Soft, thin skin-mounted power management systems and their use in wireless thermography.

Power supply represents a critical challenge in the development of body-integrated electronic technologies. Although recent research establishes an impressive variety of options in energy storage (batteries and supercapacitors) and generation (triboelectric, piezoelectric, thermoelectric, and photovoltaic devices), the modest electrical performance and/or the absence of soft, biocompatible mechanical properties limit their practical use. The results presented here form the basis of soft, skin-compatible means for efficient photovoltaic generation and high-capacity storage of electrical power using dual-junction, compound semiconductor solar cells and chip-scale, rechargeable lithium-ion batteries, respectively. Miniaturized components, deformable interconnects, optimized array layouts, and dual-composition elastomer substrates, superstrates, and encapsulation layers represent key features. Systematic studies of the materials and mechanics identify optimized designs, including unusual configurations that exploit a folded, multilayer construct to improve the functional density without adversely affecting the soft, stretchable characteristics. System-level examples exploit such technologies in fully wireless sensors for precision skin thermography, with capabilities in continuous data logging and local processing, validated through demonstrations on volunteer subjects in various realistic scenarios.

Quantitative Operando Visualization of Electrochemical Reactions and Li Ions in All-Solid-State Batteries by STEM-EELS with Hyperspectral Image Analyses.

All-solid-state lithium-ion batteries (LIBs) are one of the promising candidates to overcome some issues of conventional LIBs with liquid electrolytes. However, high interfacial resistance of Li-ion transfer at the electrode/solid electrolyte limits their performance. Thus, it is important to clarify interfacial phenomena in a nanometer scale. Here, we present a new method to dynamically observe the Li-ion distribution and Co-ion electronic states in a LiCoO2 cathode of the all-solid-state LIB during charge and discharge reactions using operando scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS). By applying a hyperspectral image analysis of non-negative matrix factorization (NMF) to the STEM-EELS, we succeeded in clearly observing the quantitative Li-ion distribution in the operando condition. We found from the operando observation with NMF that the Li ions did not uniformly extract/insert during the charge/discharge reactions, and the activity of the electrochemical reaction depended on the Li-ion concentration in a pristine state. An electrochemically inactive region was formed about 10-20 nm near the LiCoO2/Li2O-Al2O3-TiO2-P2O5-based solid electrolyte interfaces. The STEM-EELS, electron diffraction, and Raman spectroscopy experimentally showed that the inactive region was a mixture of LiCoO2 and Co3O4, leading to the higher interfacial resistance of the Li-ion transfer because Co3O4 does not have pathways of Li-ion diffusion in its crystal.

Solution-processed poly(vinylidene difluoride)/cellulose acetate/Li1+xAlxTi2-x(PO4)3 composite solid electrolyte for improving electrochemical performance of solid-state lithium-ion batteries at room temperature.

To enhance energy density and secure the safety of lithium-ion batteries, developing solid-state electrolytes is a promising strategy. In this study, a composite solid-state electrolyte (CSE) composed of poly(vinylidene difluoride) (PVDF)/cellulose acetate (CA) matrix, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, and Li1.3Al0.3Ti1.7(PO4)3 (LATP) fillers is developed via a facile solution-casting method. The PVDF/CA ratio, LiTFSI, and LATP fractions affect the crystallinity, structural porosity, and thermal and electrochemical stability of the PVDF/CA/LATP CSE. The optimized CSE (4P1C-40LT/20F) presents a high ionic conductivity of 4.9 × 10-4 S cm-1 and a wide electrochemical window up to 5.0 V vs. Li/Li+. A lithium iron phosphate-based cell containing the CSE delivers a high discharge capacity of over 160 mAh g-1 at 25 °C, outperforming its counterpart containing PVDF/CA polymer electrolyte. It also exhibits satisfactory cycling stability at 1C with approximately 90 % capacity retention at the 200th cycle. Additionally, its rate performance is promising, demonstrating a capacity retention of approximately 80 % under varied rates (2C/0.1C). The increased amorphous region, Li+ transportation pathways, and Li+ concentration of the 4P1C-40LT/20F CSE membrane facilitate Li+ migration within the CSE, thus improving the battery performance.

