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At least 847 records · Page 47

Liquid electrolytes for low-temperature lithium batteries: main limitations, current advances, and future perspectives

Lithium-ion batteries (LIBs) can now be used in almost all modern electronic devices and electric vehicles. However, as the range of applications increases, the challenges increase as well, especially at very low temperatures. Many individual processes could result in capacity loss of LIBs at low temperatures; however, most of them are associated with the liquid electrolyte inside the battery. In this review, we first discuss the main limitations in developing liquid electrolytes used in low-temperature LIBs, and then we summarize the current advances in low-temperature electrolytes, including lithium salts, solvents, additives, and new strategies. Finally, we present some perspectives on the current state of low-temperature electrolytes for LIBs, outlining the most promising research areas in this field. In conclusion, this review will provide useful insights into the design of cryogenic electrolytes and the path forward to the widespread use of LIBs in cryogenic environments.

25 ENERGY STORAGE↗

Understanding fluorine-free electrolytes via small-angle X-ray scattering

Fluorine-free electrolytes have attracted great attention because of its low-cost and environmental friendliness. However, so far, little is known about the solution structures of these electrolytes. Here, we compare the solvation phenomenon of sodium tetraphenylborate (NaBPh 4 ) salt dissolved in organic solvents of propylene carbonate (PC), 1,2-dimethoxyethane (DME), acetonitrile (ACN) and tetrahydrofuran (THF). Small-angle X-ray scattering (SAXS) reveals a unique two-peak structural feature in this salt concentrated PC electrolyte, while solutions using other solvents only have one scattering peak. Molecular dynamics (MD) simulations further reveal that there are anion-based clusters in addition to the short-range charge ordering in the concentrated NaBPh4/PC electrolyte. Raman spectroscopy confirms the existence of considerable contact ion pairs (CIPs). Here, this work emphasizes the importance of global and local structural analysis, which will provide valuable clues for understanding the structure performance relationship of electrolytes.

25 ENERGY STORAGE↗

Synthesis of UO 2 nanoparticles via coulometric titration: influence of electrolytes and ligands on synthesized particle properties

Here, this study investigates the controlled synthesis of uranium oxide nanoparticles (UO 2 NPs) via coulometric titration under ambient conditions, focusing on the impact of electrolyte anions, salt concentrations, and strongly complexing ligands on particle formation and properties. Using dilute solutions of mineral acids (HNO 3 , HCl, and HClO 4 ), we demonstrate that the choice of electrolyte anion affects particle size, polydispersity, and surface charge. Particle characterization using dynamic light scattering and transmission electron microscopy shows that particles synthesized in perchlorate are largest and show a high degree of polydispersity. In comparison, particles synthesized in chloride are smaller and more uniform in size. Synthesis in nitrate yields a wide variety of particle sizes, with the major fraction (>65 %) having a smaller size than that obtained in the other two electrolytes. The presence of more strongly coordinating ligands such as sulfate and acetate modulate hydrolysis and condensation reactions, with sulfate suppressing nanoparticle formation across a wide concentration range ([SO 4 2- ] > 5 mM) and acetate enabling stable colloidal suspensions at [HOAc] ≤ 0.1 M. Synthesis in concentrated electrolytes (2 M NaNO 3 , NaCl, or NaClO 4 ) accelerates reaction kinetics but introduces challenges, as particles showed increased polydispersity and aggregation, and were more prone to oxidation. Electrolyte effects on actinide oxide nanoparticle formation are discussed and a short comparison to established nanoparticle syntheses is drawn. This work underscores the importance of tailoring synthesis parameters to achieve desired nanoparticle properties, providing valuable insights for optimizing UO 2 NP production for various applications.

