http://onlinelibrary.wiley.com/rss/journal/10.1002/(ISSN)1521-4095

As an empirical tool in materials science and engineering, the iconic phase diagram owes its robustness and practicality to the topological characteristics rooted in the celebrated Gibbs phase law (F = C – P + 2). When crossing the phase diagram boundary, the structure transition occurs abruptly, bringing about an instantaneous change in physical properties and limited controllability on the boundaries (F = 1). Here, we expand the sharp phase boundary to an amorphous transition region (F = 2) by partially disrupting the long-range translational symmetry, leading to a sequential crystalline-amorphous-crystalline (CAC) transition in a pressurized In2Te5 single crystal. Through detailed in-situ synchrotron diffraction, we elucidate that the phase transition stems from the rotation of immobile blocks [In2Te2]2+, linked by hinge-like [Te3]2− trimers. Remarkably, within the amorphous region, the amorphous phase demonstrates a notable 25% increase of the superconducting transition temperature (T c), while the carrier concentration remains relatively constant. Furthermore, we propose a theoretical framework revealing that the unconventional boost in amorphous superconductivity might be attributed to an intensified electron correlation, triggered by a disorder-augmented multifractal behavior. These findings underscore the potential of disorder and prompt further exploration of unforeseen phenomena on the phase boundaries.

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Smart windows with radiative heat management capability using the sun and outer space as zero-energy thermodynamic resources have gained prominence, demonstrating a minimum carbon footprint. However, realizing on-demand thermal management throughout all seasons while reducing fossil energy consumption remains a formidable challenge. Herein, an energy-efficient smart window that enables actively tunable passive radiative cooling (PRC) and multimode heating regulation is demonstrated by integrating the emission-enhanced polymer-dispersed liquid crystal (SiO2@PRC PDLC) film and a low-emission layer deposited with carbon nanotubes. Specifically, this device can achieve a temperature close to the chamber interior ambient under solar irradiance of 700 W m−2, as well as a temperature drop of 2.3 °C at sunlight of 500 W m−2, whose multistage PRC efficiency can be rapidly adjusted by a moderate voltage. Meanwhile, synchronous cooperation of passive radiative heating, solar heating, and electric heating endows this smart window with the capability to handle complicated heating situations during cold weather. Energy simulation reveals the substantial superiority of this device in energy savings compared with single-layer SiO2@PRC PDLC, normal glass, and commercial low-E glass when applied in different climate zones. This work provides a feasible pathway for year-round thermal management, presenting a huge potential in energy-saving applications.

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Spinel oxides with tunable chemical compositions have emerged as versatile electrocatalysts, however their performance is greatly limited by small surface area and low electron conductivity. Here, we rationally design ultrathin high-entropy Fe-based spinel oxides nanosheets (i.e., (Co0.2Ni0.2Zn0.2Mg0.2Cu0.2)Fe2O4; denotes A5Fe2O4) in thickness of ∼4.3 nm with large surface area and highly exposed active sites via a modified sol-gel method. Theoretic and experimental results confirm that the bandgap of A5Fe2O4 nanosheets is significantly smaller than that of ordinary Fe-based spinel oxides, realizing the transformation of binary spinel oxide from semiconductors to metalloids. As a result, such A5Fe2O4 nanosheets manifest excellent performance for the nitrate reduction reaction (NO3 −RR) to ammonia (NH3), with a NH3 yield rate of ∼2.1 mmol h−1 cm−2 at −0.5 V versus Reversible Hydrogen Electrode (RHE), outperforming other spinel-based electrocatalysts. Systematic mechanism investigations reveal that the NO3 −RR is mainly occurred on Fe sites, and introducing high-entropy compositions in tetrahedral sites regulates the adsorption strength of N and O-related intermediates on Fe for boosting the NO3 −RR. The above findings offer a high-entropy platform to regulate the bandgap and enhance the electrocatalytic performance of spinel oxides.

