.85 Co 0.1 Mn 0.05 O 2 exhibits a long life of >3,000 cycles with 80% capacity retention at room temperature. Additionally, high cathode loadings are also demonstrated in ASSBs with stable capacity retention of >4 mAh cm -2 (~190 mAh g -1 ).

25 ENERGY STORAGE↗

The DUNE Vertical Drift Photon Detection System

The Deep Underground Neutrino Experiment (DUNE) is a long-baseline neutrino experiment designed to mainly investigate oscillation parameters, supernova physics and proton decay. Its far detector will be composed of four liquid argon time projection chamber (LArTPC) underground modules, in South Dakota-USA, which will detect a neutrino beam produced at Fermilab, 1300 km away, where a near detector will be in place. The second DUNE far detector module, Vertical Drift, will be a single phase LArTPC with electron drift along the vertical axis with two volumes of 13.5 m x 6.5 m x 60 m dimensions separated by a cathode plane. The charge collection will be performed by two anode planes placed at the top and bottom of the module, each composed by stacked layers of a perforated PCB technology with electrode strips. The photon detection system (PDS) will make use of large size X-Arapuca tiles distributed over three detection planes. One plane will consist of a horizontal arrangement of double sided tiles installed on the high voltage cathode plane and two vertical planes, each placed on the longest cryostat membrane walls. A light active coverage of 14.8% over the cathode and 7.4% over the laterals should allow improvements in the low energy physics range that can be probed in DUNE, especially regarding supernova neutrinos (~10 MeV). We present the initial characterization of the Vertical Drift PDS using a Monte Carlo simulation and preliminary studies on its reconstruction capabilities at the MeV scale. The information obtained with the PDS alone should allow determination of a neutrino interaction region with a precision of at least 65 cm for events with deposited energy above 5 MeV and the deposited energy can be reconstructed with precision better than 10%, both at the center of the volume.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

High-Voltage Sodium–Metal Batteries with Asymmetric Fluoroalkoxylated Organoborate Anion Chemistry

The high reactivity of sodium (Na) metal restricts its compatibility to ether-based electrolytes, while the poor oxidative stability of ethers precludes their coupling to high-voltage cathodes, fundamentally limiting the operating voltage and energy density of sodium–metal batteries (SMBs). We present here a coordination-asymmetry strategy to reconcile this thermodynamic mismatch by generating in situ an asymmetric fluoroalkoxylated organoborate anion, [FB(OCH(CF 3 ) 2 ) 3 ] − (BOF – ), via a Lewis acid–base adduct reaction in ether electrolyte. The asymmetric ligand architecture differentiates oxidative and fluorination pathways: oxidizable B–O moieties mediate controlled interfacial reconstruction, whereas the terminal B–F units supply fluorine for chemical passivation. This self-adaptive chemistry yields nanoscale, conformal, compositionally graded interphases: a boron-oxide/boron-oxycarbide-rich cathode-electrolyte interphase (CEI) that mitigates ether oxidation and a bilayered inorganic–organic solid–electrolyte interphase (SEI) that regulates Na deposition. The nanostructured interphases enable highly reversible Na plating/stripping with an average Coulombic efficiency (CE) of 99.98% and sustain stable 4.3 V operation of anode-free SMBs in oxidation-prone ether electrolytes. Furthermore, this work establishes asymmetric boron coordination as a molecular-level design principle for creating chemically adaptive interphases that overcome the redox asymmetry in energy-dense electrochemical systems.

Anions↗

Terminally fluorinated glycol ether electrolyte for lithium metal batteries

Despite being an excellent candidate for lithium metal batteries due to its stability towards lithium metal, ethereal solvent suffers from relatively low anodic stability, rendering it incompatible with high voltage cathode. Although the anodic stability of ethereal solvent can be enhanced by fluorination, the lithium solvating ability of fluorinated ethers is largely reduced. As a result, common hydrofluoroethers, such as 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether (TTE) and bis(2,2,2-trifluoroethyl) ether (BTFE) are not able to dissolve any lithium salt, albeit enhanced oxidation potential. Therefore, new fluorinated glycol ethers were synthesized in this research. The diglyme analog, which was terminally fluorinated, demonstrated high anodic stability and excellent capability to facilitate lithium plating/stripping. Unlike its non-fluorinated counterpart, the fluorinated diglyme analog displayed outstanding compatibility with lithium hexafluorophosphate, which is an essential salt in lithium-ion batteries. Here it was shown that the electrolyte based on fluorinated diglyme analog with fluoroethylene carbonate as co-solvent enabled highly stable cycling of Li-metal batteries pairing with layered oxide cathode.

