Free-standing Films Research Articles

Determination of Biogenic Amine Level Variations upon Storage, in Chicken Breast Coated with Edible Protective Film.

A new chitosan-based protective film containing rosemarinic acid (0.282% w/w) has been elaborated. The film was formed from a water-oil emulsion system and applied to poultry meat samples using a dip-coating technique. Various physicochemical parameters of the coatings, such as thickness, Young's modulus, elongation at break, water vapor transmission rates, and antioxidant activity, were tested with free-standing film samples peeled from a Petri dish. Compared to neat chitosan films obtained similarly, new films cast from the emulsion showed significantly better elasticity (Young's modulus was diminished from 1458 MPa to about 29 MPa). Additionally, barrier properties for moisture transition decreased from 7.3 to 5.8 g mm m-2 day-1 kPa-1. The coated poultry samples were subsequently evaluated in juxtaposition with uncoated ones in a storage test. Levels of selected biogenic amines (histamine, tyramine, tryptamine, phenylethylamine, putrescine, cadaverine, spermine, and spermidine), total bacterial count, and lipid oxidation levels in the meat samples were analyzed during storage at 4 °C (up to 96 h). The results obtained for the biogenic amines, total bacterial content, calculated biogenic amine index, and the ratio of spermidine to spermine in meat samples suggest the advantage of the proposed coatings with rosmarinic acid in protecting poultry meat against environmental factors and rapid spoilage.

The Impact of Grain Growth on the Functional Properties in Room-Temperature Powder Aerosol Deposited Free-Standing (Ba,Ca)(Zr,Ti)O3 Thick Films

This study investigates the development of freestanding thick films (FSFs) of lead-free (Ba,Ca)(Zr,Ti)O3 and the role of grain growth on the electromechanical response. During deposition, room temperature powder aerosol deposition rapidly produces thick films with a nano-grain structure that limits the electromechanical properties. In this study, the films are removed from the substrate using a sacrificial buffering layer to avoid thermal treatment and allow for an initial as-processed state. Following this, FSFs were thermally treated at various annealing temperatures from 800 °C to 1400 °C to induce grain growth, which was characterized with scanning and transmission electron microscopy. X-ray diffraction revealed an increase in the crystallite size consistent with an increase in grain size and a decrease in internal residual stress. The temperature-dependent dielectric behavior and the large-field ferroelectric response were also characterized, revealing significant differences of the FSFs from the bulk properties.

One-step growth of ultrathin CoSe2 nanobelts on N-doped MXene nanosheets for dendrite-inhibited and kinetic-accelerated lithium–sulfur chemistry

The practical application of lithium–sulfur (Li–S) batteries is inhibited by the shuttle effect of lithium polysulfides (LiPSs) and slow polysulfide redox kinetics on the S cathode as well as the uncontrollable growth of dendrites on the Li metal anode. Therefore, both cathode and anode sides must be considered when modifying Li−S batteries. Herein, two-dimensional (2D) ultrathin CoSe2 nanobelts are in situ grown on 2D N-doped MXene nanosheets (CoSe2@N-MXene) via one-step solvothermal process for the first time. Owing to its unique 2D/2D structure, CoSe2@N-MXene can be processed to crumpled nanosheets by freeze-drying and flexible and freestanding films by vacuum filtration. These crumpled CoSe2@N-MXene nanosheets with abundant active sites and inner spaces can act as S hosts to accelerate polysulfide redox kinetics and suppress the shuttle effect of LiPSs owing to their strong adsorption ability and catalytic conversion effect with LiPSs. Meanwhile, the CoSe2@N-MXene film (CoSe2@NMF) can act as a current collector to promote uniform Li deposition because it contains lithiophilic CoSe2 and N sites. Under the systematic effect of CoSe2@N-MXene on S cathode and Li metal anode, the electrochemical and safety performance of Li–S batteries are improved. CoSe2@NMF also shows excellent storage performances in flexible energy storage devices.