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An understanding of the structural properties that allow for optimal cathode performance, and their origin, is necessary for devising advanced cathode design strategies and accelerating the commercialisation of next-generation cathodes. High-voltage, Fe- and Mg-substituted LiNi0.5Mn1.5O4 cathodes offer a low-cost and cobalt-free, yet energy-dense alternative to commercial cathodes. In this work, we explore the effect of substituents on several important structure properties including Ni/Mn ordering, charge distribution and extrinsic defects. In the cation-disordered samples studied, we observe a correlation between increased Fe/Mg substitution, Li-site defects and Li-rich impurity phase formation – the concentrations of which are greater for Mg-substituted samples. We attribute this to the lower formation energy of MgLi defects when compared to FeLi defects. Li-site defect-induced impurity phases consequently alter the charge distribution of the system, resulting in increased [Mn3+] with Fe/Mg substitution. In addition to impurity phases, other charge compensators were also investigated to explain the origin of Mn3+ (extrinsic defects, [Ni3+], oxygen vacancies and intrinsic off-stoichiometry), although their effects were found to be negligible.

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Single-atom catalysts (SACs) are considered prominent materials in the field of catalysis due to their high metal atom utilization and selectivity. However, the wide-ranging applications of SACs remain a significant challenge due to their complex preparation processes. Here, we report a universal strategy to prepare a series of noble metal single atoms on different non-noble metal oxides through a facile one-step thermal decomposition of molten salts. By using a mixture of non-noble metal nitrate and a small-amount noble metal chloride as the precursor, noble metal single atoms can be easily introduced into the non-noble metal oxide lattice owing to the cation-exchange in the in-situ formed molten salt, followed by the thermal decomposition of nitrate anions during the heating process. Analyses using aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and extended X-ray absorption fine structure spectroscopy confirm the formation of the finely dispersed single atoms. Specially, the as-synthesized Ir single atoms (10.97 wt%) and Pt single atoms (4.60 wt%) on the Co3O4 support demonstrate outstanding electrocatalytic activities for oxygen evolution reaction and hydrogen evolution reaction, respectively.

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Magnetic refrigeration technology can achieve higher energy efficiency based on the magnetocaloric effect. However, the practical application of MCE materials is hindered by their poor mechanical properties, making them challenging to process into devices. Conventional strengthening strategies usually lead to a trade-off with refrigeration capacity reduction. Here, a novel design is presented to overcome this dilemma by forming dual-phase alloys through in-situ precipitation of a tough magnetic refrigeration phase within an intermetallic compound with excellent MCE. In the alloy 87.5Gd-12.5Co, incorporating the interconnected tough phase Gd contributes to enhanced strength (≈ 505 MPa) with good ductility (≈ 9.2%). The strengthening phase Gd simultaneously exhibits excellent MCE, enabling the alloy to achieve a peak refrigeration capacity of 720 J∙kg−1. Moreover, the alloy shows low thermal expansion induced by the synergistic effect of the two phases. It is beneficial for maintaining structural stability during heat exchange in magnetic refrigeration. The coupling interaction between the two magnetic phases can broaden the refrigeration temperature range and reduce hysteresis. This study guides the development of new high-performance materials with an excellent combination of mechanical and magnetic refrigeration properties as needed for gas liquefaction and refrigerators.

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Automated delivery of insulin based on continuous glucose monitoring is revolutionizing the way insulin-dependent diabetes is treated. However, challenges remain for the widespread adoption of these systems, including the requirement of a separate glucose sensor, sophisticated electronics and algorithms, and the need for significant user input to operate these costly therapies. Herein, we report a user-centric glucose-responsive cannula for electronics-free insulin delivery. The cannula —made from a tough, elastomer-hydrogel hybrid membrane formed through a one-pot solvent exchange method— changes permeability to release insulin rapidly upon physiologically relevant varying glucose levels, providing simple and automated insulin delivery with no additional hardware or software. Two prototypes of the cannula were evaluated in insulin-deficient diabetic mice. The first cannula —an ends-sealed, subcutaneously inserted prototype— normalized blood glucose levels for three days and controlled postprandial glucose levels. The second, more translational version —a cannula with the distal end sealed and the proximal end connected to a transcutaneous injection port— likewise demonstrated tight, three-day regulation of blood glucose levels when refilled twice daily. This proof-of-concept study may aid in the development of “smart” cannulas and next-generation insulin therapies at a reduced burden-of-care toll and cost to end-users.