Actinide hydrolysis↗

Anode-free, Lean-Electrolyte Lithium-Sulfur Batteries Enabled by Tellurium-Stabilized Lithium Deposition

For realizing practically viable lithium-sulfur (Li-S) batteries, it is imperative to stabilize Li deposition and improve cyclability while reducing excess Li and electrolyte. We have discovered that introducing tellurium (Te) into the Li-S system as a cathode additive significantly improves the reversibility of Li plating and stripping by forming a tellurized and sulfide-rich solid-electrolyte interphase (SEI) layer on the Li surface. A remarkable improvement in cyclability is demonstrated in anode-free full cells with limited Li inventory and large-area Li-S pouch cells under lean electrolyte conditions. Tellurium reacts with polysulfides to generate soluble polytellurosulfides that migrate to the anode side and form stabilizing lithium thiotellurate and lithium telluride in situ as SEI components. A significant reduction in electrolyte decomposition on the Li surface is also engendered. This work demonstrates Te inclusion as a viable strategy for stabilizing Li deposition and establishes a robust evaluation framework for preserving electrochemical performance under limited Li and limited electrolyte conditions.

36 MATERIALS SCIENCE↗

Fluorinated Phosphazene Co-solvents for Improved Thermal and Safety Performance in Lithium-Ion Battery Electrolytes

The safety of lithium-ion batteries is coming under increased scrutiny as they are being adopted for large format applications especially in the vehicle transportation industry and for grid-scale energy storage. The primary short-comings of lithium-ion batteries are the flammability of the liquid electrolyte and sensitivity to high voltage and elevated temperatures. We have synthesized a series of non-flammable fluorinated phosphazene liquids and blended them with conventional carbonate solvents. While the use of these phosphazenes as standalone electrolytes is highly desirable, they simply do not satisfy all of the many requirements that must be met such as high LiPF6 solubility and low viscosity, thus we have used them as additives and co-solvents in blends with typical carbonates. The physical and electrochemical properties of the electrolyte blends were characterized, and then the blends were used to build 2032-type coin cells which were evaluated at constant current cycling rates from C/10 to C/1. We have evaluated the performance of the electrolytes by determining the conductivity, viscosity, flash point, vapor pressure, thermal stability, electrochemical window, cell cycling data, and the ability to form solid electrolyte interphase (SEI) films. This paper presents our results on a series of chemically similar fluorinated cyclic phosphazene trimers, the FM series, which has exhibited numerous beneficial effects on battery performance, lifetimes, and safety aspects.

25 ENERGY STORAGE↗

Bio-inspired redox mediated electrolyte for high performance flexible supercapacitor applications over broad temperature domain

For practical supercapacitors, recent advances in electrolytes have diminished long-standing problems such chemical stability, low ionic conductivity and limited electrochemical performance. Herewith, we communicate a facile method to produce anhydrous redox-active Bio-inspired electrolytes for flexible supercapacitors with application over a broad temperature range. The glycerol (Gly) gel electrolyte consists of various fractions of potassium hydroxide (KOH) and redox active unit, i.e., ammonium molybdate, (NH 4 ) 2 MoO 4 (abbreviated as Mo), in the anhydrous state. The doped glycerol matrix acts as a framework that provides a stable gel electrolyte, forming hierarchical pathway for ion diffusion. The developed gel network with Gly-KOH-MoX (X = 3, 5, 10, and 15%, w/w) provides an effective route to carry the ions onto the pores of the electrodes. The supercapacitor with Gly-KOH5-Mo10 gel provides a specific capacitance of 328 F g –1 , and the same device achieved an energy density of 45.6 Wh kg –1 at a power density of 497 W kg –1 . In addition, the supercapacitor maintained extraordinary cyclic robustness and wide temperature tolerance. Thus, the low cost and environmentally benign, cyclic durability of Gly-KOH-Mo makes these gel electrolytes a potential candidate for use in various energy storage devices.

25 ENERGY STORAGE↗

Polymer-ceramic composite electrolytes for all-solid-state lithium batteries: Ionic conductivity and chemical interaction enhanced by oxygen vacancy in ceramic nanofibers

Perovskite Li 3x La 2/3-x TiO3 (LLTO) nanofibers have been heat-treated in the hydrogen-containing atmosphere and then incorporated with the poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP) polymer to form a composite electrolyte. Hydrogen treatment has created oxygen vacancies in the LLTO nanofibers, which has reduced the activation energy of Li ion transport along intra-grains and inter-grains, leading to improvement in the ion conductivity of LLTO nanofibers. Hydrogen treatment of the LLTO nanofibers has also enhanced the chemical interaction between the LLTO nanofibers and the polymer matrix in the composite electrolyte, and favored the Li ion transport at the nanofiber/polymer interface, improving the ion conductivity of the composite electrolyte to 3.4×10- 4 S/cm at room temperature. As a result, the Li|composite-electrolyte|Li half-cell exhibits good stability during lithium plating/stripping cycling at room temperature, showing an overpotential of ~91 mV at a constant current density of 0.5 mA/cm 2 . Finally, the full-cell battery with the composite electrolyte, lithium metal anode and lithium iron phosphate cathode shows excellent rate capacity and cycling performance.