Smart Free-Standing Bilayer Polyacrylamide/DNA Hybrid Hydrogel Film-Based Sensing System Using Changes in Bending Angles as a Visual Signal Readout.

Stimuli-responsive DNA hydrogels have shown great potential in sensing applications due to their attractive properties such as programmable target responsiveness, excellent biocompatibility, and biodegradability. In contrast to the extensively developed DNA hydrogel sensing systems based on the stimuli-responsive hydrogel-to-solution phase transition of the hydrogel matrix, the quantitative sensing application of DNA hydrogels exhibiting smart shape deformations has rarely been explored. Moreover, bulk DNA hydrogel-based sensing systems also suffer from high material cost and slow response. Herein, free-standing bilayer polyacrylamide/DNA hybrid hydrogel films with programmable responsive properties directed by the sequence of functional DNA units have been constructed. Compared with bulk DNA hydrogels, these DNA hydrogel films with a thickness at the micrometer scale not only greatly reduce the consumption of DNA materials but also facilitate the mass transfer of biomacromolecular substances within the hydrogel network, thus favoring their sensing applications. Therefore, a target-responsive smart DNA hydrogel film-based sensor system is further demonstrated based on the large amplitude macroscopic shape deformation of the film as a visual signal readout. As a proof of concept, Pb2+ or UO22+ ion-responsive DNA units were introduced into the active layer of the bilayer hydrogel films. In the presence of Pb2+ or UO22+ ions, the occurrence of a cleavage reaction within the DNA units leads to the release of DNA segments from the hydrogel film, inducing a dramatic shape deformation of the film, and thus sensing of Pb2+ or UO22+ ions with high specificity is achieved based on measuring the bending angle changes of these smart free-standing films. These smart DNA hydrogel film sensors with target-programmable responsiveness, simple operation, and ease of storage may hold promise for future rapid on-site testing applications.

Synthesis of Hydrophilic Poly(vinylpyrrolidone)/CuS Free-Standing Thin Films Exhibiting Photothermal Conversion.

Free-standing films without the need for any support materials attract attention because of their excellent flexibility in use and ability to be transferred to various substrates. However, free-standing films containing large amounts of inorganic crystalline particles are hard to achieve due to their low strength. In this study, we found the possibility of preparing a free-standing composite film of CuS/polyvinylpyrrolidone (PVP) at a large loading of CuS (>50%) from a concentrated colloidal dispersion of CuS nanoparticles modified with PVP. Despite the large amount of inorganic crystals contained in the free-standing film, the film was strong enough to be handled without any support materials. As a proof-of-concept application of the free-standing film, a solar water evaporation experiment was performed. The CuS/PVP free-standing film exhibited photothermal conversion under light illumination to generate heat and accelerate water evaporation, achieving an evaporation rate of 4.35 kg·m-2 h-1 and an evaporation efficiency of 96.3% at a power density of 3 suns. In addition, thanks to the free-standing feature, one side of the CuS/PVP film could be hydrophobized with polydimethylsiloxane to form a Janus thin film, allowing for floating on the water surface. As a result, effective water evaporation was achieved because of the selective evaporation of water from the air/water interface.

Circularly Polarized Luminescence of Cholesteric Liquid Crystal Polymer Networks with a Europium(III) Complex as an Emitter.

A coordination complex, Eu(C12C12dbm)3(phen), with strong emission and a high quantum yield (QY ∼ 51.9%) was synthesized. The EuIII complex, as a fluorescent emitter, was embedded in cholesteric liquid crystal polymer networks (CLCNs). A series of free-standing EuIII-CLCN films were obtained, generating a typical sharp emission band corresponding to the EuIII complex. Tunable handedness of circularly polarized luminescence (CPL) with high |glum| values (up to 0.63) was observed. A series of CPL-active CLCN-coated PET films were also prepared (|glum| values up to 0.63), which can be used for large-area preparations. Moreover, by stacking an emitter-embedded PMMA layer and a CLCN layer, a composite system was built, and a large |glum| value (∼1.42) was achieved. Fluorescence patterns were prepared, and distinct images of CLCN films were recognized under both daylight and UV light. This work not only demonstrated that coordination compounds could be incorporated with CLCN films to prepare CPL-active materials with high |glum| values but also provided a new perspective for emissive CLCN materials used for anticounterfeiting and encryption.

