Artificial Interphase Research Articles

Artificial interphase engineering to stabilize aqueous zinc metal anodes.

Aqueous Zn-ion system combining the advantages of energy density, intrinsic safety, and environmental benignity, has been regarded as a promising power source for future electronics. Besides cathodes and electrolytes, more attention should be paid to stabilizing zinc metal anodes since the main challenges in current aqueous Zn-ion batteries are still the hydrogen evolution and dendrite growth of the zinc anode. Thereupon, artificial interphase engineering that integrates the highly tunable, selectable, and controllable characteristics becomes one of the most effective ways to stabilize zinc anodes. In this mini-review, state-of-the-art knowledge on the rational interphase engineering of aqueous zinc metal anodes in the functional layer coating and in situ solid electrolyte interphase formation are covered. The main focus of this work is to summarize the most recent development of artificial interphases in chemical composition, structure, and function. The potential issues and perspectives regarding materials and methods are presented.

Manipulation of porosity and electrochemical artificial separator interphase for durable lithium-sulfur batteries

The diffusion and shuttle of polysulfides leading to fast capacity decay and poor cyclability have severely hindered the practical application of lithium-sulfur batteries (LSBs). Here, we used a double-effect strategy to improve the cycle stability and specific capacity of LSBs. That is, the hole effect with the alteration of the pore size of the mesoporous carbon spheres (MCS) as the cathode host materials, and the confinement effect with the usage of the carbon cloth (CC) as an intermediate layer in the middle of cathode and separator to inhibit the polysulfides diffusion and shuttle phenomenon. As a result, appropriate pore size and inner space were obtained by controlling the content of ammonium hydroxide solution (NH3·H2O) catalyst to 1000 μL (denoted as MCS-4) in the synthesis of MCS. When MCS-4 is used as the sulfur host material, the obtained electrode material with a CC interlayer modification showed distinguished electrochemical performance in cells, including a high initial discharge capacity (1250 mAh g−1 at 0.1 C) and long cycle stability (510 mAh g−1 at 2 C after 500 cycles and 507 mAh g−1 at 0.5 C after 1000 cycles).

Application of Artificial Interphase on Highly Active NCM811 Cathode Materials

The Ni-rich LiNi0.8Co0.1Mn0.1O2 layered oxide (NCM811) is a kind of high-capacity cathode materials for rechargeable Li-ion batteries. However, due to the high Ni content, NCM811 becomes very active and unstable, especially under high temperature environment. This is the reason why NCM811 cathodes often suffer from electrolyte decomposition and then generate a SEI layer on the surface during charge-discharge cycling.To solve the unstable problems of NCM811, this work is to construct a layer of fluorinated soft artificial interphase on the surface of the NCM811 electrode material by means of simple and convenient polymer-coating and partial-thermal-treatment. When the surface becomes more hydrophobic, the less moisture in the air will adsorb, and it avoids the detrimental reaction with the electrolyte. Also, the coating reacts to some extent with the residue lithium to form lithium fluoride and stabilizes the surface. Electron-conductive additive was added as electron channel to enhance the overall performance of intercalation/deintercalation. The results demonstrate that the artificial surface layer led to substantial improvement in cycle stability.(This work is supported by Industrial Technology Research Institute, Taiwan.)

Application of Artificial Interphase on Ni-Rich Cathode Materials in All Solid State Li-Ion Batteries

Among many cathode materials, nickel-rich LiNi0.8Co0.1Mn0.1O2 (NCM 811) has been spotlighted as one of the most feasible candidates for next-generation LIBs because of its high discharge capacity (~200 mAh/g). However, NCM 811 shows significant performance degradation, which is mostly attributed to cation mixing, surface side reactions, and intrinsic structural instability originating from the large volume changes during repeated cycling.Conventional lithium ion batteries (LIB) normally use flammable nonaqueous liquid electrolytes, resulting in a serious safety issue in use. In this respect, all solid state lithium ion batteries (SSLIBs) are regarded as a fundamental solution to address the safety issue by using a solid state electrolyte (SSE) in place of the conventional liquid one.This study assess the performance of NCM811 cathode for all-solid-state batteries based on hybrid PEO-ceramic solid electrolyte. Artificial CEI coating layer has been developed in order to prevent direct contact of electrolyte with the cathode, thus avoid the negative effects, such as side reactions, on NCM 811. The incorporation of ceramic materials results composite electrolytes, containing inert fillers, offer improved mechanical stability under high operating temperature.It is demonstrated that the polymer of hybrid electrolytes can penetrate into cathode, providing a good Li+ transfer channel inside the battery under high operating temperature. Moreover, the protective coating on NCM811 effectively improve the electrochemical stability.(This work is supported by Ministry of Science and Technology, Taiwan under contract number: MOST 108-3116-F002-008)