Optimization of Porous Structures of Carbon Matrices for Loading Red Phosphorus to Achieve High-Capacity and Long-Life Anodes for All-Solid-State Lithium-Ion Batteries.

All-solid-state lithium-ion batteries (ASSLIBs) using sulfide electrolytes and high-capacity alloy-type anodes have attracted sizable interest due to their potential excellent safety and high energy density. Encapsulating insulating red phosphorus (P) inside nanopores of a carbon matrix can adequately activate its electrochemical alloying reaction with lithium. Therefore, the porosity of the carbon matrix plays a crucial role in the electrochemical performance of the resulting red P/carbon composites. Here, we use zeolite-templated carbon (ZTC) with monodisperse micropores and mesoporous carbon (CMK-3) with uniform mesopores as the model hosts of red P. Our results reveal that micropores enable more effective pore utilization for the red P loading, and the P@ZTC material can achieve a record-high content (65.0 wt %) of red P confined within pores. When used as an anode of ASSLIBs, the P@ZTC electrode delivers an ultrahigh capacity of 1823 mA h g-1 and a high initial Coulombic efficiency of 87.44%. After 400 deep discharge-charge cycles (running over 250 days) at 0.2 A g-1, the P@ZTC electrode still holds a reversible capacity of 1260 mA h g-1 (99.92% capacity retention per cycle). Moreover, a P@ZTC||LiNi0.8Co0.1Mn0.1O2 full cell can deliver a reversible areal capacity of over 3 mA h cm-2 at 0.1C after 100 cycles.

Coating Robust Layers on Ni-Rich Cathode Active Materials while Suppressing Cation Mixing for All-Solid-State Lithium-Ion Batteries.

This study focused on addressing the challenges associated with the incompatibility between sulfide solid electrolytes and Ni-rich cathode active materials (CAMs) in all-solid-state lithium-ion batteries. To resolve these issues, protective layers have been explored for Ni-rich materials. Lithium lanthanum titanate (LLTO), a perovskite-type material, is recognized for its excellent chemical stability and ionic conductivity, which render it a potential protective layer in CAMs. However, traditional methods of achieving the perovskite structure involve temperatures exceeding 700 °C, resulting in challenges such as LLTO agglomeration, secondary phase formation between LLTO and CAM, and cation mixing within the CAM. In this study, a rapid technique known as flash-light sintering (FLS) was employed to fabricate a uniform and pure perovskite protective layer without inducing cation mixing within the CAM. The LLTO-coated LiNi0.8Co0.1Mn0.1O2 (NCM811) with FLS treatment demonstrated minimal cation mixing and formed a fully covered dense layer. This resulted in a high initial capacity and effectively addressed the incompatibility issues between the sulfide electrolytes and CAM. The rapid FLS method not only streamlines the fabrication of LLTO-coated NCM811 but also provides opportunities for its broader application to materials that were previously deemed impractical because of high sintering temperatures.

Effect of Li6.4La3Zr1.4Ta0.6O12 Fillers on the Interfacial Properties between Composite PEO-LiTFSI Electrolytes with Li Metal during Cycling.