25 ENERGY STORAGE↗

Enabling fast discharge of Li-ion batteries via electrolyte formulations for urban air mobility applications

High-power discharge requirements are critical for lithium-ion batteries (LIBs) used in electric Vertical Takeoff and Landing (eVTOL) vehicles that are increasingly considered in urban mobility. This investigation places a particular emphasis on understanding the impact of electrolytes on discharge processes and rate capability. We aim to compare the discharge behavior of LiBs using a conventional electrolyte (Gen 2: 1.2 M LiPF 6 in EC:EMC) and the dual salt LiTFSI-LiBOB-based electrolyte. Here we carefully examine the profiles of charging and discharging, the behavior during extended cycles, impedance spectroscopy results, and the characteristics of the electrode surface. Our research findings demonstrate the complex relationship between the composition of electrolytes and the specific high-power discharge requirements of electric vertical takeoff and landing (eVTOL) systems. This research highlights the importance of customizing electrolyte compositions to optimize energy storage density while simultaneously enabling higher power extraction to enhance performance in short-range electric aviation.

25 ENERGY STORAGE↗

Mapping of fracture and ionic conductivity changes in ion implanted solid electrolytes: Insights from molecular dynamics

Ion implantation emerges as a promising technique to address the persistent challenge of lithium (Li) filament growth in solid-state electrolytes as it can induce compressive stresses inhibiting crack growth and deflect dendrites, de facto mitigating early electrolyte failure. In this study, we examine the potential paradox of ion implantation: while aiming to enhance electrolyte performance, the radiation damage associated with implantation might inadvertently compromise both the ionic conductivity and the intrinsic fracture toughness of the material, rendering the material unsuitable for battery applications. Specifically, we employed molecular dynamics simulations to examine the scope of the downsides of ion implantation, specifically: (i) reduced ionic conductivity (due to radiation-induced amorphization) and (ii) mechanical stability (due to radiation-induced embrittlement) in ion-implanted Li 7 La 3 Zr 2 O 12 (LLZO) solid-state electrolytes. We explore how radiation damage impacts LLZO’s crystalline structure, Li-ion diffusion, and fracture properties at various temperatures and radiation damage levels. The study aims to provide insights into the competing effects of ion implantation and suggest potential engineering strategies for developing more robust solid-state electrolytes with improved conductivity and dendrite resistance.

Conductivity↗

Dual phase polymer gel electrolyte based on non-woven poly(vinylidenefluoride-co-hexafluoropropylene)–layered clay nanocomposite fibrous membranes for lithium ion batteries

Graphical abstract: Display Omitted Highlights: ► P(VdF-co-HFP)–clay nanocomposite based electrospun membranes are prepared. ► The membranes are used as polymer gel electrolyte (PGE) in lithium ion batteries. ► The composite PGE shows ionic conductivity of 5.5 mS cm{sup −1} at room temperature. ► Li/PGE/LiFePO{sub 4} cell delivers initial discharge capacity of 160 mAh g{sup −1}. ► The use of prepared electrolyte significantly improved the cell performance. -- Abstract: A new approach for fabricating polymer gel electrolytes (PGEs) based on electrospun poly(vinylidenefluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) incorporated with layered nanoclay has been employed to enhance the ionic conductivity and electrochemical properties of P(VdF-co-HFP) without compromising its mechanical strength. The effect of layered nanoclay on properties of membranes has been evaluated by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Surface morphology of the membranes has been studied using field-emission scanning electron microscopy (FE-SEM). Polymer gel electrolytes are prepared by soaking the fibrous membrane into 1 M LiPF{sub 6} in EC/DEC. The electrochemical studies show that incorporation of layered nanoclay into the polymer matrix greatly enhanced the ionic conductivity and compatibility with lithium electrodes. The charge–discharge properties and cycling performance of Li/LiFePO{sub 4} cells comprising nanocomposite polymer gel electrolytes have been evaluated at room temperature.