Effect of Artificial SEI Content on Lithium Metal Anode Morphology and Performance

Lithium metal is often deemed the “Holy Grail” of rechargeable battery technology, due to its high theoretical capacity and low electrochemical potential. However, the cascading heterogeneity from the formation of the solid-electrolyte interphase (SEI) up to the non-uniform current distribution leads to both poor efficiency via rapid consumption of active materials as well as safety issues from treacherous dendrite growth. An SEI that is ionically conductive while electrically resistive, viscoelastic, electrochemically stable, and possesses good mechanical properties is paramount for hindering these failure mechanisms. The discovery of novel approaches to producing an ideal SEI is a crucial piece to solving the lithium metal anode puzzle.One route of controlling the SEI is through interface engineering by producing a stable artificial SEI. In this work, a mixed artificial SEI was produced with aim toward improving ionic conductivity while retaining electrochemical stability and mechanical properties. This mixed SEI embraces the unavoidable surface heterogeneity, all the while preventing dendrite growth that plagues lithium metal batteries. A mixed artificial SEI, as well as a single-component artificial SEI, were produced through a simple and rapid deposition method and tested to observe their failure mechanisms compared to bare lithium.Symmetric cells (i.e., Li||Li) were utilized to isolate the failure mechanisms of these different anode treatments. The failure mechanism of the single-component artificial SEI cells shifted to failure via electrolyte consumption rather than short circuiting seen with bare lithium. This revealed that artificial interphases led to reduced dendrite propagation. Additionally, a reduction in cell potential range was observed with the mixed artificial SEI when compared to the single-component artificial SEI, as well as improved cyclability. Upon further investigation, it appears that the added component of the mixed artificial SEI, which was meant to improve the ionic conductivity, dissolved into the electrolyte upon initial exposure. This dissolution left behind a new SEI structure, theoretically producing easier ionic pathways and thus resulting in decreased cell overpotential. Dissolution was confirmed with high-resolution surface characterization techniques. Additionally, symmetric cell electrodes rinsed with solvent prior to testing retained superior cell performance. Though this dissolution should lead to increased available “hot spots”, the growth of dendrites was hindered. This work discusses the effect an artificial SEI has on failure mechanisms, as well as provides insight into the methods of producing stable, long-life lithium metal batteries. This includes a focus on how nanoscale heterogeneity effects cell-scale performance via high-resolution characterization and computational simulations.Different surface to sub-surface characterization techniques were utilized to measure properties of artificial SEIs and bare lithium. Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS) provided elemental make-up and distribution, as well as morphological characteristics. X-ray photoelectron spectroscopy (XPS) provided the chemical state of surfaces, as well as sub-surfaces with the use of depth profiling. Different atomic force microscopy (AFM) techniques were used to spatially measure nanoscale properties such as work functions with the Kelvin probe technique (SKPFM) and quantifiable nanomechanical properties (QNM), as well as observe kinetic mechanisms with in-situ electrochemical methods (EC-AFM). Lastly, computational simulations from the atomistic scale via density functional theory (DFT) up to molecular dynamics (MD) were utilized to support assumptions on the reaction mechanisms derived from experimental observations. Figure 1

Revealing and Elucidating ALD‐Derived Control of Lithium Plating Microstructure

AbstractThe practical implementation of Li metal batteries is hindered by difficulties in controlling the Li metal plating microstructure. While previous atomic layer deposition (ALD) studies have focused on directly coating Li metal with thin films for the passivation of the electrode–electrolyte interface, a different approach is adopted, situating the ALD film beneath Li metal and directly on the copper current collector. A mechanistic explanation for this simple strategy of controlling the Li metal plating microstructure using TiO2 grown on copper foil by ALD is presented. In contrast to previous studies where ALD‐grown layers act as artificial interphases, this TiO2 layer resides at the copper–Li metal interface, acting as a nucleation layer to improve the Li metal plating morphology. Upon lithiation of TiO2, a LixTiO2 complex forms; this alloy provides a lithiophilic surface layer that enables uniform and reversible Li plating. The reversibility of lithium deposition is evident from the champion cell (5 nm TiO2), which displays an average Coulombic efficiency (CE) of 96% after 150 cycles at a moderate current density of 1 mA cm−2. This simple approach provides the first account of the mechanism of ALD‐derived Li nucleation control and suggests new possibilities for future ALD‐synthesized nucleation layers.