PEO-LiX solid polymer electrolyte (SPE) with the addition of Li6.4La3Zr1.4Ta0.6O12 (LLZTO) fillers is considered as a promising solid-state electrolyte for solid-state Li-ion batteries. However, the developments of the SPE have caused additional challenges, such as poor contact interface and SPE/Li interface stability during cycling, which always lead to potentially catastrophic battery failure. The main problem is that the real impact of LLZTO fillers on the interfacial properties between SPE and Li metal is still unclear. Herein, we combined the electrochemical measurement and in situ synchrotron-based X-ray absorption near-edge structure (XANES) imaging technology to study the role of LLZTO fillers in directing SPE/Li interface electrochemical performance. In situ XRF-XANES mapping during cycling showed that addition of an appropriate amount of LLZTO fillers (50 wt %) can improve the interfacial contact and stability between SPE and Li metal without reacting with the PEO and Li salts. Additionally, it also demonstrated the beneficial effect of LLZTO particles for suppressing the interface reactions between the Li metal and PEO-LiTFSI SPE and further inhibiting Li-metal dendrite growth. The Li|LiFePO4 batteries deliver long cycling for over 700 cycles with a low-capacity fade rate of 0.08% per cycle at a rate of 0.3C, revealing tremendous potential in promoting the large-scale application of future solid-state Li-ion batteries.

Chemical speciation changes of an all-solid-state lithium-ion battery caused by roasting determined by sequential acid leaching.

All-solid-state lithium-ion batteries (ASS-LIBs) are expected to replace current liquid-based LIBs in the near future owing to their high energy density and improved safety. It would be preferable if ASS-LIBs could be recycled by the current recycling processes used for liquid-based LIBs, but this possibility remains to be determined. Here, we subjected an ASS-LIB test cell containing an argyrodite-type solid electrolyte (Li6PS5Cl) and nickel-manganese-cobalt-type active material (Li(Ni0.5Mn0.3Co0.2)O2) to roasting, a treatment process commonly used for recycling of the valuable metals from liquid-based LIBs, and investigated the changes in chemical speciation. Roasting was performed at various temperatures (350-900 °C), for various times (60-360 min), and under various oxygen fugacity (air or O2) conditions. The chemical speciation of each metal element after roasting was determined by sequential elemental leaching tests and X-ray diffraction analysis. Li formed sulfates or phosphates over a wide temperature range. Ni and Co followed very complicated reaction paths owing to coexistence of S, P, and C, and they formed sulfides, phosphates, and complex oxides. The optimum conditions for minimizing formation of insoluble compounds, such as complex oxides, were a roasting temperature of 450-500 °C and a roasting time of 120 min. The results indicated that although ASS-LIBs can be treated by the same roasting processes as those used for current liquid-based LIBs, the optimal roasting conditions have narrow ranges. Thus, careful process control will be needed to achieve high extraction percentages of the valuable metals from ASS-LIBs.

Origin of the Seriously Limited Anionic Redox Reaction of Li-Rich Cathodes in Sulfide All-Solid-State Batteries.

Li-rich layered oxide (LLO) cathode materials with mixed cationic and anionic redox reactions display much higher specific capacity than other traditional layered oxide materials. However, the practical specific capacity of LLO during the first cycle in sulfide all-solid-state lithium-ion batteries (ASSLBs) is extremely low. Herein, the capacity contribution of each redox reaction in LLO during the first charging process is qualitatively and quantitatively analyzed by comprehensive electrochemical and structural measurements. The results demonstrate that the cationic redox of the LiTMO2 (TM = Ni, Co, Mn) phase is almost complete, while the anionic redox of the Li2MnO3 phase is seriously limited due to the sluggish transport kinetics and severe LLO/Li6PS5Cl interface reaction at high voltage. Therefore, the poor intrinsic conductivity and interface stability during the anionic redox jointly restrict the capacity release or delithiation/lithiation degree of LLO during the first cycle in sulfide ASSLBs. This study reveals the origin of the seriously limited anionic redox reaction in LLO, providing valuable guidance for the bulk and interface design of high-energy-density ASSLBs.

Low-Temperature Sintering of a Garnet-Type Li6.5La3Zr1.5Ta0.5O12 Solid Electrolyte and an All-Solid-State Lithium-Ion Battery.