Design and Synthesis of Transferrable Macro-Sized Continuous Free-Standing Metal-Organic Framework Films for Biosensor Device.

Metal organic framework (MOF) films have attracted abundant attention due to their unique characters compared with MOF particles. But the high-temperature reaction and solvent corrosion limit the preparation of MOF films on fragile substrates, hindering further applications. Fabricating macro-sized continuous free-standing MOF films and transferring them onto fragile substrates are a promising alternative but still challenging. Here, a universal strategy to prepare transferrable macro-sized continuous free-standing MOF films with the assistance of oxide nanomembranes prepared by atomic layer deposition and studied the growth mechanism is developed. The oxide nanomembranes serve not only as reactant, but also as interfacial layer to maintain the integrality of the free-standing structure as the stacked MOF particles are supported by the oxide nanomembrane. The centimeter-scale free-standing MOF films can be transferred onto fragile substrates, and all in one device for glucose sensing is assembled. Due to the strong adsorption toward glucose molecules, the obtained devices exhibit outstanding performance in terms of high sensitivity, low limit of detection, and long durability. This work opens a new window toward the preparation of MOF films and MOF film-based biosensor chip for advantageous applications in post-Moore law period.

Ptychographic Nanoscale Imaging of the Magnetoelectric Coupling in Freestanding BiFeO3.

Understanding the magnetic and ferroelectric ordering of magnetoelectric multiferroic materials at the nanoscale necessitates a versatile imaging method with high spatial resolution. Here, soft X-ray ptychography is employed to simultaneously image the ferroelectric and antiferromagnetic domains in an 80nm thin freestanding film of the room-temperature multiferroic BiFeO3 (BFO). The antiferromagnetic spin cycloid of period 64nm is resolved by reconstructing the corresponding resonant elastic X-ray scattering in real space and visualized together with mosaic-like ferroelectric domains in a linear dichroic contrast image at the Fe L3 edge. The measurements reveal a near perfect coupling between the antiferromagnetic and ferroelectric ordering by which the propagation direction of the spin cycloid is locked orthogonally to the ferroelectric polarization. In addition, the study evinces both a preference for in-plane propagation of the spin cycloid and changes of the ferroelectric polarization by 71°between multiferroic domains in the epitaxial strain-free, freestanding BFO film. The results provide a direct visualization of the strong magnetoelectric coupling in BFO and of its fine multiferroic domain structure, emphasizing the potential of ptychographic imaging for the study of multiferroics and non-collinear magnetic materials with softX-rays.

High Ionic Conductive, Mechanical Robust Sulfide Solid Electrolyte Films and Interface Design for All‐Solid‐State Lithium Metal Batteries

AbstractAll‐solid‐state lithium batteries (ASSLBs) are considered a promising technology for next‐generation energy storage systems due to their inherent safety. However, the conventional laboratory‐scale ASSLBs reported to date are based on pellet‐type structures with thick solid electrolyte layers, leading to challenges related to low energy densities and poor electrochemical performance. In this study, porous adhesive poly(ethylene vinyl acetate) (PEVA) scaffolds and polytetrafluoroethylene (PTFE) binders are utilized to interweave sulfide solid electrolytes into freestanding films with an ultra‐low thickness of 40 µm, high ionic conductivity of 1.1 mS cm−1, and a high tensile strength of 74 MPa. To mitigate the reduction reaction between the PTFE binder and the lithium metal anode, a Li3N‐rich solid electrolyte interphase (SEI) in situ on lithium metal is formed, and the assembled symmetric cell shows excellent cycling stability within 800 h at the current density of 0.2 mA cm−2 and room temperature. Additionally, the ASSLBs using oxidatively stable Li2ZrCl5F in the composite cathode and the prepared solid electrolyte film demonstrate exceptional cycling performance and fast‐charging capability, with a high cell‐level energy density of 354.4 Wh kg−1. The ASSLBs prepared by coupling E‐LPSCl film and stable interface design exhibit excellent electrochemical performance and a high cell‐level energy density.