36 MATERIALS SCIENCE↗

Stability of the solid electrolyte Li{sub 3}OBr to common battery solvents

Graphical abstract: The stability of the anti-perovskite phase Li{sub 3}OBr has been assessed in a variety of battery solvents. - Highlights: • Lithium stable solid electrolyte Li{sub 3}OBr unstable to polar organic solvents. • Solvation with no dissolution destroys long-range structure. • Ion exchange with protons observed. - Abstract: Recently a new class of solid lithium ion conductors was reported based on the anti-perovskite structure, notably Li{sub 3}OCl and Li{sub 3}OBr. For many beyond lithium-ion battery uses, the solid electrolyte is envisioned to be in direct contact with liquid electrolytes and lithium metal. In this study we evaluated the stability of the Li{sub 3}OBr phase against common battery solvents electrolytes, including diethylcarbonate (DEC) and dimethylcarbonate (DMC), as well as a LiPF{sub 6} containing commercial electrolyte. In contact with battery-grade organic solvents, Li{sub 3}OBr was typically found to be insoluble but lost its crystallinity and reacted with available protons and in some cases with the solvent. A low temperature heat treatment was able to restore crystallinity of the samples; however evidence of proton ion exchange was conserved.

36 MATERIALS SCIENCE↗

Lithium stoichiometry of solid electrolytes based on tetragonal Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}

Graphical abstract: - Highlights: • We prepared Li{sub x}La{sub 3}Zr{sub 2}O{sub 8.5+0.5x} (x = 6, 7, 8, 9, 10) by the citrate–nitrate method. • We studied phase composition and conductivity of Li{sub x}La{sub 3}Zr{sub 2}O{sub 8.5+0.5x}. • We proposed a simple method to determine the carbonate impurity content in the solid electrolytes. • The synthesized solid electrolytes Li{sub x}La{sub 3}Zr{sub 2}O{sub 8.5+0.5x} (x = 7–9) have 1.32–3.49 wt.% Li{sub 2}CO{sub 3}. • The composition with x = 9 has high total conductivity, 7.5 × 10{sup −6} S cm{sup −1}, at room temperature. - Abstract: Samples of Li{sub x}La{sub 3}Zr{sub 2}O{sub 8.5+0.5x} (x = 6, 7, 8, 9, 10) were synthesized with the citrate–nitrate method. Neutron diffraction studies have shown the presence of lithium carbonate impurities in the synthesized compounds. We propose a simple and effective method to determine the carbonate impurity content in the solid electrolytes. The technique is based on the measurement of the carbon dioxide volume produced from the interaction of the investigated material with acid. Determined in this way, the content of Li{sub 2}CO{sub 3} in the synthesized electrolytes Li{sub 7}La{sub 3}Zr{sub 2}O{sub 12}, Li{sub 8}La{sub 3}Zr{sub 2}O{sub 12.5} and Li{sub 9}La{sub 3}Zr{sub 2}O{sub 13} are 1.32 ± 0.04, 1.95 ± 0.06 and 3.49 ± 0.10 wt.%, respectively. From the obtained data, the actual lithium content per formula unit of complex oxide was calculated for the synthesized compounds. The composition with x = 9 had the highest total conductivity, σ = 7.5 × 10{sup −6} S cm{sup −1}, at room temperature. All the investigated electrolytes have an activation energy of approximately 50 kJ mol{sup −1}.