Garnet-type Ta-substituted Li7La3Zr2O12 materials attract considerable attention as solid electrolytes for use in future oxide-based all-solid-state lithium-ion batteries owing to their superior ionic conductivity and chemical and electrochemical stabilities. However, high-temperature sintering above 1000 °C, which is needed to realize high lithium-ion conductivity, results in the formation of insulating interface impurities at the electrode-electrolyte interface. Herein, the low-temperature sintering of the Li6.5La3Zr1.5Ta0.5O12 (LLZT) solid electrolyte at a remarkably low temperature of 400 °C was demonstrated using the submicrometer-sized garnet-type LLZT fine powder sample prepared at 600 °C through a reaction of Li2O and La2.4Zr1.2Ta0.4O7. The lithium-ion conductivity at 25 °C was 4.54 × 10-5 S cm-1 without any additives through low-temperature sintering at 400 °C. In addition, the preliminary battery performance of the oxide-based all-solid-state LiNi1/3Co1/3Mn1/3O2-Li4Ti5O12 full-battery cell fabricated at 400 °C using the present LLZT fine powder sample as the solid electrolyte was demonstrated.

Scalable fabrication of Solvent-Free composite solid electrolyte by a continuous Thermal-Extrusion process.

Composite solid-state electrolytes (CSEs) are regarded as a promising alternative for the next-generation lithium-ion batteries because they integrate the advantages of inorganic electrolytes and organic electrolytes. However, there are two issues faced by current CSEs: 1) a green and feasible approach to prepare CSEs in large scales is desired; and 2) the trace solvents, remaining from the preparation processes, lead to some serious concerns, such as safety hazard issues, electrolyte-electrode interfacial issues, and reduced durability of batteries. Here, a continuous thermal-extrusion process is presented to realize the large-scale fabrication of solvent-free CSE. A 38.7-meter CSE membrane was prepared as a demonstration in this study. Thanks to the elimination of residual solvents, the electrolyte membrane exhibited a high tensile strength of 3.85 MPa, satisfactory lithium transference number (0.495), and excellent electrochemical stability (5.15 V). Excellent long-term stability was demonstrated by operating the symmetric lithium cell at a stable current density of 0.1 mA cm-2 for over 3700 h. Solvent-free CSE lithium metal batteries showed a discharge capacity of 155.7 - 25.17 mAh g-1 at 0.1 - 2.0C, and the discharge capacity remained 78.1% after testing for 380cycles.

Effect of Solvents on a Li10GeP2S12-Based Composite Electrolyte via Solution Method for Solid-State Battery Applications.

Using a solution approach to process composite electrolytes for solid-state battery applications is a viable strategy for lowering the thickness of electrolyte layers and boosting the cell energy density. To fully utilize the super ionic conductivity of sulfides, more research about their solvent and binder compatibility is needed. Herein, the allowable solvent polarity is discovered through systematically pairing the solid electrolyte Li10GeP2S12 (LGPS) with eight types of aprotic solvents. To further consider the influence of oxygen and moisture solvation that is important to practical manufacturing scenario, we also design experiments to flow dry air and N2, or further mixed with water vapor, through these solvents to unveil their detrimental effects. Finally, a low polar solvent, dimethyl carbonate (DMC), and a previously unfavored commercial polymer, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), are chosen to fabricate a ∼40 µm thick LGPS-based composite electrolyte, giving 2 mS·cm-1 conductivity. It cycles between lithium/graphite composite electrodes at 0.5 mA·cm-2 for over 450 h with a capacity of 0.5 mAh·cm-2 and can withstand a 10-fold current surge.

Thiotetrelates Li2ZnXS4 (X = Si, Ge, and Sn) As Potential Li-Ion Solid-State Electrolytes.