The Effect of 1-Ethyl-3-Methylimidazolium Acetate on the Structural, Morphological and Electrical Properties of Poly (methyl methacrylate) (PMMA)-based Electrolyte Films

In this study, the ionic liquid (IL) of 1-ethyl-3-methylimidazolium acetate, [EMIM][Ac] was incorporated into the PMMA-based electrolyte via solution casting technique. Lithium triflate (LiTf) was also doped into the system to provide additional charge carrier. The effect of various amount [EMIM] [Ac] towards the structural, morphological, and electrical properties of PMMA-based PE films were determined using Fourier transform infrared spectroscopy (FTIR), optical microscope (OM) and electrochemical impedance spectroscopy (EIS) respectively. Solid, flexible, and free-standing films of PMMA-based electrolyte were successfully obtained after the addition of IL. As confirmed from FTIR analyses, there occurs interaction between the oxygen atoms of PMMA with the imidazolium cation of the IL. With the addition of IL, the ionic conductivity was also observed to increase which can be related to the large structure of IL that occupy the space between PMMA chain hence reduced the formation of hydrogen bonding. This has been further confirmed by the OM analyses which showed the increase in grain size for the modified PMMA system after the doping of IL. The highest conductivity of 9.86 x 10-7 S cm-1 was obtained when 42 wt.% IL (PMMAIL5) was incorporated into the PMMA-based electrolyte system. This is due to the increase in the amorphosity of the sample which improved the ion diffusion within the polymer complex. The increase in the amorphosity of the sample is confirmed by the reduced in the number of grains as observed in the optical micrograph of PMMAIL5.

Enhancement of the mechanical properties in ultra-low weight SWCNT sandwiched PDMS composites using a novel stacked architecture

This study focuses on enhancing the mechanical properties of thin, soft, free-standing films via a layer-by-layer (LBL) fabrication process called LBL-FP. Soft polymer nanocomposite (PNC) thin films, combining polydimethylsiloxane (PDMS) and single-walled carbon nanotubes (SWCNT) at ultra-low loadings using a unique bottom-up LBL-FP, are examined. Two different structures of layered composites, (i) LBL PNCs- Layered composites with alternating layers of PDMS and SWCNT, (ii) Bulk PNCs- Layered composites with SWCNT dispersed in the bulk of PDMS, are comparatively investigated for their structural and mechanical properties. Silane-functionalized SWCNT strengthens the chemical bonding with PDMS, improving adhesion and dispersion. Mechanical analysis using nanoindentation, delamination, and dynamic analysis highlights the advantages of LBL PNCs with alternating layers of PDMS and SWCNT. Notably, LBL PNC (0.5 wt%) exhibits significant improvements, such as 2.6X increased nanoindentation resistance, 3X improved viscoelasticity, and (2–5)X enhanced tensile properties in comparison with neat PDMS. Due to this, LBL PNCs offer potential for soft, lightweight applications like wearables, electromagnetic interference shielding materials, and strain sensors while advancing composite thin film mechanics. The study emphasizes using a stacked architecture to produce PDMS-SWCNT multilayered PNCs with improved mechanics utilizing ultra-low concentrations of SWCNT. This first-of-its-kind stack design facilitates possibilities for lightweight composites utilizing less fillers. The LBL assembly involves the stacking of alternating layers of different materials, each contributing specific properties to enhance the overall strength and toughness of the structure.