Interface Between Solid-State Electrolytes and Li-Metal Anodes: Issues, Materials, and Processing Routes.

Li metal, which has a high theoretical capacity and negative electrochemical potential, is regarded as the "holy grail" in Li-ion batteries. However, the flammable nature of liquid electrolyte leads to safety issues. Hence, the cooperation of solid-state electrolyte and Li-metal anode is demanded. However, the short cycle life induced by interfacial issues is the main challenge faced by their cooperation. In this review, dendrite and interfacial side reactions are comprehensively analyzed as the main interfacial problems. Meanwhile, the "state-of-the-art" interphase materials are summarized. The challenges faced by each kind of material are underscored. Moreover, different processing routes to fabricate artificial interphase are also investigated from an engineering perspective. The processing routes suitable for mass production are also underscored.

Artificial interphases enable dendrite-free Li-metal anodes

Li-metal is an ideal anode that can provide rechargeable batteries with high energy density, but its application in large scale is restricted by its high activity that leads to the severe decomposition of electrolyte components (solvents and salts) and the growth of Li dendrites. These parasitic reactions are responsible for the cycle life deterioration and the safety accidents of rechargeable Li-metal batteries. Correspondingly, much effort has been made to regulate Li/electrolyte interface chemistry. In this review, we summarize some strategies that have been developed recently to stabilize Li/electrolyte interface by constructing protective interphases on Li-metal anodes. Firstly, the currently available understandings on the instability of Li/electrolyte interface are outlined. Then, artificial interphases recently constructed ex-situ and in-situ are illustrated in detail. Finally, possible approaches to acquire more efficiently protective interphases are prospected.

Structure Design of Cathode Electrodes for Solid‐State Batteries: Challenges and Progress

Solid‐state lithium batteries have aroused wide interest with the probability to guarantee safety and high energy density at the same time. In the past decade, fruitful endeavors have been devoted to promoting each component of these batteries, including solid electrolyte with high conductivity, dendrite‐free lithium anode, and high‐capacity cathode. However, the currently achieved cell performances are still inconsistent with the original expectations, in which interfaces severely hamper the energy output and cycling stability for practical application. Herein, particular attentions are paid to the interface between cathode and solid electrolyte. The huge resistance caused at this interface can be found throughout the entire life of batteries from preparation to operation. Accordingly, these issues are divided into physical contact, thermal interdiffusion, space‐charge layer, electrochemomechanical breakdown, and undesirable side reactions and further elucidated in detail. Moreover, representative developments concerning the cathode/solid electrolyte interface in terms of compositional and morphological control in cathode, architecture and manufacture design in solid electrolyte, and artificial interphase building are summarized. With these efforts, the emphasis of the fundamental issues and perspectives of interface between cathode and solid electrolyte may eventually contribute to high‐energy long‐cycling solid‐state lithium batteries.

Tailoring the Mechanical and Electrochemical Properties of an Artificial Interphase for High‐Performance Metallic Lithium Anode

AbstractLithium metal is regarded as the “Holy Grail” of anode materials due to its low electrochemical potential and high theoretical capacity. Unfortunately, its unstable solid electrolyte interphase (SEI) leads to low Coulombic efficiency (CE) and serious safety issues. Herein, a hybrid nanoscale polymeric protective film with tunable composition and improved stiffness is developed by incorporating aluminum crosslinkers into the polymer chains. The Li plating/stripping process is regulated through the protective coating and the dendrite growth is effectively suppressed. Promisingly, the protected Li can deliver stable performance for more than 350 h with a cycling capacity of 2 mAh cm−2 without a notable increase in overpotential. Moreover, a stable charge/discharge cycling in Li–O2 batteries with the protected Li can be maintained for more than 600 h. This work provides guidance on the rational design of electrode interfaces and opens up new opportunities for the fabrication of next‐generation energy storage systems.