A novel inorganic solid-state electrolyte (ISSE) with high ionic conductivity is a crucial part of all-solid-state lithium-ion (Li-ion) batteries (ASSLBs). Herein, we first report on Li2ZnXS4 (LZXS, X = Si, Ge, and Sn) semiconductor-based ISSEs, crystallizing in the corner-sharing tetrahedron orthorhombic space group, to provide valuable insights into the structure, defect chemistry, phase stability, electrochemical stability, H2O/CO2 chemical stability, and Li-ion conduction mechanisms. A key feature for the Li-ion transport and low migration barrier is the interconnected and corner-shared [LiS4] units along the a-axis, which allows Li-ion transport via empty or occupied tetrahedron sites. A major finding is the first indication that Li-ion migration in Li2ZnSiS4 (LZSiS) has lower energy barriers (∼0.24 eV) compared to Li2ZnGeS4 (LZGS) and Li2ZnSnS4 (LZSnS), whether through vacancy migration or interstitial migration. However, LZGS and LZSnS exhibit greater H2O/CO2 stability compared to LZSiS. The novel framework of LZXS with relatively low Li-ion migration barriers and moderate electrochemical stability could benefit the ASSLB communities.

Epoxy-Based Interlocking Membranes for All Solid-State Lithium Ion Batteries: The Effects of Amine Curing Agents on Electrochemical Properties.

In this study, a series of crosslinked membranes were prepared as solid polymer electrolytes (SPEs) for all-solid-state lithium ion batteries (ASSLIBs). An epoxy-containing copolymer (glycidyl methacrylate-co-poly(ethylene glycol) methyl ether methacrylate, PGA) and two amine curing agents, linear Jeffamine ED2003 and hyperbranched polyethyleneimine (PEI), were utilized to prepare SPEs with various crosslinking degrees. The PGA/polyethylene oxide (PEO) blends were cured by ED2003 and PEI to obtain slightly and heavily crosslinked structures, respectively. For further optimizing the interfacial and the electrochemical properties, an interlocking bilayer membrane based on overlapping and subsequent curing of PGA/PEO/ED2003 and PEO/PEI layers was developed. The presence of this amino/epoxy network can inhibit PEO crystallinity and maintain the dimensional stability of membranes. For the slightly crosslinked PGA/PEO/ED2003 membrane, an ionic conductivity of 5.61 × 10-4 S cm-1 and a lithium ion transference number (tLi+) of 0.43 were obtained, along with a specific capacity of 156 mAh g-1 (0.05 C) acquired from an assembled half-cell battery. However, the capacity retention retained only 54% after 100 cycles (0.2 C, 80 °C), possibly because the PEO-based electrolyte was inclined to recrystallize after long term thermal treatment. On the other hand, the highly crosslinked PGA/PEO/PEI membrane exhibited a similar ionic conductivity of 3.44 × 10-4 S cm-1 and a tLi+ of 0.52. Yet, poor interfacial adhesion between the membrane and the cathode brought about a low specific capacity of 48 mAh g-1. For the reinforced interlocking bilayer membrane, an ionic conductivity of 3.24 × 10-4 S cm-1 and a tLi+ of 0.42 could be achieved. Moreover, the capacity retention reached as high as 80% after 100 cycles (0.2 C, 80 °C). This is because the presence of the epoxy-based interlocking bilayer structure can block the pathway of lithium dendrite puncture effectively. We demonstrate that the unique interlocking bilayer structure is capable of offering a new approach to fabricate a robust SPE for ASSLIBs.

Potential Solid-State Electrolytes with Good Balance between Ionic Conductivity and Electrochemical Stability: Li5-xM1-xMx'O4 (M = Al and Ga and M' = Si and Ge).

Exploring new solid-state electrolyte (SSE) materials with good electrochemical stability and high Li-ion conductivity for all-solid-state Li-ion batteries is vital for the development of technologies. Herein, we employ two lithium aluminates, α- and ß-Li5AlO4 (α- and ß-LAO), as the model framework, which have an orthorhombic crystal structure and isolated AlO4 tetrahedron units connected in lithium atoms, exhibiting large band gaps, low migration barriers (0.30-0.40 eV), fast Li-ion conductivity (LIC, in a magnitude of 10-4 S/cm), and a good electrochemical stability window (ESW, [0.01-3.20 V] vs Li+/Li). We tabulate the expected decomposition products at the interface, while considering cathodes in combination with the LAO electrolyte to discuss their compatibility. We also examine the electrochemical stability, H2O/CO2 stability, and Li-ion mobility of Li4.6Al0.6Si0.4O4 (LASO), Li5GaO4 (LGaO), and Li4.6Ga0.6Ge0.4O4 (LGaGeO) compounds. In general, there is usually a trade-off between the LIC and the ESW; however, LAO features a good balance between an outstanding LIC and a wide ESW, making the compound a promising candidate for next-generation SSE materials.

