In this work, we have developed a new type of sandwiched structured ionic liquid (IL)–carbon nanotube (CNT)–graphene film (GF) synthesized by a facile and effective inkjet printing method. Owing to the synergistic effects of different components in the nanohybrid material, the IL–CNT–GF material demonstrates outstanding properties including large surface area, sufficient surface active sites, and fast charge transferability. When used in electrochemical determination of cadmium ion (Cd2+) and lead ion (Pb2+), it exhibits a good sensing performance of high sensitivity, a wide linear range up to 1 μM, a low detection limit down to 0.1 nM for Cd2+ and 0.2 nM for Pb2+ (S/N = 3), and good selectivity as well. These outstanding electrochemical sensing performances allow it to be used for heavy metal detection in environment water samples.

•CuO@MnAl NSs have been fabricated by co-precipitation and hydrothermal approach.•MnAl layered doubled hydroxide can be used to wrap n-type CuO nanoparticles.•MnAl layered doubled hydroxide serves as p-type semiconductive material.•CuO@MnAl NSs electrode demonstrates excellent electrochemical performance towards the nonenzymatic sensing of H2O2.•Real-time monitoring of H2O2 from blood serum, urine and secreted by live tumorigenic and normal cells.Structurally integrated metal oxide intercalated layered double hydroxide (LDH) nanospheres (NSs) hybrid material has been of considerable current interest because of their unique structure and synergistic combination of multi- functional properties of nanocomposites. In this work, we report a new type of MnAl LDH wrapped CuO (CuO@MnAl LDHs) NSs by anchoring CuO nanoparticles (NPs) with MnAl LDHs via a facile co-precipitation and hydrothermal approach, and explore its practical application as high-efficient electrocatalyst towards H2O2 reduction for biological application. Our findings demonstrate that the integration of n-type spinel of CuO and p-type semiconductive channels of MnAl LDHs can accelerate electron transfer at breakdown voltage of p-n junction. Owing to the synergistic effect of the high surface area of CuO NPs, superb intercalation features of semiconductive MnAl LDHs for encapsulating NSs, and their intrinsic p-n junction characteristics, CuO@MnAl NSs have exhibited excellent electrocatalytic activity towards the reduction of H2O2. When implemented in electrochemical sensor system, the CuO@MnAl NSs modified electrode displays high nonenzymatic sensing performances towards H2O2 including a broad linear range 6 μM–22 mM, a low detection limit of 0.126 μM, good selectivity and long term stability, which can be exploited for in vitro detection of H2O2 in human serum and urine samples, as well as real-time tracking H2O2 secreted from different human live cells.

In this work, we report the development of well-ordered hydrogenated CoMoO4 (H-CoMoO4) and hydrogenated Fe2O3 (H-Fe2O3) nanoplate arrays on 3D graphene foam (GF) and explore their practice application as binder-free electrodes in assembling flexible all-solid-state asymmetric supercapacitor (ASC) devices. Our results show that the monolithic 3D porous GF prepared by solution casting method using Ni foam template possesses large surface area, superior electrical conductivity, and sufficient surface functional groups, which not only facilitate in situ growth of CoMoO4 and Fe2O3 nanoplates but also contribute the double-layer capacitance of the resultant supercapacitor. The well-ordered pseudocapacitive metal oxide nanoplate arrays standing up on 3D GF scaffold can provide efficient space and shorten the length for electrolyte diffusion from the outer to the inner region of the electrode material for Faradaic energy storage. Furthermore, one of our major findings is that the introduction of oxygen vacancies in CoMoO4 and Fe2O3 nanoplates by hydrogenation treatment can increase their electronic conductivity as well as improve their donor density and surface properties, which gives rise to a substantially improved electrochemical performance. Benefiting from the synergistic contributions of different components in the nanohybrid electrode, the resultant flexible ASC device with GF/H-CoMoO4 as the positive electrode and GF/H-Fe2O3 as the negative electrode achieves a wide operation voltage of 1.5 V and a maximum volumetric specific capacitance of 3.6 F cm–3, which is two times larger than that of the Ni/GF/CoMoO4//Ni/GF/Fe2O3 device (1.8 F cm–3), and the rate capability is up to 70% as the current density increases from 2 to 200 mA cm–3. Moreover, the Ni/GF/H-CoMoO4//Ni/GF/H-Fe2O3 device also exhibits a high energy density of 1.13 mWh cm–3 and a high power density of 150 mW cm–3, good mechanical flexibility with the decrease in capacitance of less than 4% after being bent inward to different angles and inward to 90° 200 times, and good cycling stability of 93.1% capacitance retention after 5000 cycles.Keywords: all-solid-state asymmetric supercapacitor; binder-free flexible electrode; hydrogenated transition-metal oxide; ordered nanoplate arrays; three-dimensional graphene foam;