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Advancing biofabrication towards manufacturing living constructs with well-defined architectures and increasingly biologically relevant cell densities is highly desired to mimic the biofunctionality of native human tissues. The formulation of tissue-like, cell-dense inks for biofabrication remains, however, challenging at various levels of the bioprinting process. Promising advances have been made towards this goal, and relatively high cell densities have been achieved, surpassing the limited cell densities of conventional platforms, pushing the current boundaries a step closer to achieving tissue-like cell densities. On this focus, herein we discuss the overarching challenges in the bioprocessing of cell-rich living inks into clinically-grade engineered tissues, as well as highlight the most recent advances in cell-rich living ink formulations and their processing technologies. Additionally, an overview of the foreseen developments in the field is provided and critically discussed.

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Disorders in the regulatory arm of the adaptive immune system result in autoimmune-mediated diseases. While systemic immunosuppression is the prevailing approach to manage them, it fails to achieve long-lasting remission due to concomitant suppression of the regulatory arm and carries the risk of heightened susceptibility to infections and malignancies. Alopecia Areata is a condition characterized by localized hair loss due to autoimmunity. The accessibility of the skin provides an opportunity for local rather than systemic intervention to avoid broad immunosuppression. We hypothesized that expansion of endogenous regulatory T cells (Tregs) at the site of antigen encounter can restore the immune balance and generate a long-lasting tolerogenic response. We therefore utilized a hydrogel microneedle (MN) patch for delivery of CCL22, a chemoattractant for Tregs, and IL-2, a Treg survival factor to amplify them. In an immune-mediated murine model of alopecia, we showed local bolstering of Treg numbers leading to sustained hair regrowth and attenuation of inflammatory pathways. In a humanized skin transplant mouse model, we confirmed expansion of Tregs within human skin without engendering peripheral immunosuppression. The MN patch offered high-loading capacity and shelf-life stability for prospective clinical translation. By harmonizing immune responses locally, we aspire to reshape the landscape of autoimmune skin disease management.

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Peritoneal metastasis (PM) is considered one of the most dreaded forms of cancer metastases for both patients and physicians. Aggressive cytoreductive surgery (CRS) is the primary treatment for peritoneal metastasis. Unfortunately, this intensive treatment frequently causes clinical complications, such as postoperative recurrence, metastasis, and adhesion formation. Emerging evidence suggest that neutrophil extracellular traps (NETs) released by inflammatory neutrophils contribute to these complications. Effective NET-targeting strategies thus show considerable potential in counteracting these complications but remain challenging. Here, we synthesized and screened one type of sulfoxide-containing homopolymer, PMeSEA, with potent fouling-resistant and NET-inhibiting capabilities. Hydrating sulfoxide groups endow PMeSEA with superior non-fouling ability, significantly inhibiting protein/cell adhesion. Besides, the polysulfoxides can be selectively oxidized by ClO– which is required to stabilize the NETs rather than H2O2, and ClO– scavenging effectively inhibits NETs formation without disturbing redox homeostasis in tumor cells and quiescent neutrophils. As a result, PMeSEA potently prevents postoperative adhesions, significantly suppresses peritoneal metastasis, and shows synergetic antitumor activity with chemotherapeutic 5-Fluorouracil. Moreover, coupling aggressive cytoreductive surgery (CRS) with PMeSEA potently inhibits CRS-induced tumor metastatic relapse and postoperative adhesions. Notably, PMeSEA exhibits low in vivo acute and subacute toxicities, implying significant potential for clinical postoperative adjuvant treatment.