Tuning Site Energy by XO6 Units in LiX2(PO4)3 Enables High Li Ion Conductivity and Improved Stability.

Solid-state electrolytes (SSEs) with high ion conductivity are necessary for all-solid-sate lithium ion batteries. Here, a less studied NASICON-type LiZr2(PO4)3 (LZP) is screened out from seven LXP compounds (LiX2(PO4)3, X = Si, Ge, Sn, Ti, Zr, Hf, and Mo), which combines the electrochemical stability with high Li conductivity. The bond valence site energy (BVSE), climbing image nudged elastic band (Cl-NEB) method, and electrochemical phase diagram prove LZP has a lower Li migration barrier and the largest electrochemical stability window. The underlying reason for high Li conductivity is analyzed from the structural features to the electronic structures. Furthermore, the XO6 unit mixed frameworks Li1.667Ca0.333Zr1.667(PO4)3 (LCZP) and Li1.667Mg0.333Zr1.667(PO4)3 (LMZP) exhibit high Li ion conductivity associated with a very low Li migration barrier (∼0.20 eV). This work opens a new avenue of broad compositional spaces in LXP for SSEs.

Study of a composite solid electrolyte made from a new pyrrolidone-containing polymer and LLZTO.

Improving the safety and performance of lithium ion batteries (LIB) sparked the idea of using a solid electrolyte to construct all-solid-state ones. In this study, a composite solid polymer electrolyte based on Li6.40La3Zr1.40Ta0.60O12 (LLZTO) nanoparticles and a random copolymer, poly(vinyl pyrrolidone-co-poly(oligo(ethylene oxide) methyl ether methacrylate) (PPO), was successfully prepared and investigated in detail. The copolymer PPO is mixed with LiTFSI and LLZTO at different ratios and the Li conductivity and other electrochemical properties were studied. The copolymer matrix shows the highest ionic conductivity, 2.43 × 10-5 S/cm at 60 °C, at the content of 20 wt% LiTFSI, the highest lithium ion transference number is determined to be 0.33 at room temperature, and the electrochemical stability reaches 4.3 V vs. Li+/Li. Interestingly, when compounded with LLZTO nanoparticles, the ionic conductivity is not improved much. For example, the highest ionic conductivity increases a little to 2.74 × 10-5 S/cm at 60 °C when 5 wt% LLZTO is added. However, a large increase in electrochemical stability to 5.0 V is obtained for the sample of PPO-20%-10LLZTO. Both PPO and the composite electrolyte show good cycling performance during a plating/stripping experiment at a current density of 0.01 mA/cm2. The limited improvement of properties is possibly due to the poor interface contact between PPO and LLZTO nanoparticles. The result may shed light on the complexity of fabricating composite electrolytes using mixtures of polymer and lithium-conducting ceramics.

Detecting dynamic responses of materials and devices under an alternating electric potential by phase-locked transmission electron microscopy.