36 MATERIALS SCIENCE↗

Electrolyte design for Li metal-free Li batteries

Li metal, with the lowest thermodynamically achievable negative electrochemical potential and the highest specific capacity (3860 mAh g -1 ), is the ultimate anode choice for Li batteries. However, the highest reported Li plating/stripping Coulombic efficiency (CE) of 99.5% after extensive efforts is still too low for the Li metal-free (all the Li metal in cycling comes from cathode, without anode pre-lithiation) Li metal batteries. The low CE is attributed to both non-uniform Li plating/stripping on the lithiophobic Cu current collector and Li dendrite growth through lithiophilic organic–inorganic solid electrolyte interphase (SEI) formed in carbonate electrolytes. Here, we use a lithiophilic Bismuth graphite blend (Bi–Gr) substrate to replace lithiophobic Cu current collector to seed a uniform Li nucleation, and form a lithiophobic LiF-rich SEI rather than lithiophilic organic-rich SEI to suppress Li dendrite growth. Molecular dynamics simulations reveal the preferential reduction of anions in 2.0 M LiPF 6 in tetrahydrofuran/2-methyl tetrahydrofuran (2.0 M LiPF 6 –mixTHF) electrolyte to generate LiF-rich SEI on plated Li. Bi–Gr substrate and 2.0 M LiPF 6 –mixTHF electrolyte enable the Li anodes to achieve a record high CE of 99.83% at a high capacity of 1.0 mAh cm -2 and current of 0.5 mA cm -2 . The Bi particles serve as dispersed nucleation centers that promote uniform Li deposition with strong adhesion to the substrate to avoid dead Li, while the lithiophobic LiF-rich SEI promotes lateral Li growth and suppresses the vertical Li dendrite growth even at a high current density of 3.0 mA cm -2 and high areal capacities of 3.0 mAh cm -2 . The regulation of Li nucleation and growth enables the Li metal-free LiFePO 4 full cells to achieve 100 cycles at a practical areal capacity of >2.0 mAh cm -2 . This article highlights the benefits of simultaneous substrate design to improve Li nucleation and electrolyte design to promote lithiophobic SEI growth, enabling a promising and practical route Li metal-free Li metal batteries.

36 MATERIALS SCIENCE↗

Molecular-level insights into structure and dynamics in ionic liquids and polymer gel electrolytes

We report designing new electrolytes requires a better understanding of the correlation between their transport properties and their molecular structure. In this work, we present a detailed study of ionic liquids and polymer gel electrolytes probing their structure and dynamics by nuclear magnetic resonance (NMR) spectroscopy. In particular, ammonium- and phosphonium-based ionic liquids (ILs) are combined with different LiTFSI concentrations, and then with different ratios of poly(methylmethacrylate) polymer. The temperature dependence of self-diffusion coefficients of mobile species, D Li+ , D TFSI- and D P4441+ or D N4441+ , measured by pulsed field gradient (PFG) NMR spectroscopy obeys the Arrhenius equation. Diffusivity of [P4441][TFSI] ILs is found to be greater than those of the [N4441][TFSI] ILs in both liquid and gel electrolytes. Solid state NMR experiments including 13 C and 19 F MAS, 13 C{ 19 F}, 13 C{ 1 H} CPMAS probe the local structure and molecular-level interactions between ions and polymer in gel electrolytes, particularly for samples with higher PMMA content (≥25 wt%). Finally, the fast field cycling relaxometry has been used to unveil the rotational and translational dynamics of P4441 + or N4441 + and TFSI - by measuring 1 H and 19 F R 1 relaxation rate profiles at different temperatures. A comprehensive NMR analysis including relaxation studies at low magnetic field provides decisive new insights regarding the formation of ionic clusters and the interaction of ions with the polymer chain in the case of the gel electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Liquid perfluoropolyether electrolytes with enhanced ionic conductivity for lithium battery applications

Here, we prepared nonflammable liquid polymer electrolytes for lithium-ion batteries by mixing ethoxylated perfluoropolyethers (PFPEs) with LiN(SO 2 CF 3 ) 2 salt. Interestingly, we identified the presence of chain coupling in the PFPE polymers and their functionalized derivatives, resulting in a mixture of PFPEs with varying molecular weights. The distribution of molecular weights, along with PFPE's multiple functionalities, allows systematic manipulation of structure to enhance electrochemical and physical properties. Furthermore, the electrolytes exhibited a wide thermal stability window (5% degradation temperature >180°C). Despite substantial increases in viscosity upon loading the PFPEs with lithium salt, the conductivity (σ ≈ 5 × 10 -5 S cm -1 at 28°C) of the novel electrolytes was about an order of magnitude higher than that of our previously reported PFPE electrolytes. Ethoxylated derivatives of PFPE electrolytes exhibit elevated conductivity compared to non-ethoxylated derivatives, demonstrating our capability to enhance the conductive properties of the PFPE platform by attaching various functional groups to the polymer backbone.