Electrolyte, Solvation Shell and Interphase for Ca and Mg Metal Anode Based Batteries

Various metals have been used as battery anodes in electrochemical cells ever since the birth of the batteries with Volta’s pile and in the first commercialized primary (Zn/MnO2, Leclanché 1866) and secondary (Pb/acid, Planté 1859) batteries. Li-MoS2 cells, employing Li metal anodes, with specific energies two to three times higher than both Ni/Cd and Pb/acid cells, were withdrawn from the market due to safety issues related to dendrites growth. Instead, electrodeposition of Mg and Ca appears to be less prone to dendrite formation.[1,2] Pioneering work by Aurbach et al. in the early 1990’s showed a surface-film controlled electrochemical behavior of Ca and Mg metal anodes in electrolytes with conventional organic solvents.[3,4] The lack of metal plating was attributed to the poor divalent cation migration through the passivation layer.Nevertheless, recent demonstration of Ca and Mg plating and stripping in the presence of a passivation layer or an artificial interphase [2,5,6] has paved the way for assessment of new electrolyte formulations with high resilience towards oxidation. However, several challenges remain to be tackled for the development of Ca and Mg based batteries.[7,8] Among these, the need for reliable electrochemical test protocols, mass transport limitations and high desolvation energies (due to strong cation-solvent and cation–anion interactions) are implied.[9, 10] Here, the reliability of electrochemical set-ups involving multivalent chemistries is discussed, and a systematic investigation on the impact of the electrolyte formulation on the cation solvation structure and transport is presented.

A Biphasic Interphase Design Enabling High Performance in Room Temperature Sodium-Sulfur Batteries

Summary Room temperature sodium-sulfur batteries possess higher specific energy and improved inherent safety compared to their high-temperature analogs used in stationary grid storage. The viability of room temperature sodium batteries depends critically on the mechanical and ionic transport properties of the solid electrolyte interphase. However, little emphasis has been placed on developing sodium anode interphases that combine high Young’s modulus (stiffness), high critical strain (ductility), and low ionic diffusion barrier for cycling at high rates. Here, we report an artificial biphasic interphase comprising two chemically distinct phases, NaOH and NaNH2, which combines high stiffness and high ductility. In addition, the biphasic interphase exhibits a low diffusion barrier for sodium ions, enabling reversible sodium plating and stripping behavior even at extremely high current densities (up to 50 mA cm−2) in symmetric cell configuration. Stable and reversible cycling of a room temperature sodium-sulfur battery is also demonstrated over 500 cycles.

An artificial metal-alloy interphase for high-rate and long-life sodium–sulfur batteries

Room-temperature sodium–sulfur battery is considered to be a promising candidate for next-generation batteries due to its high theoretical energy density (~1274 ​Wh kg−1) and natural abundance of elements. There are however, a number of concomitant challenges, including large volume change, low ionic conductivity, rapid dendrite growth, and high chemical reactivity, which limit the viability of sodium anodes. Solid electrolyte interphases that address all 4 challenges simultaneously to enable high-rate cycling of sodium anodes remain scarce in the literature. Here we report an artificial metal-alloy interphase (MAI) comprising sodium-tin alloy, which was synthesized using a facile solid-vapor reaction of metallic sodium with tin tetrachloride vapors, instead of using typical liquid electrolytes with tin-based additives (solid-liquid reaction). The MAI was found to facilitate reversible deposition of sodium at relatively high current densities (2–7 ​mA ​cm−2), and allows sodium electrodes to cycle stably for over 650 cycles at 2 ​mA ​cm−2 in sodium symmetric cells. Owing to the unique properties of MAI, such as strong electrode adhesion (to accommodate volume change), high ionic conductivity (to minimize overpotential), high Young’s modulus (to suppress dendrite growth), and low electrolyte permeability (to minimize electrolyte reduction), the sodium anode with MAI can endure extended cycling test in sodium–sulfur batteries for over 500 cycles with a high Coulombic efficiency of 99.7%. This solid-vapor chemistry concept to synthesize MAIs can also be generalized to other material systems such as sodium-silicon and sodium-titanium alloys.

L-Tryptophan: Antioxidant as a Film-Forming Additive for a High-Voltage Cathode.

l-tryptophan (TrP) was investigated as a functional film-forming additive on a lithium-rich layered oxide cathode because it has a much lower oxidation potential than other common carbonate-based electrolytes. Owing to its prior oxidation to a base electrolyte, an artificial cathode-electrolyte interphase (CEI) was formed on the cathode surface, which could be confirmed via X-ray photoelectron spectroscopy and scanning electron microscopy and verified through density functional theory calculations. The functional film formed on the cathode surface suppressed the side reactions between the cathode and electrolyte during cell cycling. As a result, the film prevented CEI thickening and performance deterioration. The optimum weight of TrP was determined to be 0.4 wt % for obtaining the best performance.