An apparatus is developed for transmission electron microscopy (TEM) to acquire image and spectral data, such as TEM images, electron holograms, and electron energy loss spectra, synchronized with the measurement of the dynamic response of a specimen under an applied alternating current (AC) electric potential (voltage, denoted VAC). From a VAC of frequency f, a shutter pulse signal is generated to open and close a pre-specimen shutter in a base TEM apparatus. A pulse is generated per VAC cycle from the targeted phase Φ to Φ +∆Φ with phase width ∆Φ (∆Φ <2π). ∆Φ corresponds to the temporal pulse width τ (τ < 1/f) of an electron beam; i.e., ∆Φ =2πfτ. Because of the high sensitivity of the TEM camera used in this study, the images and spectra that are acquired at the same target phase are integrated by means of stroboscopic illumination to obtain the final phase-locked images and spectra with sufficiently small S/N ratio. Phase-locked (strobe) images and/or spectra are obtained for model specimens of polycrystalline aluminum and an all-solid-state lithium ion battery (LIB). In the phase-locked TEM conditions, f ranges from 1Hz to about 40kHz and ∆Φ from 2π/80 to π. VAC ranges from 2mV to 1V depending on observation conditions. The quality of phase-locked strobe images can be improved markedly using a phase-locked strobe electron beam. Under specific conditions, the spatial resolution in images is better than 0.12nm, even though the spatial resolution generally depends on VAC, f, the base TEM, and the conductivity of the specimen. For the model specimens, it is shown that electrochemical impedance spectroscopy and cyclic voltammetry can be performed in a TEM apparatus, and could potentially be synchronized with phase-locked (strobe) imaging and spectroscopy. Severe electron irradiation damage is detected during phase-locked (strobe) electron holography of the model LIB.

Union operation image processing of data cubes separately processed by different objective filters and its application to void analysis in an all-solid-state lithium-ion battery.

In this article, we propose a smart image-analysis method suitable for extracting target features with hierarchical dimension from original data. The method was applied to three-dimensional volume data of an all-solid lithium-ion battery obtained by the automated sequential sample milling and imaging process using a focused ion beam/scanning electron microscope to investigate the spatial configuration of voids inside the battery. To automatically fully extract the shape and location of the voids, three types of filters were consecutively applied: a median blur filter to extract relatively larger voids, a morphological opening operation filter for small dot-shaped voids and a morphological closing operation filter for small voids with concave contrasts. Three data cubes separately processed by the above-mentioned filters were integrated by a union operation to the final unified volume data, which confirmed the correct extraction of the voids over the entire dimension contained in the original data.

Effective Infiltration of Gel Polymer Electrolyte into Silicon-Coated Vertically Aligned Carbon Nanofibers as Anodes for Solid-State Lithium-Ion Batteries.

This study demonstrates the full infiltration of gel polymer electrolyte into silicon-coated vertically aligned carbon nanofibers (Si-VACNFs), a high-capacity 3D nanostructured anode, and the electrochemical characterization of its properties as an effective electrolyte/separator for future all-solid-state lithium-ion batteries. Two fabrication methods have been employed to form a stable interface between the gel polymer electrolyte and the Si-VACNF anode. In the first method, the drop-casted gel polymer electrolyte is able to fully infiltrate into the open space between the vertically aligned core-shell nanofibers and encapsulate/stabilize each individual nanofiber in the polymer matrix. The 3D nanostructured Si-VACNF anode shows a very high capacity of 3450 mAh g(-1) at C/10.5 (or 0.36 A g(-1)) rate and 1732 mAh g(-1) at 1C (or 3.8 A g(-1)) rate. In the second method, a preformed gel electrolyte film is sandwiched between an Si-VACNF electrode and a Li foil to form a half-cell. Most of the vertical core-shell nanofibers of the Si-VACNF anode are able to penetrate into the gel polymer film while retaining their structural integrity. The slightly lower capacity of 2800 mAh g(-1) at C/11 rate and ∼1070 mAh g(-1) at C/1.5 (or 2.6 A g(-1)) rate have been obtained, with almost no capacity fade for up to 100 cycles. Electrochemical impedance spectroscopy does not show noticeable changes after 110 cycles, further revealing the stable interface between the gel polymer electrolyte and the Si-VACNFs anode. These results show that the infiltrated flexible gel polymer electrolyte can effectively accommodate the stress/strain of the Si shell due to the large volume expansion/contraction during the charge-discharge processes, which is particularly useful for developing future flexible solid-state lithium-ion batteries incorporating Si-anodes.