25 ENERGY STORAGE↗

Interlayer Design for Halide Electrolytes in All‐Solid‐State Lithium Metal Batteries

Abstract All‐solid‐state lithium‐metal batteries (ASSLMBs) are promising for transportation electrification due to their superior safety and high energy density. Lithium halide electrolytes provide excellent processing flexibility, high ionic conductivity, and anodic stability (>4.1 V), making them highly compatible with high‐voltage cathodes, surpassing sulfide electrolytes (<2.1 V). Nevertheless, halide electrolytes suffer from low cathodic stability and form an electronically conductive interphase with lithium, resulting in a critical current density (CCD) of nearly zero. Herein, Li 3 YbCl 6 electrolytes are synthesized that are kinetically stable with lithium by forming an electronic insulating solid electrolyte interphase. Guided by critical overpotential criteria, a PI 3 interlayer is designed that transforms into Li 6 PI 3 upon contact with lithium, substantially reducing the interfacial resistance of Li 3 YbCl 6 against lithium to 34 Ω and achieving a high critical overpotential of 114 mV. By substituting Yb with Lu, Li 3 LuCl 6 electrolytes with Li 6 PI 3 interlayers reach a CCD of 1.0 mA cm −2 at a capacity of 1.0 mAh cm −2 , comparable to sulfide electrolytes but with higher oxidation stability. Additionally, Li 6 PI 3 enables stable cycling of Li//Li cells with Li 3 LuCl 6 electrolytes at 0.5 mA cm −2 for 400 cycles and maintains 86.5% capacity in Li//LiCoO 2 cells after 220 cycles at 30 °C, paving the way for high‐performance ASSLMBs.

Chemistry↗

Status and prospect of in situ and operando characterization of solid-state batteries

Electrification of the transportation sector relies on radical re-imagining of energy storage technologies to provide affordable, high energy density, durable and safe systems. Next generation energy storage systems will need to leverage high energy density anodes and high voltage cathodes to achieve the required performance metrics (longer vehicle range, long life, production costs, safety). Solid-state batteries (SSBs) are promising materials technology for achieving these metrics by enabling these electrode systems due to the underlying material properties of the solid electrolyte (viz. mechanical strength, electrochemical stability, ionic conductivity). Electro-chemo-mechanical degradation in SSBs detrimentally impact the Coulombic efficiencies, capacity retention, durability and safety in SSBs restricting their practical implementation. Solid|solid interfaces in SSBs are hot-spots of dynamics that contribute to the degradation of SSBs. Characterizing and understanding the processes at the solid|solid interfaces in SSBs is crucial towards designing of resilient, durable, high energy density SSBs. This work provides a comprehensive and critical summary of the SSB characterization with a focus on in situ and operando studies. Additionally, perspectives on experimental design, emerging characterization techniques and data analysis methods are provided. Furthermore, this work provides a thorough analysis of current status of SSB characterization as well as highlights important avenues for future work.

25 ENERGY STORAGE↗

Structured for success: conjugated polymer binders with tailored composition and architecture for lithium-ion batteries

Conjugated polymer binders are replacing conventional binders in lithium-ion batteries. Herein, we examine how molecular engineering and hierarchical nanostructuring govern binder functionality and electrochemical performance. Lithium-ion batteries (LIBs) are the leading energy storage technology, yet enhancing their energy density and cycle life remains critical. Significant progress has been made in high-capacity anodes and high-voltage cathodes, but their performance is hindered by electrode degradation, where it is related to the behaviors of binders at the surface and interface. Conventional non-conductive binders like poly(vinylidene difluoride) (PVDF), combined with conductive additives, often fail to maintain electrical pathways under repeated volume changes. Alternatively, conjugated polymer binders have emerged as a superior alternative, simultaneously offering intrinsic conductivity, mechanical flexibility, and strong adhesion through π-conjugated backbones and functional groups. Their tunable molecular structure enables efficient electron/ion transport while mitigating electrode cracking. Additionally, the development of hierarchically ordered nanostructures in conjugated polymer binder can further enhance their electrochemical performance. This review examines the design principles of conjugated polymer binders, focusing on molecular engineering and nanostructural control to optimize their performance in high-loading electrodes, such as silicon-based anodes. By addressing key challenges in binder functionality, these advanced materials pave the way for next-generation high-energy-density LIBs.