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Cellulose-based nanocomposites are highly appealing for the development of next-generation sustainable functional materials. Although many advances have been made in this direction, the true potential of fibrillar nanocomposites has yet to be realized because available fabrication approaches are inadequate for achieving precise structural control at the sub-micrometer scale. Here a spray-assisted alignment methodology of cellulose nanofibrils is combined with the layer-by-layer assembly into an additive manufacturing process in which the alignment direction of each cellulose layer is rationally selected to achieve thin films with a helicoidal arrangement of the nanofibrils. The helicoidal structure of the films is verified by measuring the circular dichroism (CD) of the samples. The sign and position of the structural CD peak show that the handedness and the pitch of the chiral structures can be easily tuned by deliberately selecting simple parameters, such as the number of consecutive cellulose layers sprayed in the same direction, and the angle of rotation between successive stacks of layers. To our knowledge, our approach is unique as it offers the possibility to prepare complex nanocomposite architectures with various nanoscale-controlled sub-structures from different anisometric objects, which is enabling novel designs of composite films with damage-resistant and/or optical filtering functionalities.

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Sorption-based atmospheric water harvesting (SAWH) is a promising technology to alleviate freshwater scarcity. Recently, hygroscopic salt-hydrogel composites (HSHCs) have emerged as attractive candidates with their high water uptake, versatile designability, and scale-up fabrication. However, achieving high-performance SAWH applications for HSHCs has been challenging because of their sluggish kinetics, attributed to their limited mass transport properties. Herein, a universal network engineering of hydrogels using a cryogelation method is presented, significantly improving the SAWH kinetics of HSHCs. As a result of the entangled mesh confinements formed during cryogelation, a stable macroporous topology is attained and maintained within the obtained entangled-mesh hydrogels (EMHs), leading to significantly enhanced mass transport properties compared to conventional dense hydrogels (CDHs). With it, corresponding hygroscopic EMHs (HEMHs) simultaneously exhibit faster moisture sorption and solar-driven water desorption. Consequently, a rapid-cycling HEMHs-based harvester delivers a practical freshwater production of 2.85 Lwater kgsorbents −1 day−1 via continuous eight sorption/desorption cycles, outperforming other state-of-the-art hydrogel-based sorbents. Significantly, the generalizability of this strategy has been validated by extending it to other hydrogels used in HSHCs. Overall, this work offers a new approach to efficiently address long-standing challenges of sluggish kinetics in current HSHCs, promoting them toward the next-generation SAWH applications.

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The dilemma between the thickness and accessible active site triggers the design of porous crystalline materials with mono-layered structure for advanced photo-catalysis applications. Here, we report a kind of sub-nanometer mono-layered nanosheets (Co-MOF MNSs) through the exfoliation of a specifically designed Co3 cluster-based metal-organic frameworks (MOFs). The sub-nanometer thickness and inherent light-sensitivity endow Co-MOF MNSs with fully exposed Janus Co3 sites that can selectively photo-reduce CO2 into formic acid under simulated flue gas. Notably, the production efficiency of formic acid by Co-MOF MNSs (0.85 mmol g−1 h−1) is ∼13 times higher than that of bulk counterpart (0.065 mmol g−1 h−1) under simulated flue gas atmosphere, which is highest in reported works up to date. Theoretical calculations prove that the exposed Janus Co3 sites with simultaneously available sites possess higher activity when compared with single Co site, validating the importance of mono-layered nanosheet morphology. Our results might facilitate the development of functional nanosheet materials for CO2 photo-reduction in potential flue gas treatment.

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Bistable electrochromic (EC) materials and systems offer significant potential for building decarbonization through their optical modulation and energy efficiency. However, challenges such as limited design strategies and bottlenecks in cost, fabrication, and color have hindered the full commercialization of energy-saving EC windows and displays, with few materials achieving true bistability. Herein, a novel strategy for designing bistable electrochromic materials is proposed by leveraging supramolecular interactions. These interactions facilitate reversible color transitions, stabilize the colored structure, and enable spatial confinement to inhibit diffusion, thereby achieving bistable electrochromism. The mechanisms and materials underlying these unconventional electrochromic systems are substantiated through detailed characterization. This strategy enables the preparation of low-cost and sustainable transparent electrochromic displays with high performance. Notably, the display information remains clearly visible for more than 2 hours without consuming energy. Involving biomass materials and removable device structures also enhances the sustainability and scalability of EC technology applications and development. Our results demonstrate the crucial role of supramolecular chemistry in the development of cutting-edge materials for applications such as energy-saving smart windows.