•Core-shell Fe3O4@CuAl NSs have been synthesized by hydrothermal and co-precipitation approach.•Fe3O4@CuAl NSs electrode exhibits marvelous electrochemical performance towards the nonenzymatic sensing of H2O2.•Real-time monitoring of H2O2 from blood serum, urine and secreted by various live cancer cells before and after treatment.•Atmospheric pressure plasmas have been used as potential therapeutic approach for cancer therapy.In this work, we develop a new type of multifunctional core-shell nanomaterial by controllable integration of CuAl layered double hydroxides (LDHs) over the surface of iron oxides (Fe3O4) nanospheres (NSs) to fabricate (Fe3O4@CuAl NSs) hybrid material with interior tunability of LDH phase and explore its practical application in ultrasensitive detection of emerging biomarker, i.e., H2O2 as cancer diagnostic probe. In addition, atmospheric pressure plasmas (APPs) have also been used as potential therapeutic approach for cancer treatment. Due to the synergistic combination of p-type semiconductive channels of LDHs with multi-functional properties, unique morphology and abundant surface active sites, the Fe3O4@CuAl NSs modified electrode exhibited attractive electrocatalytic activity towards H2O2 reduction. Under the optimized conditions, the proposed biosensor demonstrated striking electrochemical sensing performances to H2O2 including linear range as broad as 8 orders of magnitude, low real detection limit of 1 nM (S/N = 3), high sensitivity, good reproducibility and long-term stability. Arising from the superb efficiency, the electrochemical biosensor has been used for in vitro determination of H2O2 concentrations in human urine and serum samples prior to and following the intake of coffee, and real-time monitoring of H2O2 efflux from different cancer cell lines in normal state and after plasma treatment. We believe that this novel nano-platform of structurally integrated core-shell nanohybrid materials combined with APPs will enhance diagnostic as well as therapeutic window for cancer diseases.Download high-res image (197KB)Download full-size image

•Recent developments in 2D nanomaterials based electrochemical biosensors for cancer diagnosis.•Preparation of 2D graphene, graphene derivatives and graphene-like nanomaterials.•Electrochemical platform of 2D nanomaterials for detecting different types of cancer biomarkers.Cancer is a leading cause of death in the world. Increasing evidence has demonstrated that early diagnosis holds the key towards effective treatment outcome. Cancer biomarkers are extensively used in oncology for cancer diagnosis and prognosis. Electrochemical sensors play key roles in current laboratory and clinical analysis of diverse chemical and biological targets. Recent development of functional nanomaterials offers new possibilities of improving the performance of electrochemical sensors. In particular, 2D nanomaterials have stimulated intense research due to their unique array of structural and chemical properties. The 2D materials of interest cover broadly across graphene, graphene derivatives (i.e., graphene oxide and reduced graphene oxide), and graphene-like nanomaterials (i.e., 2D layered transition metal dichalcogenides, graphite carbon nitride and boron nitride nanomaterials). In this review, we summarize recent advances in the synthesis of 2D nanomaterials and their applications in electrochemical biosensing of cancer biomarkers (nucleic acids, proteins and some small molecules), and present a personal perspective on the future direction of this area.

Electrochemical water-splitting provides an effective strategy to convert electrical energy into renewable energy resource. In this work, we report a bifunctional gas-evolving fibrous electrode based on nonprecious heterostructured Ni@NiO wrapped carbon fiber (CF) for overall water-splitting reaction. The proposed Ni@NiO wrapped CF (CF@Ni@NiO) was fabricated through a simple and controllable electrodeposition and subsequent low-temperature calcination procedure, which can easily be scaled up for practical use. Benefitting from the exposed heterojunction-like Ni@NiO nanointerfaces and the formation of Ni (III) species, the resultant CF@Ni@NiO electrode exhibits excellent catalytic activity, favorable kinetics, as well as strong durability toward both cathodic hydrogen evolution reactions (HER) and anodic oxygen evolution reactions (OER) in alkaline electrolyte, with an overall water-splitting current of 20 mA cm–2 at 1.73 V (iR uncorrected), which outperforms that of other reported nonprecious electrocatalysts. Moreover, owing to their intrinsic mechanical flexibility, these fibrous gas-evolving electrodes can be readily woven into textile structures for practical applications. The simple, low-cost, and scalable fabrication process of heterostructured materials modified fibrous electrode, coupled with recent progress in nonprecious electrocatalysts for both HER and OER, offers the possibilities to systematically study the dependence of catalytic performance on the structural parameters of the electrocatalysts, which also open new horizon for the development of next-generation flexible water-splitting devices.Keywords: Bifunctional electrodes; Carbon fiber; Electrocatalysis; Nickel/nickel oxide; Water splitting;

