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At least 73 records · Page 4

Ionic Conductive and Highly-Stable Interface for Alkali Metal Anodes

Alkali metals are regarded as the most promising candidates for advanced anode for the next-generation batteries due to their high specific capacity, low electrochemical potential, and lightweight. However, critical problems of the alkali metal anodes, especially dendrite formation and interface stabilization, remain challenging to overcome. The solid electrolyte interphase (SEI) is a key factor affecting Li and Na deposition behavior and electrochemical performances. Herein, a facile and universal approach is successfully developed to fabricate ionic conductive interfaces for Li and Na metal anodes by modified atomic layer deposition (ALD). In this process, the Li metal (or Na metal) plays the role of Li (or Na) source without any additional Li (or Na) precursor during ALD. Moreover, the key questions about the influence of ALD deposition temperature on the compositions and structure of the coatings are addressed. The optimized ionic conductive coatings have significantly improved the electrochemical performances. In addition, the electrochemical phase-field model is performed to prove that the ionic conductive coating is very effective in promoting uniform electrodeposition. Further, this approach is universal and can be potentially applied to other different metal anodes. At the same time, it can be extended to other types of coatings or other deposition techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In Situ Formation of Polycyclic Aromatic Hydrocarbons as an Artificial Hybrid Layer for Lithium Metal Anodes

Nonuniform Li deposition causes dendrites and low Coulombic efficiency (CE), seriously hindering the practical applications of Li metal. Herein, we developed an artificial solid-state interphase (SEI) with planar polycyclic aromatic hydrocarbons (PAHs) on the surface of Li metal anodes by a facile in situ formation technology. The resultant dihydroxyviolanthron (DHV) layers serve as the protective layer to stabilize the SEI. In addition, the oxygen-containing functional groups in the soft and conformal SEI film can regulate the diffusion and transport of Li ions to homogenize the deposition of Li metal. The artificial SEI significantly improves the CEs and shows superior cyclability of over 1000 h at 4 mAh cm –2 . The LiFePO 4 /Li cell (2.8 mAh cm –2 ) enables a long cyclability for 300 cycles and high CEs of 99.8%. Furthermore, this work offers a new strategy to inhibit Li dendrite growth and enlightens the design on stable SEI for metal anodes.

25 ENERGY STORAGE↗

In situ Diagnostics of Coupled Electrochemical-Mechanical Properties of Solid Electrolyte Interphases on Lithium Metal Rechargeable Batteries (Final Technical Report)

The fundamental understanding of the coupled mechanical/chemical degradation of the SEI layer during lithium cycling will enable the project to identify the desirable mechanical properties on SEI/lithium as a system and the specific transport properties that enable the homogenous lithium stripping/plating while avoiding the mossy structure. Furthermore, it will allow the project to develop a highly impactful strategy to protect lithium metal and achieve dendrite free high cycle efficiency, which can dramatically increase the energy density of lithium batteries for EV applications. During past three years, four coherent steps have been taken to solve the coupled mechanical and electrochemical degradation: (1) Developed a comprehensive set of in-situ diagnostic techniques to investigate the coupled mechanical/chemical properties of SEI layer and its impact on lithium striping/plating. (2) Identified failure mechanisms of SEI/Li as a whole electrode system using in-situ electrochemical tools. (3) Established a design strategy of protective coatings on Li metal to extend the cycle life Li meal electrode. (4) Developed novel surface coatings as the artificial SEI layer to protect Li metal and significantly extend cycle life. During past 3-year budget period, we have published over 16 peer-reviewed paper, filed 7 patents, and given over 30 invited talks. 5 graduated students and 2 postdocs were supported by this project.