25 ENERGY STORAGE↗

Critical role of polymer-ceramic ion exchange for high conductivity composite electrolytes

Polymer-ceramic composites offer a path to enhance the transport and mechanical properties of solid electrolytes. However, an in-depth understanding of the extent and role of ion transport along and across polymer-ceramic interfaces in these systems is lacking. We have recently shown that Li-conducting Li 0.11 Na 0.24 K 0.02 La 0.43 TiO 2.82 (LMTO) nanorods can be prepared by a molten flux method, and the addition of 30–50 weight (wt.)% LMTO to a bis[(trifluoromethyl)sulfonyl]imide-vinyl ethylene carbonate-based single-ion conducting (SIC) polymer electrolyte leads to a two-fold enhancement in Li-ion conductivity, from 1.4 to 3.0 × 10 −5 S/cm at 30 °C. In the present study, we use NMR methods to identify the Li-ion transport pathways and determine the timescale of chemical exchange between the SIC polymer and LMTO ceramic components. Tracer exchange NMR indicates preferential transport through the polymer or polymer-interfacial regions, and exchange spectroscopy (EXSY) and a new isotope exchange method reveal negligible Li exchange between the SIC polymer and LMTO ceramic up to several days. Here, LMTO nanorods act as a passive filler. Our results further highlight that significant (e.g., 10- or 100-fold) conductivity enhancements in composite electrolytes can only be achieved 1) with ionically-conductive fillers, and 2) when both the ceramic and polymer components actively participate in long-range transport. For this, fast interfacial ion exchange is needed. In conclusion, this leads us to introduce a critical interfacial ion exchange time to evaluate whether a filler actively contributes to conduction in a composite electrolyte, and screen for promising polymer-ceramic pairings to accelerate the development of high conductivity solid electrolytes.

Battery, Solid electrolyte↗

Reprocessable and Recyclable Polymer Network Electrolytes via Incorporation of Dynamic Covalent Bonds

Mechanically durable polymer network electrolytes are desirable for batteries; however, covalent cross-linking adversely affects their large-scale manufacturing, and they are difficult to recycle post-lifespan. In this work, we address the electrolyte reprocessability and recyclability challenges through the use of dynamic covalent bonds for polymer network solid electrolytes. Specifically, the associative dynamic vinylogous urethane motif is incorporated into a poly(ethylene oxide) network electrolyte containing lithium bis(fluorosulfonyl)imide (LiFSI) salt. The resulting dynamic covalent network electrolyte possesses a modest ion conductivity (~10–5 S/cm at room temperature) and good reprocessability. Stress–relaxation studies indicate that the LiFSI salt can catalyze the bond exchange and enhance the network dynamics. Furthermore, the reprocessability associated with bond exchange can be tuned by simply adjusting the formulation of reagent compositions, in which increasing the amount of excess amine or using a shorter chain of PEO prepolymer can further enhance the network dynamics and corresponding reprocessability.

25 ENERGY STORAGE↗

Relationship of the Molecular Structure and Transport Properties of Imide-Based Lithium Salts of “Acetonitrile/Water-in-Salt” Electrolytes

“Water-in-salt” (WIS) electrolytes exhibit excellent safety and electrochemical performance. However, they possess high concentrations, relatively low diffusion coefficient, and high viscosity. “Acetonitrile/water in salt” (AWIS) electrolytes can overcome the disadvantages of WIS electrolytes. Under relatively low concentrations, AWIS electrolytes show good electrochemical performance comparable to WIS electrolytes and low conductivity. Herein, we investigate the relationship between the solvation structures and the transport properties using small-angle X-ray scattering and molecular dynamics simulation. We observed two solvation behaviors of AWIS: anions dissolved in acetonitrile forming small acetonitrile/anion clusters and additional water further dissolving the small acetonitrile/anion clusters. The introduction of acetonitrile weakens the water–solute interaction and enhances the cation–anion interaction, which results in an enhanced dynamical slowdown as the concentration increases. In conclusion, this work provides molecular-level understanding of the connection between two-stage solvation structures and transport properties for imide-based lithium salt solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