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Lithium-based batteries (LBBs) are highly researched and recognized as a mature electrochemical energy storage (EES) system in recent years. However, their stability and effectiveness are primarily confined to room temperature conditions. At temperatures significantly below 0 °C or above 60 °C, LBBs experience substantial performance degradation. Under such challenging extreme contexts, sodium-ion batteries (SIBs) emerge as a promising complementary technology, distinguished by their fast dynamics at low temperature region and superior safety under elevated temperatures. Notably, developing SIBs suitable for wide-temperature usage still presents significant challenges, particularly for specific applications such as electric vehicles, renewable energy storage, and deep-space/polar explorations, which requires a thorough understanding of how SIBs perform under different temperature conditions. By reviewing the development of wide-temperature SIBs, we systematically and comprehensively analyze the influence of temperature on the parameters related to battery performance, such as reaction constant, charge transfer resistance, etc. The review emphasizes challenges encountered by SIBs in both low and high temperatures while exploring recent advancements in SIB materials, specifically focusing on strategies to enhance battery performance across diverse temperature ranges. Overall, insights gained from these studies will drive the development of SIBs that can handle the challenges posed by diverse and harsh climates.

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Alkali metal–air batteries (AMABs) promise ultrahigh gravimetric energy densities, while the inherent poor cycle stability hinders their practical application. To address this challenge, most previous efforts were devoted to advancing the air cathodes with high electrocatalytic activity. Recent studies have underlined the solid–liquid–gas triple-phase interface around the anode can play far more significant roles than previously acknowledged by the scientific community. Besides the bottlenecks of uncontrollable dendrite growth and gas evolution in conventional alkali metal batteries, the corrosive atmospheric gases, intermediate oxygen species, and redox mediators in AMABs cause more severe anode corrosion and structural collapse, posing greater challenges to the stabilization of the anode triple-phase interface. This work aims to provide a timely perspective on the anode interface engineering for durable AMABs. Taking the Li–air battery as a typical example, we have a critical review of the latest developed anode stabilization strategies, including formulating novel electrolytes to build protective interphases and alleviate corrosive attacks, fabricating advanced anodes to improve their anti-corrosion capability, and designing functional separator to shield the corrosive species. Finally, we highlight the remaining scientific and technical issues from the prospects of anode interface engineering, particularly materials system engineering, for the practical use of AMABs.

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Polymer cubosomes (PCs) have well-defined inverse bicontinuous cubic mesophases formed by amphiphilic block copolymer bilayers. The open hydrophilic channels, large periods and robust physical properties of PCs are advantageous to many host-guest interactions and yet not fully exploited, especially in the fields of functional nanomaterials. Here, we systematically investigate the self-assembly of poly(ethylene oxide)-block-polystyrene block copolymers and develop a series of robust PCs via a cosolvent method. Ordered nanoporous metal oxide particles are obtained by selectively filling the hydrophilic channels of PCs via an impregnation strategy, followed by a two-step thermal treatment at high temperatures. Based on this versatile PCs platform, we demonstrate the general synthesis of a library of ordered porous particles with different pore structures (Pm3¯$\bar{3}$m and Fd3¯$\bar{3}$m), tunable large pore size (18–78 nm) and periodicity (36.1–92.4 nm), high specific surface areas (up to 123.3 m2·g−1 for WO3) and diverse framework compositions, such as transition and non-transition metal oxides, rare earth chloride oxides, perovskite, pyrochlore and high-entropy metal oxides. As typical materials obtained via this method, ordered porous WO3 particles have advantages of highly opened continuous structure and semiconducting properties, thus showing superior gas sensing performances towards hydrogen sulfide, a typical toxic gas that threatens the environment.