36 MATERIALS SCIENCE↗

A Discrete Dendrite Dynamics Model for Epitaxial Columnar Grain Growth in Metal Additive Manufacturing with Application to Inconel

Epitaxial columnar grain growth is a prevalent microstructural feature in the additive manufacturing (AM) of metal components such as Inconel, with cubic unit cell crystal lattice structure (face centered cubic (FCC) or body centered cubic (BCC)). These columnar grains evolve from the partly molten grains in the substrate or the solidified metal. This work proposes an efficient model to simulate the competitive growth of epitaxial columnar dendritic grains. The proposed model tracks the dynamic changes in the dendrites emanating from discrete points along the solid/liquid interface of a quasi-steady melt pool (MP). These dynamic changes include convergence and divergence of growing dendrites. The model is extended to predict the microstructure of large 3D parts and experimentally validated by comparing the simulation results for laser powder bed fusion (L-PBF) and wire-arc additive manufacturing (WAAM) processes. The microstructure and pole figures are predicted for Inconel 718 samples produced by L-PBF and Inconel 740H samples produced by WAAM processes. Finally, the model predictions compare well with the observed microstructure and pole figures results for both the L-PBF and WAAM processes.

20 FOSSIL-FUELED POWER PLANTS↗

Dendrite Suppression by a Polymer Coating: A Coarse‐Grained Molecular Study

Abstract A major hurdle to the successful deployment of high‐energy‐density lithium metal based batteries is dendrite growth during battery cycling, which raises safety and cycle life concerns. Coating the Li metal anode with a soft polymer layer has been previously shown to be effective in suppressing dendrite growth, leading to uniform lithium deposition even at high current densities. A 3D coarse‐grained molecular model to study the mechanism of dendrite suppression is presented. It is found that the most effective coatings delay or even prevent dendrites from penetrating the polymer layer during deposition. The optimal deposition can be achieved by jointly tuning the polymer stiffness and relaxation time. Higher polymer dielectric permittivity and coating thickness are also effective, but the deposition rate and, therefore, the charging current density is reduced. These findings provide the basis for rational design of soft polymer coatings for stable lithium deposition.

Kong, Xian↗

Radiation Damage Mechanisms in Oxide-Based Solid Electrolytes

Ion implantation is a promising approach to mitigate dendrite formation in metal anode solid-state batteries by modifying the chemical and mechanical properties of oxide-based electrolyte surfaces such as Li 7 La 3 Zr 2 O 12 (LLZO). Yet, the detailed atomistic mechanisms and potentially adverse side effects of ion implantation remain poorly understood. In this study, we used molecular dynamics simulations to elucidate the evolution of radiation-induced damage in LLZO. The results reveal that radiation damage is primarily driven by recoils from heavy ions in the lattice, producing antisite defect clusters whose density decreases as recoil energy increases, a counterintuitive finding that highlights complex cascade fragmentation. Radiation-induced disruption to the crystal sublattice connectivity, especially in the La–O network critical for Li-ion transport, leads to degradation in ionic pathways at low energies, while higher energy cascades can form new conduction pathways via enhanced Zr–O network connectivity. These findings provide a mechanistic foundation for optimizing ion implantation strategies that balance disruption of the lattice for surface modification for dendrite resistance with preservation of essential ionic conductivity.

Defects↗

Engineering Approaches to Dendrite free Lithium Anodes

This is the Final Technical Report of the work that was completed related to development of dendrite free anodes for Li-metal batteries. The report contains full details of all the strategies that were employed to overcome this pernicious problems of dendrite formation of lithium metal during cycling of Li-metal and Li-ion batteries. Various approaches were developed to understand the formation of dendrites and mitigation strategies were then developed to overcome this severe problem. In doing so novel multi-component alloys as well as structurally isomorphous alloys have been developed. In addition coating strategies were also developed to overcome the formation of dendrites. The novel approaches related to development of novel alloys using economic cost effective and scalable approaches. The new approaches will easily advance the science of lithium metal alloys and dendrite free anodes including current collectors. Development of this new technology will have immense benefit to providing new high energy density batteries of tremendous benefit to the public since cost effective and safe high energy density batteries will be possible with this new technology.