Recent advances in flexible fiber-based microelectrodes have opened a new horizon for sensitive real-time near-cell and even intracellular measurements. In this work, we develop a new type of hierarchical nanohybrid microelectrode based on three-dimensional (3D) porous graphene-wrapped activated carbon fiber (ACF) via a facile and effective electrodeposition of graphene oxide (GO) nanosheets on ACF using a green ionic liquid (IL) as the electrolyte. This technique enables the simultaneous electrodeposition and electrochemical reduction of GO nanosheets on ACF to form 3D porous IL functionalized electrochemically reduced GO (ERGO)-wrapped ACF (IL–ERGO/ACF). The adsorbed IL molecules on the ERGO surface provide sufficient active sites and act as the template for the in situ electrodeposition of highly dense and well-dispersed bimetal PtAu nanoflowers on the 3D IL–ERGO scaffold. By virtue of the unique array of structural and chemical properties of bimetal PtAu nanocatalysts and 3D porous IL–ERGO on ACF, the resultant PtAu nanoflowers-decorated IL–ERGO/ACF (PtAu/IL–ERGO/ACF) microelectrode demonstrates a variety of excellent sensing performances, including high sensitivity, a wide linear range and good selectivity in the electrochemical detection of a newly emerged cancer biomarker, hydrogen peroxide (H2O2). When used for the real-time tracking of H2O2 secreted from female cancer cells, such as breast cancer cells and gynecological cancer cells, the electrochemical sensor based on the PtAu/IL–ERGO/ACF microelectrode provides important information for distinguishing between different cancer cells and normal cells and for evaluating the therapeutic activity of antitumor drugs towards live cancer cells, which are of great clinical significance for cancer diagnosis and management.

The development of carbon based hollow-structured nanospheres (HNSs) materials has stimulated growing interest due to their controllable structure, high specific surface area, large void space, enhanced mass transport, and good biocompatibility. The incorporation of functional nanomaterials into their core and/or shell opens new horizons in designing functionalized HNSs for a wider spectrum of promising applications. In this work, we report a new type of functionalized HNSs based on Pd nanoparticles (NPs) decorated double shell structured N-doped graphene quantum dots (NGQDs)@N-doped carbon (NC) HNSs, with ultrafine Pd NPs and “nanozyme” NGQDs as dual signal-amplifying nanoprobes, and explore their promising application as a highly efficient electrocatalyst in electrochemical sensing of a newly emerging biomarker, i.e., hydrogen peroxide (H2O2), for cancer detection. Due to the synergistic effect of the robust and conductive HNS supports and catalytically active Pd NPs and NGQD in facilitating electron transfer, the NGQD@NC@Pd HNS hybrid material exhibits high electrocatalytic activity toward the direct reduction of H2O2 and can promote the electrochemical reduction reaction of H2O2 at a favorable potential of 0 V, which effectively restrains the redox of most electroactive species in physiological samples and eliminates interference signals. The resultant electrochemical H2O2 biosensor based hybrid HNSs materials demonstrates attractive performance, including low detection limit down to nanomole level, short response time within 2 s, as well as high sensitivity, reproducibility, selectivity, and stability, and have been used in real-time tracking of trace amounts of H2O2 secreted from different living cancer cells in a normal state and treated with chemotherapy and radiotherapy.Keywords: cancer detection; carbon hollow nanospheres; electrocatalyst; electrochemical biosensor; graphene quantum dots; Pd nanoparticles