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Quasi-solid-state batteries (QSSBs) are gaining widespread attention as a promising solution to improve battery safety performance. However, the safety improvement and the underlying mechanisms of QSSBs remain elusive. Herein, a novel strategy combining high-safety ethylene carbonate-free liquid electrolyte and in situ polymerization technique is proposed to prepare practical QSSBs. The Ah-level QSSBs with LiNi0.83Co0.11Mn0.06O2 cathode and graphite-silicon anode demonstrate significantly improved safety features without sacrificing electrochemical performance. As evidenced by accelerating rate calorimetry tests, the QSSBs exhibit increased self-heating temperature and onset temperature (T 2), and decreased temperature rise rate during thermal runaway (TR). The T 2 has a maximum increase of 48.4 °C compared to the conventional liquid batteries. Moreover, the QSSBs do not undergo TR until 180 °C (even 200 °C) during the hot-box tests, presenting significant improvement compared to the liquid batteries that run into TR at 130 °C. Systematic investigations show that the in-situ-formed polymer skeleton effectively mitigates the exothermic reactions between lithium salts and lithiated anode, retards the oxygen release from cathode, and inhibits crosstalk reactions between cathode and anode at elevated temperatures. The findings offer an innovative solution for practical high-safety QSSBs and open up a new sight for building safer high-energy-density batteries.

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Identifying nerves during prostatectomy poses a significant challenge due to their small size, translucency, and narrowness of the pelvis. To address this issue, a library of nerve-specific fluorophores based on a phenoxazine scaffold has been developed. Formulated derivatives have been shown to be compatible with the robotic-assisted da Vinci system, allowing for high-fidelity imaging of prostatic nerves during fluorescence-guided surgery.

Fluorescence-guided surgery (FGS) is poised to revolutionize surgical medicine through near-infrared (NIR) fluorophores for tissue- and disease-specific contrast. Clinical open and laparoscopic FGS vision systems operate nearly exclusively at NIR wavelengths. However, tissue-specific NIR contrast agents compatible with clinically available imaging systems are lacking, leaving nerve tissue identification during prostatectomy a persistent challenge. Here, it is shown that combining drug-like molecular design concepts and fluorophore chemistry enabled the production of a library of NIR phenoxazine-based fluorophores for intraoperative nerve-specific imaging. The lead candidate readily delineated prostatic nerves in the canine and iliac plexus in the swine using the clinical da Vinci Surgical System that has been popularized for minimally invasive prostatectomy procedures. These results demonstrate the feasibility of molecular engineering of NIR nerve-binding fluorophores for ready integration into the existing surgical workflow, paving the path for clinical translation to reduce morbidity from nerve injury for prostate cancer patients.

An advanced tape electrolyte is realized by harnessing high-entropy condensed microstructures of polymers. The high-entropy tape electrolyte brings a promising solution to not only the challenging interface issues in solid-state batteries, but also future flexible energy storage devices.

Advanced solid electrolytes with strong adhesion to other components are the key for the successes of solid-state batteries. Unfortunately, traditional solid electrolytes have to work under high compression to maintain the contact inside owing to their poor adhesion. Here, a concept of high-entropy tape electrolyte (HETE) is proposed to simultaneously achieve tape-like adhesion, liquid-like ion conduction, and separator-like mechanical properties. This HETE is designed with adhesive skin layer on both sides and robust skeleton layer in the middle. The significant properties of the three layers are enabled by high-entropy microstructures which are realized by harnessing polymer–ion interactions. As a result, the HETE shows high ionic conductivity (3.50 ± 0.53 × 10−4 S cm−1 at room temperature), good mechanical properties (toughness 11.28 ± 1.12 MJ m−3, strength 8.18 ± 0.28 MPa), and importantly, tape-like adhesion (interfacial toughness 231.6 ± 9.6 J m−2). Moreover, a compression-free solid-state tape battery is finally demonstrated by adhesion-based assembling, which shows good interfacial and electrochemical stability even under harsh mechanical conditions, such as twisting and bending. The concept of HETE and compression-free solid-state tape batteries may bring promising solutions and inspiration to conquer the interface challenges in solid-state batteries and their manufacturing.