25 ENERGY STORAGE↗

3D Artificial Solid-Electrolyte Interphase for Lithium Metal Anodes Enabled by Insulator–Metal–Insulator Layered Heterostructures

Despite considerable efforts to prevent lithium (Li) dendrite growth, stable cycling of Li metal anodes with various structures remains extremely difficult due to the direct contact of the liquid electrolyte with Li. Rational design of solid-electrolyte interphase (SEI) for 3D electrodes is a promising but still challenging strategy for preventing Li dendrite growth and avoiding lithium–electrolyte side reactions in Li-metal batteries. Here, a 3D architecture is constructed with g-C 3 N 4 /graphene/g-C 3 N 4 insulator–metal–insulator sandwiched nanosheets to guide uniform Li plating/stripping in the van der Waals gap between the graphene and the g-C 3 N 4 , and the function of which can be regarded as a 3D artificial SEI. Li deposition on the surface of g-C 3 N 4 is suppressed due to its insulating nature. However, its uniform lithiophilic sites and nanopore channels enable homogeneous lithium plating between the graphene and the g-C 3 N 4 , prohibiting the direct contact of the electrolyte with the Li metal. The use of the g-C 3 N 4 -layer-modified 3D anode enables long-term Li deposition with a high Coulombic efficiency and stable cycling of full cells under high cathode loading, limited Li excess, and lean electrolyte conditions. The concept of a 3D artificial SEI will shed light on developing safe and stable Li-metal anodes.

25 ENERGY STORAGE↗

A Self-Healing, Flowable, Yet Solid Electrolyte Suppresses Li-Metal Morphological Instabilities

In this article, lithium metal (Li 0 ) solid-state batteries encounter implementation challenges due to dendrite formation, side reactions, and movement of the electrode–electrolyte interface in cycling. Notably, voids and cracks formed during battery fabrication/operation are hot spots for failure. Here, a self-healing, flowable yet solid electrolyte composed of mobile ceramic crystals embedded in a reconfigurable polymer network is reported. This electrolyte can auto-repair voids and cracks through a two-step self-healing process that occurs at a fast rate of 5.6 µm h -1 . A dynamical phase diagram is generated, showing the material can switch between liquid and solid forms in response to external strain rates. The flowability of the electrolyte allows it to accommodate the electrode volume change during Li 0 stripping. Simultaneously, the electrolyte maintains a solid form with high tensile strength (0.28 MPa), facilitating the regulation of mossy Li 0 deposition. The chemistries and kinetics are studied by operando synchrotron X-ray and in situ transmission electron microscopy (TEM). Solid-state NMR reveals a dual-phase ion conduction pathway and rapid Li + diffusion through the stable polymer-ceramic interphase. This designed electrolyte exhibits extended cycling life in Li 0 –Li 0 cells, reaching 12 000 h at 0.2 mA cm -2 and 5000 h at 0.5 mA cm -2 . Furthermore, owing to its high critical current density of 9 mA cm -2 , the Li 0 –LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) full cell demonstrates stable cycling at 5 mA cm -2 for 1100 cycles, retaining 88% of its capacity, even under near-zero stack pressure conditions.

25 ENERGY STORAGE↗

Industrializable interlayer with catalytic conversion of dead lithium for Ah–level Nickel–rich lithium metal batteries

The growth of lithium (Li) dendrites and the accumulation of dead Li (i.e., Li metal regions which are electronically disconnected from the current collector) significantly undermine the safety and performance of Li metal batteries. This study employs kilogram-scale atomic layer deposition technology to construct zinc oxide with a preferential (002) crystal orientation, which homogeneously forms on commercial carbon nanotube papers. Our approach emphasizes the importance of achieving a moderate Li adsorption energy and low Li migration energy barriers to suppress Li dendrite growth. In this work, we introduce the concept of "catalytic" effect for dead Li reconversion, as validated through time-of-flight secondary ion mass spectrometry, leading to a Li plating/stripping efficiency of 99.89%. The Ah-level Li metal pouch cells with high-nickel positive electrodes achieve a specific energy of 380 Wh kg -1 (based on the mass of the whole pouch cell) and demonstrate stable cycling under demanding conditions. Analysis of the cycled pouch cells confirms the structural integrity and provides insights into the mechanism of the dead Li "catalytic" conversion.