Stabilization of Lithium Cobalt Phosphate Cathodes via Artificial Interphases

Olivine LiCoPO4 (LCP) exhibits a rare combination of high theoretical capacity (167 mAh g−1), excellent thermal stability, and high redox potential (4.8 V vs vs Li/Li+), making it a promising candidate for high voltage lithium batteries. Despite these attractive properties, practical implementation of this electrode chemistry has been limited by stability issues at the cathode-electrolyte interface, including parasitic electrolyte reactions, surface decomposition of the electrode material, and Co dissolution. Carbon coating and substitutions of Co by Fe and other cations improve the performance, however the cycling stability needs further improvement. In an effort to address these issues, we deposited thin, conformal metal oxide surface coatings on substituted LCP powder and investigated the effects of these coatings on the performance of carbon-coated substituted LCP/MCMB graphite full cells with a standard carbonate electrolyte. Remarkably, some of these coatings clearly improved operation of carbon-coated substituted LCP cells as compared to the as-prepared cathode powder. Observed improvements in capacity retention relate to stabilization of the cathode-electrolyte interface and suppression of electrolyte oxidation, as measured by online electrochemical mass spectroscopy (OEMS) of evolved gases within the cell. Together, these results suggest artificial interphases are a viable pathway toward stabilizing LCP and achieving commercial viability.

Uniformizing the electric field distribution and ion migration during zinc plating/stripping via a binary polymer blend artificial interphase

The PAM/PVP interphase prevents direct contact of the metal Zn anode with the aqueous electrolyte and uniformizes electric field distribution and ion migration during zinc plating/stripping, suppressing the zinc dendrite growth and side reactions.

Cation Solvation and Physicochemical Properties of Ca Battery Electrolytes.

Divalent-cation-based batteries are being considered as potential high energy density storage devices. The optimization of electrolytes for these technologies is, however, still largely lacking. Recent demonstration of the feasibility of Ca and Mg plating and stripping in the presence of a passivation layer or an artificial interphase has paved the way for more diverse electrolyte formulations. Here, we exhaustively evaluate several Ca-based electrolytes with different salts, solvents, and concentrations, via measuring physicochemical properties and using vibrational spectroscopy. Some comparisons with Mg- and Li-based electrolytes are made to highlight the unique properties of the Ca2+ cation. The Ca-salt solubility is found to be a major issue, calling for development of new highly dissociative salts. Nonetheless, reasonable salt solubility and dissociation are achieved using bis(trifluoromethanesulfonyl)imide (TFSI), BF4, and triflate anion based electrolytes and high-permittivity solvents, such as ethylene carbonate (EC), propylene carbonate (PC), γ-butyrolactone (gBL), and N,N-dimethylformamide (DMF). The local Ca2+ coordination is concentration-dependent and rather complex, possibly involving bidentate coordination and participation of the nitrogen atom of DMF. The ionicity and the degree of ion-pair formation are both investigated and found to be strongly dependent on the nature of the cation, solvent donicity, and salt concentration. The large ion–ion interaction energies of the contact ion pairs, confirmed by density functional theory (DFT) calculations, are expected to play a major role in the interfacial processes, and thus, we here provide electrolyte design strategies to engineer the cation solvation and possibly improve the power performance of divalent battery systems.

(IBA Early Career Award) Challenges and Opportunities for Interphased Ca Metal Anode Batteries