•Mechanical strong and stable graphene paper severs as flexible electrode substrate.•3D nanoporous gold scaffold facilitates immobilization of PtCo alloy nanoparticles.•PtCo alloy nanoparticles on scaffold are highly dense, well dispersed and ultrafine.•The nanohybrid paper electrode exhibits good performance in electrochemical glucose detection.Recent advances in on-body wearable medical apparatus and implantable devices drive the development of light-weight and bendable electrochemical sensors, which require the design of high-performance flexible electrode system. In this work, we reported a new type of freestanding and flexible electrode based on graphene paper (GP) supported 3D monolithic nanoporous gold (NPG) scaffold (NPG/GP), which was further modified by a layer of highly dense, well dispersed and ultrafine binary PtCo alloy nanoparticles via a facile and effective ultrasonic electrodeposition method. Our results demonstrated that benefited from the synergistic effect of the electrocatalytically active PtCo alloy nanoparticles, the large-active-area and highly conductive 3D NPG scaffold, and the mechanically strong and stable GP electrode substrate, the resultant PtCo alloy nanoparticles modified NPG/GP (PtCo/NPG/GP) exhibited high mechanical strength and good electrochemical sensing performances toward nonenzymatic detection of glucose, including a wide linear range from 35 μM– to 30 mM, a low detection limit of 5 μM (S/N = 3) and a high sensitivity of 7.84 μA cm−2 mM−1 as well as good selectivity, long-term stability and reproducibility. The practical application of the proposed PtCo/NPG/GP has also been demonstrated in in vitro detection of blood glucose in real clinic samples.

A three-dimensional graphene wrapped nickel foam (Ni/GF) architecture has been prepared by a facile yet effective and scalable interfacial reduction method. Inspired by the porous and conductive network structures of Ni/GF, we have deposited manganese dioxide (MnO2) and polypyrrole (PPy) nanostructures on the Ni/GF substrates and successfully fabricated a flexible solid-state asymmetric supercapacitor assembled with Ni/GF/MnO2 as the positive electrode and Ni/GF/PPy as the negative electrode in a gel electrolyte. Benefiting from the high capacitance and fast ion transport properties of our hierarchically porous electrodes, the optimized asymmetric supercapacitor exhibits an excellent stability in a high-voltage region of 1.8 V and remarkable cycling stability with only 9.8% decrease of capacitance after 10000 cycles. Moreover, the device can deliver a high energy density of 1.23 mW h cm−3, which is substantially enhanced compared to most of the reported solid-state supercapacitors. The impressive results presented here may pave the way for promising applications in future energy storage systems.

Fiber based supercapacitors are promising energy storage devices for flexible electronics because of their integration of lightweight, high flexibility and tiny volume. Here, a facile yet effective method is developed to synthesize two types of functionalized carbonaceous fibers, i.e., carbon fiber@reduced graphene oxide@manganese dioxide (CF@RGO@MnO2) and CF@thick RGO (CF@TRGO), by dip coating and subsequent electrochemical strategies. The assembled asymmetric supercapacitor device using CF@RGO@MnO2 as the positive electrode and CF@TRGO as the negative electrode can be operated with a high voltage region of 1.6 V and exhibits a high volumetric energy density of 1.23 mW h cm−3. Additionally, our device has an excellent long-term cycling stability with more than 91% retention after 10000 cycles. To demonstrate potential applications of our prepared fiber based all-solid-state asymmetric supercapacitors, we successfully use them to power a flexible integrated copper phthalocyanine (CuPc) photodetector and a light-emitting diode.

Recent progress in the in situ molecular detection of living cells has attracted tremendous research interests due to its great significance in biochemical, physiological, and pathological investigation. Especially for the electrochemical detection of hydrogen peroxide (H2O2) released by living cells, the highly efficient and cost-effective electrocatalysts are highly desirable. In this work, we develop a novel type of microporous Co3O4 hollow nanospheres containing encapsulated Pd nanoparticles (Pd@Co3O4). Owing to the synergy effect between the permeable microporous Co3O4 shell and the ultrafine Pd nanoparticles that encapsulated in it, the resultant Pd@Co3O4 based electrode exhibits excellent electrochemical sensor performance toward H2O2, even when the content of Pd in Pd@Co3O4 hollow nanospheres is as low as 1.14 wt %, which enable it be used for real-time tracking of the secretion of H2O2 in different types of living human cells.Keywords: biosensors; electrochemistry; living cell tracking; microporous hollow nanospheres; ultrafine Pd nanoparticles