Shen, Huasen [Jianghan University, Wuhan (China)]↗

Non‐Linear Kinetics of The Lithium Metal Anode on Li 6 PS 5 Cl at High Current Density: Dendrite Growth and the Role of Lithium Microstructure on Creep

Abstract Interfacial instability, viz., pore formation in the lithium metal anode (LMA) during discharge leading to high impedance, current focusing induced solid–electrolyte (SE) fracture during charging, and formation/behaviour of the solid–electrolyte interphase (SEI), at the anode, is one of the major hurdles in the development of solid‐state batteries (SSBs). Also, understanding cell polarization behaviour at high current density is critical to achieving the goal of fast‐charging battery and electric vehicle. Herein, via in situ electrochemical scanning electron microscopy (SEM) measurements, performed with freshly deposited lithium microelectrodes on transgranularly fractured fresh Li6PS5Cl (LPSCl), the LiǀLPSCl interface kinetics are investigated beyond the linear regime. Even at relatively small overvoltages of a few mV, the LiǀLPSCl interface shows non‐linear kinetics. The interface kinetics possibly involve multiple rate‐limiting processes, i.e., ion transport across the SEI and SE|SEI interfaces, as well as charge transfer across the LiǀSEI interface. The total polarization resistance R P of the microelectrode interface is determined to be ≈ 0.8 Ω cm 2 . It is further shown that the nanocrystalline lithium microstructure can lead to a stable LiǀSE interface via Coble creep along with uniform stripping. Also, spatially resolved lithium deposition, i.e., at grain surface flaws, grain boundaries, and flaw‐free surfaces, indicates exceptionally high mechanical endurance of flaw‐free surfaces toward cathodic load (>150 mA cm −2 ). This highlights the prominent role of surface defects in dendrite growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lithicone‐Protected Lithium Metal Anodes for Lithium Metal Batteries with Nickel‐Rich Cathode Materials

The high energy density advantage of lithium (Li) metal batteries (LMBs) makes them increasingly desirable; however, problems such as strong reactivity and dendrite growth of Li metal anode limit their practical uses. In this work, a novel Li‐containing glycerol (LiGL) or lithicone protection layer on a 50 μm thick Li metal anode is employed for improving the performance of LMBs. This LiGL layer was accurately deposited via a molecular layer deposition (MLD) process at 150 °C, using lithium tert‐butoxide and glycerol as precursors. The as‐formed LiGL coating layer is highly tunable in its thickness by simply adjusting MLD cycles and shows a good stability and outstanding ionic transport properties. The LiGL layer is found to effectively mitigate side reactions and enhance cycling stability in both symmetric cells and full cells. Specifically, the LMBs with LiGL@Li anode of 400 MLD cycles and LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode enable a capacity retention of ≈87%, much higher than ≈35% of the cells with bare Li after 200 cycles at a charge/discharge current density of 2.1 mA cm −2 . This work paves a feasible way for practical LMBs with improved capacity and stability through applying an innovative protection layer on Li metal anodes.