Jin, Xiuyu↗

Prospects for Employing Lithium Copper Phosphates as High-Voltage Li-Ion Cathodes

Three compositions of lithium copper phosphates: Li 2 CuPO 4 , Li 2 Cu 5 (PO 4 ) 4 , and Li 2 CuP 2 O 7 have been studied as potential high-voltage cathode materials for Li-ion batteries, following computational predictions of high operating voltages. An assisted-microwave preparation of Li 2 CuPO 4 , which is otherwise difficult to prepare in nearly pure form, has been developed. The electrochemical performance of all three compounds has been investigated. Additionally, the cyclability of these materials is found to be poor due to structural changes, irreversible reduction to metallic copper at potentials as high as 2.5 V, and the possibility of dissolution into the electrolyte. Some general understanding in regard to the use of Cu compounds in redox electrodes is presented.

25 ENERGY STORAGE↗

Unravelling the Nature of the Intrinsic Complex Structure of Binary‐Phase Na‐Layered Oxides

Abstract The layered sodium transition metal oxide, NaTMO 2 (TM = transition metal), with a binary or ternary phases has displayed outstanding electrochemical performance as a new class of strategy cathode materials for sodium‐ion batteries (SIBs). Herein, an in‐depth phase analysis of developed Na 1− x TMO 2 cathode materials, Na 0.76 Ni 0.20 Fe 0.40 Mn 0.40 O 2 with P2‐ and O3‐type phases (NFMO‐P2/O3) is offered. Structural visualization on an atomic scale is also provided and the following findings are unveiled: i) the existence of a mixed‐phase intergrowth layer distribution and unequal distribution of P2 and O3 phases along two different crystal plane indices and ii) a complete reversible charge/discharge process for the initial two cycles that displays a simple phase transformation, which is unprecedented. Moreover, first‐principles calculations support the evidence of the formation of a binary NFMO‐P2/O3 compound, over the proposed hypothetical monophasic structures (O3, P3, O′3, and P2 phases). As a result, the synergetic effect of the simultaneous existence of P‐ and O‐type phases with their unique structures allows an extraordinary level of capacity retention in a wide range of voltage (1.5–4.5 V). It is believed that the insightful understanding of the proposed materials can introduce new perspectives for the development of high‐voltage cathode materials for SIBs.

Paidi, Anil K.↗

Stabilizing Ni-rich layered cathode for high-voltage operation through hierarchically heterogeneous doping with concentration gradient

High-nickel LiNi x Mn y Co 1-x-y O 2 (NMC) cathodes have demonstrated superior energy density, yet their stability is compromised under high voltage conditions. To address this, here we propose a strategy of heterogeneous doping with a concentration gradient, specifically through Sr–Zr co-modification. We synthesized Ni-rich NMC particles featuring several micron-sized secondary particles composed of micron-sized primary grains. This design aims to harness the structural robustness of single-crystalline grains and the favorable diffusion kinetics of polycrystalline secondary particles. Systematic characterization using a combination of electrochemical measurements and synchrotron analytics reveals an intriguing pattern of hierarchically heterogeneous Sr–Zr co-doping. It demonstrates a depth-dependent concentration gradient at the secondary particle level and competing dopant segregation over the buried grain boundaries. This unique characteristic creates opportunities for enhancing battery performance, particularly by optimizing precursors and implementing advanced modulation techniques. We also investigate the dissolution and precipitation of the cathode's transition metal cations upon high-voltage cycling. These insights suggest that a tailored compositional variation can be a viable approach to effectively design the next-generation high-Ni NMC cathode materials for high-voltage lithium batteries.

36 MATERIALS SCIENCE↗

Conformal hetero-electrolyte interface between soft oxyhalides and garnet enables low-pressure lithium-reservoir-free solid-state batteries