On-Chip Micro Temperature Controllers Based on Freestanding Thermoelectric Nano Films for Low-Power Electronics

HighlightsDense and flat freestanding Bi2Te3-based thermoelectric nano films were successfully fabricated by sputtering technology using a newly developed nano graphene oxide membrane as a substrate.On-chip micro temperature controllers were integrated using conventional micro-electromechanical system technology, to achieve energy-efficient temperature control for low-power electronics.The tunable equivalent thermal resistance enables an ultrahigh temperature control capability of 100 K mW−1 and an ultra-fast cooling rate exceeding 2000 K s−1, as well as excellent reliability of up to 1 million cycles.

TiO2/PDA Multilayer Nanocomposites with Exceptionally Sharp Large-Scale Interfaces and Nitrogen Doping Gradient.

The evolving field of photocatalysis requires the development of new functional materials, particularly those suitable for large-scale commercial systems. One particularly promising approach is the creation of hybrid organic/inorganic materials. Despite being extensively studied, materials such as polydopamine (PDA) and titanium oxide continue to show significant promise for use in such applications. Nitrogen-doped titanium oxide and free-standing PDA films obtained at the air/water interface are particularly interesting. This study introduces a straightforward and reproducible approach for synthesizing a novel class of large-scale multilayer nanocomposites. The method involves the alternate layering of high-quality materials at the air/water interface combined with precise atomic layer deposition techniques, resulting in a gradient nitrogen doping of titanium oxide layers with exceptionally sharp oxide/polymer interfaces. The analysis confirmed the presence of nitrogen in the interstitial and substitutional sites of the TiO2 lattice while maintaining the 2D-like structure of the PDA films. These chemical and structural characteristics translate into a reduction of the band gap by over 0.63 eV and an increase in the photogenerated current by over 60% compared with pure amorphous TiO2. Furthermore, the nanocomposites demonstrate excellent stability during the 1 h continuous photocurrent generation test.

Flashlight treatment for instantaneous structuring of dense MXene film into porous MXene/TiO2 nanocomposite for lithium-ion battery anodes

MXenes, the two-dimensional metal carbides and nitrides, have been considered a new class of electrode materials with their noticeable performance in various energy storage systems. Furthermore, the unique property and morphology allow MXenes to be assembled into freestanding films, which can be applied in energy storage devices with lightweight and high energy density. However, their tendency to restack and aggregate remains a challenge to enhance the electrochemical performance of MXenes. In this study, we propose a facile method to fabricate a porous MXene-TiO2 freestanding anode with the help of a flashlight. Simply heating the MXene films with a flashlight in milliseconds increases the interlayer spacing of the MXenes and simultaneously forms TiO2 on the MXene surface. Along with the widened interlayer and formation of TiO2, improved wettability, easy electrolyte penetration, and reduced electrode resistance were achieved. As a result, this freestanding anode exhibits nearly 50 times higher Li+ storage capacity (148 mAh/g) than pristine MXene film (3 mAh/g) at 0.05 A/g and excellent cycle stability up to 1500 cycles without degradation.

Free-standing carboxymethyl cellulose film incorporating nanoformulated pomegranate extract for meat packaging

This study aimed to explore an innovative approach to enhancing the shelf-life and quality of meat products through the application of an active packaging system. The study involved the development of new free-standing carboxymethyl cellulose (CMC) nanocomposite films incorporated with nanoencapsulated flavonoids derived from pomegranate extract. The loaded flavonoids, known for their antioxidant and antimicrobial properties, were nanoencapsulated via a self-assembly approach in a mixture of chitosan and sodium alginate to improve their stability, solubility, and controlled release characteristics. Chemical structure, size, and morphology of the obtained nanoparticles (Pg-NPs) were studied with FTIR, zeta-sizer, and TEM. The Pg-NPs showed particle size of 232 nm, and zeta-potential of −20.7 mV. Various free-standing nanocomposite films were then developed via incorporation of Pg-NPs into CMC-casted films. FTIR, SEM, thermal and mechanical properties, and surface wettability were intensively studied for the nanocomposite films. Barrier properties against water vapor were investigated at 2022 g·m−2d−1. The nanocomposite films possessed superior properties for inhibiting bacterial growth and extending the shelf-life of beef and poultry meat for 12 days compared with the Pg-NPs-free CMC films. This study presented a promising approach for development of active packaging systems with improved antimicrobial and antioxidant properties, and economic and environmental impacts.