Various metals have been used as battery anodes in electrochemical cells ever since the birth of the batteries with Volta’s pile and in the first commercialized primary (Zn/MnO2, Leclanché 1866) and secondary (Pb/acid, Planté 1859) batteries. Li-MoS2 cells, employing Li metal anodes, with specific energies two to three times higher than both Ni/Cd and Pb/acid cells, were withdrawn from the market due to safety issues related to dendrites growth. Instead, electrodeposition of Mg and Ca appears to be less prone to dendrite formation.[1,2] Pioneering work by Aurbach et al. in the early 1990’s showed a surface-film controlled electrochemical behavior of Ca and Mg metal anodes in electrolytes with conventional organic solvents.[3,4] The lack of metal plating was attributed to the poor divalent cation migration through the passivation layer. Nevertheless, recent demonstration of Ca and Mg plating and stripping in the presence of a passivation layer or an artificial interphase [2,5,6] has paved the way for assessment of new electrolyte formulations with high resilience towards oxidation. However, several challenges remain to be tackled for the development of Ca based batteries.[7] Among these, the need for reliable electrochemical test protocols, mass transport limitations and high desolvation energies (due to strong cation-solvent and cation–anion interactions) are implied.[8] Here, the reliability of electrochemical set-ups involving multivalent chemistries is discussed, and a systematic investigation on the impact of the electrolyte formulation on the cation solvation structure and transport is presented. Finally, a systematic characterization of the SEI formed on the Ca metal anode in various electrolyte formulations using complementary techniques allowed for the identification of the most suitable SEI compounds in terms of divalent cation mobility. Reference s : [1] M. Matsui, J. Power Sources, 196 (2011) 7048. [2]. A. Ponrouch, C. Frontera, F. Bardé, M.R. Palacín, Nat. Mater., 15 (2016) 169. [3] D. Aurbach, R. Skaletsky, Y. Gofer, J. Electrochem. Soc.138 (1991) 3536. [4] Z. Lu, A. Schechter, M. Moshkovich, D. Aurbach, J. Electroanal. Chem. 466 (1999) 203. [5] D. Wang, X. Gao, Y. Chen, L. Jin, C. Kuss, P. G. Bruce, Nat. Mater. 17 (2018) 16. [6] S.-B. Son, T. Gao, S. P. Harvey, K. X. Steirer, A. Stokes, A. Norman, C. Wang, A. Cresce, K. Xu, C. Ban, Nat. Chem. 10 (2018) 532. [7] A. Ponrouch, M.R. Palacín, Current Opinion in Electrochemistry 2018,doi.org/10.1016/j.coelec.2018.02.001. [8] D. S. Tchitchekova, D. Monti, P. Johansson, F. Bardé, A. Randon-Vitanova, M. R. Palacı́n, A. Ponrouch, J. Electrochem. Soc., 164 (2017) A1384. Figure 1: Scheme of a Ca metal anode-based battery with the main problems/ requirements outlined.[7] Figure 1

Investigation of Atomic Layer Deposited Al2O3 High Energy Nickel Cobalt Manganese Oxide Cathode Materials

High-Energy Nickel Cobalt Manganese Oxide (HED-NCM) is a state-of-art positive electrode material which achieves a high specific capacity (~250 mAh/g). Overall cycling life is limited by electrode degradation, stemming mainly from oxygen release as well as transition metal dissolution. To mitigate the latter problem, a thin layer of aluminum oxide (Al2O­3­) can be applied to the active material by atomic layer deposition (ALD) to form an artificial cathode-electrolyte interphase (CEI). Testing has shown that the Al2O3 coating improves overall reversible capacity, most notably at high temperature (40oC). However, effect of the Al2O3 on the CEI and SEI formed upon cycling has yet to be understood. The cycling performance and surface chemistry Al2O3 coated HED-NCM materials cycled at room temperature and 40°C were investigated via ATR-FT-IR and XPS spectroscopies, and ICP-MS after the first and 50th cycles. Overall, electrodes made with Al2O3 coated material had lower concentrations of polyethylene carbonate and fluorine species, and Al2O­3­ coating helps in preventing transition metal dissolution.

Artificial cathode-electrolyte interphases on nickel-rich cathode materials modified by silyl functional group

Nickel-rich nickel-cobalt-manganese layered oxides receive significant attention as advanced cathode materials, however, they suffer from poor cycling performance at elevated temperature because of surface instability. In this study, we develop nickel-rich cathode materials modified by an artificial cathode-electrolyte interphase layer embedding silyl ether functional groups. An artificial cathode-electrolyte interphase layer-functionalized nickel-rich cathode materials are simply synthesized via a wet-coating-based thermal treatment using a dimethoxydimethylsilane as an organic precursor. The task-specific silyl ether functional groups are effective in selectively scavenging nucleophilic fluoride species, which potentially triggers the dissolution of transition metal components into the electrolyte. Microscopic analyses indicate that the artificial cathode-electrolyte interphase layer is well developed on the surface of the nickel-rich cathode materials with several nanometers-thickness. The cells cycled with functionalized nickel-rich cathodes exhibit much higher cycling retentions (∼70.0%) than the cell cycled with bare nickel-rich cathode (47.1%) at high temperature. Additional systematical analyses indicate that the artificial cathode-electrolyte interphase layers effectively mitigate the electrolyte decomposition and the dissolution of transition metal components, thereby improving the cycling behavior of the cell on the basis of increased interfacial stability of nickel-rich cathode materials.