The operation of solid-state batteries with a lithium metal anode and a high voltage cathode requires solid electrolytes (SEs) that are chemically stable with lithium, have a wide electrochemical window, and accommodate volume changes in the electrodes. Unfortunately, no SE has exhibited satisfactory mechanical and electrochemical properties that fit these requirements to date. Dual solid electrolyte systems that use a different SE for the anolyte and catholyte present a viable solution. Here, we focus on oxyhalide SEs that demonstrate superior ionic conductivity and cathode compatibility, where their lithium metal reactivity and poor reduction stability can be resolved using a lithium garnet (Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 , LLZTO) separator. Nonetheless, this imposes a new hetero-electrolyte (H-E) interface at the anolyte|catholyte contact that defines the ion transport across the boundary. We report its promising properties, which are deconvoluted from the electrical measurements of bilayer symmetric cells, for three representative oxyhalide catholytes, LiNbOCl 4 , LiTaOCl 4 , and Li 3 Al 3 O 2 Cl 8 . Pressure-dependent measurements reveal that the relative softness of the oxyhalides (hardness ≤0.4 GPa) enables H-E resistances lower than 150 Ω cm 2 at 2–3 MPa. Mesoscale modelling reveals that the transfer-active contact area of oxyhalides with LLZTO is about 2–3-fold higher than that of argyrodite, Li 6 PS 5 Cl. The low H-E resistance of the LiNbOCl 4 |Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 dual electrolyte enables the cycling of a Li|LiNi 0.82 Mn 0.07 Co 0.11 O 2 full cell with a high discharge capacity (200 mA h g −1 ) at 60 °C and ∼7 MPa. Importantly, we demonstrate a Li-reservoir-free full cell with high Coulombic efficiency (>99.5%) and capacity at 1 MPa using this approach coupled with a garnet-silver interlayer.

Palmer, Max [University of California, Santa Barba↗

Pristine Interface between Lithium Lanthanum Zirconate and Lithium Manganese Oxide by Pulsed Laser Deposition

Solid state lithium-ion batteries have garnered increasing interest in recent years due to several potential advantages over liquid-electrolyte based systems. The possibility of integrating the lithium garnet oxide, Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 (LLZTO), with the high voltage cathode, spinel Li x Mn 2 O 4 (LMO), is evaluated here. Thin film bilayer structures are prepared by pulsed laser deposition on MgO (001) substrates and characterized by x-ray diffraction and transmission electron microscopy. The LLZTO is grown by an alternating layer-by-layer deposition of LLZTO and Li 3 N and subsequently annealed for several hours at 575 °C to promote crystallinity. Growth of crystalline LMO with a pristine interface to LLZTO is achieved by gentle heat treatment (500 °C) to remove surface carbonate from the electrolyte and by cathode growth at a low temperature of 250 °C. Higher temperature depositions (330 – 450 °C) result in reaction between the two materials and the appearance of Li 2 MnO 3 , which may be in part due to the presence of excess lithium in the electrolyte layer. Because fully lithiated LiMn 2 O 4 has a voltage of ≈3.7 V versus Li+/Li, the observation of a well-defined interface, free of impurity phases and with no interdiffusion of elements, indicates LLZTO is stable to at least 3.7 V.

Garnet LLZO↗

Mechanistic understanding of aging behaviors of critical-material-free Li 4 Ti 5 O 12 //LiNi 0.9 Mn 0.1 O 2 cells with fluorinated carbonate-based electrolytes for safe energy storage with ultra-long life span

Behind-the-meter storage (BTMS) systems - a viable method to minimize potential risk of blackout events and stabilize the grid - require a different type of cost-effective energy storage with excellent safety, ultra-long (>20 years) cycle life and reasonable energy density compared that of electric vehicles. To increase the energy density and reduce the cost of a long-term cyclable lithium-titanate-based cell, it is required to employ a critical-material-free high voltage cathode and an electrolyte with good electrochemical and transport properties. In this report the long-term electrochemical performance and behaviors of selected critical-material-free Li 4 Ti 5 O 12 (LTO)//LiNi 0.9 Mn 0.1 O 2 (LNMO) full cells for BTMS applications are evaluated and analyzed in the optimized voltage range of 1.4-2.7 V at 45 degrees C with different fluorinated carbonate-based electrolytes. The fluoroethylene carbonate (FEC)-based electrolyte cell shows the highest capacity retention of 57.9% and Coulombic efficiency (CE) of 99.96% after 1000 cycles, potentially attributed to a dense, homogenous and less resistive LiF-rich solid-electrolyte interphase (SEI) layer formed on the surface of LTO that may mitigate electrolyte decomposition and maintain relatively low cell impedance during cycling. The 3,3,3-fluoroethylmethyl carbonate (F-EMC)-based electrolyte cell, however, presents the worst performance with lower capacity and a sharp decrease of CE, due to unstable and non-uniform SEI formation and continuous oxidative electrolyte decomposition. This mechanistic understanding of cell aging behaviors and failure mechanisms with detailed analysis of surface chemistry and electrode morphology can guide design of new electrode chemistries and electrolyte formulations for the development of BTMS batteries.

25 ENERGY STORAGE↗