Free-standing iridescent films: Crafting circularly polarized luminescence from blue to NIR-II for enhanced anti-counterfeiting performance

Circularly polarized luminescence (CPL) has recently garnered significant attention due to its promising applications. Current research efforts are predominantly concentrated on enhancing CPL emission with a specific focus on increasing both emission efficiency and luminescence dissymmetry factor (glum). Moreover, how to achieve large-scale fabrication of chiroptical materials with excellent CPL performance still remains a challenge. In this work, we present a kind of photonic crystal films, possess excellent CPL performance with a high glum as well as large luminescent quantum yield when loaded with various luminescent inorganic nanomaterials. Based on this feature, for the first time, we have achieved a distinctive CPL emission with broad spectrum spanning from blue to second near-infrared (NIR-II). Moreover, through applying different fabrication technologies, the distribution of emitters in the CPC samples can be regulated, which holds the key for the CPL performance. Building upon this foundation, we present two illustrative examples of highly efficient chiroptical anti-counterfeiting techniques employing screen-printing technology and arbitrary cutting treatments. This work not only offers a versatile approach for crafting high-performance CPL-active materials but also underscores their potential in the anti-counterfeiting domain and the feasibility of large-scale production.

Scalable Production of Highly Conductive 2D NbSe2 Monolayers with Superior Electromagnetic Interference Shielding Performance.

Thin, flexible, and electrically conductive films are in demand for electromagnetic interference (EMI) shielding. Two-dimensional NbSe2 monolayers have an electrical conductivity comparable to those of metals (106-107 S m-1) but are challenging for high-quality and scalable production. Here, we show that electrochemical exfoliation of flake NbSe2 powder produces monolayers on a large scale (tens of grams), at a high yield (>75%, monolayer), and with a large average lateral size (>20 μm). The as-exfoliated NbSe2 monolayer flakes are easily dispersed in diverse organic solvents and solution-processed into various macroscopic structures (e.g., free-standing films, coatings, patterns, etc.). Thermal annealing of the free-standing NbSe2 films reduces the interlayer distance of restacked NbSe2 from 1.18 to 0.65 nm and consequently enhances the electrical conductivity to 1.16 × 106 S m-1, which is superior to those of MXenes and reduced graphene oxide. The optimized NbSe2 film shows an EMI shielding effectiveness (SE) of 65 dB at a thickness of 5 μm (>110 dB for a 48-μm-thick film), among the highest in materials of similar thicknesses. Moreover, a laminate of two layers of the NbSe2 film (2 μm thick) with an insulating interlayer shows a high SE of 85 dB, surpassing that of the 20-μm-thick NbSe2 film (83 dB). A two-layer theoretical model is proposed, and it agrees with the experimental EMI SE of the laminated NbSe2 films. The ability to produce NbSe2 monolayers on a tens of grams scale will enable their diverse applications beyond EMI shielding.

Plane Stress Fracture Toughness Testing of Freestanding Ultra-Thin Nanocrystalline Gold Films on Water Surface.