25 ENERGY STORAGE↗

Morphodynamics of dendrite growth in alumina based all solid-state sodium metal batteries

All solid-state batteries (ASSBs) with ceramic electrolytes and alkali metal anodes are a potential future energy storage technology for vehicle electrification and smart grids. However, uncontrollable dendrite growth toward ultimate short circuiting in solid electrolytes (SEs) has become a serious concern in the design of long-cycle, safe ASSBs, and the underlying mechanism has remained unclear. Here through multiscale imaging and morphodynamic tracking we show that Na dendrites grow in β''-Al 2 O 3 SEs through an alternating sequence of Na deposition and crack propagation. Atomic-scale imaging evidenced that electrochemical cycling causes massive delamination cracking along the Na + conduction planes, accompanied by the closure of neighboring conduction channels. In situ SEM observations revealed a dynamic interplay between Na deposition and crack propagation: Na deposition accumulates mechanical stress that induces cracking; cracking releases the local stress, which promotes further Na deposition. Thus, Na deposition and cracking alternatingly proceed until short circuits take place. A multiscale phase-field model is developed to recapitulate the morphodynamics of Na dendrite growth, predicting the tree-like fractal morphology of the growing dendrites. Importantly, our findings suggest that decoupling between Na deposition and cracking represents an important route to mitigate uncontrollable dendrite growth in ASSBs.

25 ENERGY STORAGE↗

Reactive Carbide‐Based Synthesis and Microstructure of NASICON Sodium Metal All Solid‐State Electrolyte

Reactive carbide precursor-based synthesis of NASICON-type NZSP (Na 1+x Zr 2 Si x P 3-x O 12 ) solid-state electrolyte (SSE) is demonstrated, in contrast to the established oxide-based approach. Exothermic decomposition of ZrC and SiC in air homogenizes microstructure, yielding 98% compact density after conventional sintering at 1200 °C. Quantitative stereology demonstrates that significant microstructural differences are present. Compacts of carbide-derived Carb-NZSP are 98% dense with a secondary zirconium oxide (ZrO 2 ) volume fraction of 0.2% ± 0.3%, versus 93% dense and 3% ± 1% for oxide-derived baseline. For Carb-NZSP, the secondary glassy phosphate phase is agglomerated, while for baseline, it is dispersed and percolated. Electrochemical testing combined with post-mortem analysis demonstrates how microstructural control of secondary phases is critical for dendrite suppression: Carb-NZSP critical current density (CCD) is 3.1 ± 0.8 mA cm −2 at 0.1 mAh cm −2 , versus 1.0 ± 0.7 mA cm −2 at 0.1 mAh cm −2 . Cryogenic focused ion beam (cryo-FIB) analysis demonstrates that in both materials, the porous 2D sheet-like sodium metal dendrites propagate around and subsume NZSP grains, likely following a path enriched with glassy phase and with porosity. Dendrites also flow around isolated zirconia particles. Phase field simulation reveals deflection of dendrites by mechanically tough zirconia, while brittle glassy phase accelerates dendrite growth, especially when finely distributed.

36 MATERIALS SCIENCE↗

Unveiling the mechanisms of lithium dendrite suppression by cationic polymer film induced solid–electrolyte interphase modification

It is crucial to suppress lithium dendrite formation in lithium metal batteries. Formation of a good solid–electrolyte interphase (SEI) has been considered to be effective in limiting lithium dendrite growth. However, how the SEI may be modified during lithium deposition is hard to resolve due to challenges in in situ investigation of the SEI with fine details. Here, we report an in situ study that uncovers the lithium dendrite suppression mechanism arising from SEI modification by a poly(diallyldimethylammonium chloride) (PDDA) cationic polymer film, using electrochemical liquid cell transmission electron microscopy (TEM). Lithium nanogranules are obtained in the presence of the polymer film. Chemical mapping of the deposits provides remarkable details of the SEI on individual nanogranules. It shows that lithium fluorides are uniformly distributed within the inner SEI layer of individual lithium nanogranules, arising from the instantaneous reaction of the deposited lithium with PF 6 – ions accumulated by the cationic polymer film, and thus the dendritic growth of lithium is prohibited. The ability to directly measure SEI chemistry at the nanoscale down to the individual nanograins in situ and unveil its correlation with the lithium deposition behavior opens future opportunities to explore unsolved mechanisms in batteries.

25 ENERGY STORAGE↗