Fracture toughness, which is the resistance of a material to crack propagation, is a critical material property for ensuring the mechanical reliability of damage-tolerant design. Recently, damage-tolerant design is introduced to flexible electronics by adopting micro-cracked ultra-thin nanocrystalline (NC) gold films as stretchable electrodes in a plane stress state. However, experimental investigation of the plane stress fracture toughness of those films remains challenging due to the intrinsic fragility from their sub-100nm thicknesses. Here, a quantitative method for systematically evaluating the plane stress fracture toughness of freestanding ultra-thin NC gold film on water surface platform is presented. After effectively fabricating single-edge-notched-tension samples with femtosecond laser, mode I stress intensity factors are measured in the plane stress state on water surface. Moreover, investigation regarding the effect of notch length, notch sharpness, and notch tip plasticity validates this method based on linear elastic fracture mechanics theory. As a demonstration, the thickness-dependent plane stress fracture toughness of ultra-thin NC gold films is qualitatively unveiled. It is revealed that the thickness confinement effect on grain boundary sliding induces a transition in fracture behavior. This method is expected to further clarify the fracture-related properties of various ultra-thin films for next-generation electronics.

Piezoelectric polymer based acoustic energy harvester for implantable medical devices

Wireless implantable devices (WIDs) have the potential to revolutionize biomedical sensing, but their power supplies face significant challenges. Traditional energy transfer methods such as inductive and RF have limitations due to associated tissue losses. This work demonstrates a promising approach to this problem, using a flexible implantable ultrasound energy harvester (IUEH) made of biocompatible Poly (vinylidene fluoride-co-trifluoro ethylene) (P(VDF-TrFe)) free-standing film. Unlike commonly used piezoceramic devices, IUEH can be fabricated using economical solution processing methods such as spin coating. In addition, the PVDF-TrFE Ultrasound energy harvesters are rarely reported in the literature. The device performance of the polymer IUEH was investigated in air, water, and animal meat tissue, and the results show that it can generate a power output of 1.1 mW cm−2 in meat, and 1.4 mW cm−2 in water at 80 kHz. The device fabricated using a free-standing piezoelectric thin film, offers an optimum output that is comparable to other P(VDF-TrFe) based high-frequency devices. Additionally, its flexible design, lower costs, and biocompatibility make it a promising alternative to lead-based devices; thus, offering safety, affordability, and quick customization, while promoting minimally invasive procedures and driving innovation in medical device development.

Hierarchically core-shell structured nanocellulose/carbon nanotube hybrid aerogels for patternable, self-healing and flexible supercapacitors

The flexible and self-healing supercapacitors (SCs) are considered to be promising smart energy storage devices. Nevertheless, the SCs integrated with flexibility, lightweight, pattern editability, self-healing capabilities and desirable electrochemical properties remain a challenge. Herein, an all-in-one self-healing SC fabricated with the free-standing hybrid film (TCMP) composed of the 2,2,6,6-tetramethylpiperidin-1-yloxy-oxidized cellulose nanofibers (TOCNs) carried carbon nanotubes (CNTs), manganese dioxide (MnO2) and polyaniline (PANI) as the electrode, polyvinyl alcohol/sulfuric acid (PVA/H2SO4) gel as the electrolyte and dynamically cross-linked cellulose nanofibers/PVA/sodium tetraborate decahydrate (CNF/PB) hydrogel as the self-healing electrode matrix is developed. The TCMP film electrodes are fabricated through a facile in-situ polymerization of MnO2 and PANI in TOCNs-dispersed CNTs composite networks, exhibiting lightweight, high electrical conductivity, flexibility, pattern editability and excellent electrochemical properties. Benefited from the hierarchically porous structure and high mechanical properties of TOCNs, excellent electrical conductivity of CNTs and the desirable synergistic effect of pseudocapacitance induced by MnO2 and PANI, the assembled SC with an interdigital structure demonstrated a high areal capacitance of 1108 mF cm−2 at 2 mA cm−2, large areal energy density of 153.7 μWh cm−2 at 1101.7 μW cm−2. A satisfactory bending cycle performance (capacitance retention up to 95 % after 200 bending deformations) and self-healing characteristics (∼90 % capacitance retention after 10 cut/repair cycles) are demonstrated for the TCMP-based symmetric SC, delivering a feasible strategy for electrochemical energy storage devices with excellent performance, designable patterns and desirable safe lifespan.