•MnO2–graphene paper has been fabricated by one-step electrochemical method.•MnO2–graphene paper serves as high-performance flexible electrode for nonenzymatic electrochemical sensing of hydrogen peroxide.•MnO2–graphene paper electrode has been used for real-time tracking hydrogen peroxide secretion by live cells.Recent progress in flexible and lightweight electrochemical sensor systems requires the development of paper-like electrode materials. Here, we report a facile and green synthesis of a new type of MnO2 nanowires–graphene nanohybrid paper by one-step electrochemical method. This strategy demonstrates a collection of unique features including the effective electrochemical reduction of graphene oxide (GO) paper and the high loading of MnO2 nanowires on electrochemical reduced GO (ERGO) paper. When used as flexible electrode for nonenzymatic detection of hydrogen peroxide (H2O2), MnO2–ERGO paper exhibits high electrocatalytic activity toward the redox of H2O2 as well as excellent stability, selectivity and reproducibility. The amperometric responses are linearly proportional to H2O2 concentration in the range 0.1–45.4 mM, with a detection limit of 10 μM (S/N = 3) and detection sensitivity of 59.0 μA cm−2 mM−1. These outstanding sensing performances enable the practical application of MnO2–ERGO paper electrode for the real-time tracking H2O2 secretion by live cells macrophages. Therefore, the proposed graphene-based nanohybrid paper electrode with intrinsic flexibility, tailorable shapes and adjustable properties can contribute to the full realization of high-performance flexible electrode material used in point-of-care testing devices and portable instruments for in-vivo clinical diagnostics and on-site environmental monitoring.

•Three-dimensional porous NixCo2x(OH)6x/graphene nanohybrid foam has been prepared by a facile and green one-step electrochemical method.•NixCo2x(OH)6x/graphene foam exhibits better structural integration of optimal component and improved electrochemical properties.•NixCo2x(OH)6x/graphene foam servers as binder-free electrode for supercapacitor.•NixCo2x(OH)6x/graphene foam has been used for nonenzymatic H2O2 biosensing.In this work, we present a new type of three-dimensional (3D) nanohybrid electrode based on microscopic graphene foam loaded nickel − cobalt hydroxides nanoflakes (NixCo2x(OH)6x/graphene foam) synthesized by one-step electrochemical method. This method allows for better structural integration of different electrode component and improves the electrochemical properties in terms of capacitive performance and electrocatalytic activity. When used as binder-free electrode for supercapacitor, the 3D NixCo2x(OH)6x/graphene foam exhibits a high specific capacitance of 703.6 mF cm−2 at a current density of 10 mA cm−2 and a good rate capability of 83.8% at 100 mA cm−2, and the specific capacitance retention remains 97.5% after 1000 cycles. Furthermore, for electrochemical biosensor application, the NixCo2x(OH)6x/graphene nanohybrid electrode exhibits high selectivity, reproducibility and stability towards the nonenzymatic detection of hydrogen peroxide. These enable it as a multifunctional electrode material for wide spectrum of electrochemical application.

A multifunctional magnetic 3D graphene/Fe3O4 architecture (GFA) has been fabricated by a facile and scalable one-pot self-assembled strategy through hydrothermal treatment of a mixed aqueous precursor solution of graphene oxide (GO) and Fe3O4 nanoparticles (NPs). Benefiting from the 3D porous structure and synergistic effects of the assembled graphene nanosheets and Fe3O4 NPs, the resultant GFA exhibits excellent adsorption capacities of not only organic dyes such as methylene blue (MB), but also toxic solvents such as toluene and chloroform, and improved electrochemical capacitive performances in comparison with pristine graphene architectures and Fe3O4 NPs. The impressive results presented here may have high impact on the future fabrication of functional graphene based architectures for practical applications.

We reported the development of a new type of bifunctional nanocatalyst based on three-dimensional (3D) macroscopic carbon nanotube (CNT)–graphene hydrogel (GH) supported Pd nanoparticles (i.e., Pd–CNT–GH) and explored its practical application in catalytic reduction of p-nitrophenol to p-aminophenol. The 3D Pd–CNT–GH was synthesized by a facile one-pot self-assembled approach through hydrothermal treatment of a mixed aqueous precursor solution of PdCl42–, CNT, and graphene oxide (GO). Under the appropriate condition, the spontaneous redox reaction between precursor PdCl42– and CNT–GO as well as the self-assembly of macroscopic CNT–GH occurs simultaneously, leading to the formation of 3D Pd–CNT–GH. Because of the unique structural and functional properties of different components in the nanocatalyst and the synergistic effect between them, the as-prepared Pd–CNT–GH exhibits superior catalytic performance toward the reduction of p-nitrophenol to p-aminophenol, with 100% conversion within 30 s, even when the content of Pd in it is as low as 2.98 wt %. Moreover, after 20 successive cycles of reactions, the reaction time still keeps within 46 s. Therefore, the rational design of 3D macroscopic graphene-based nanohybrid material supported highly catalytically active nanoparticles, combined with the facile one-pot self-assembled strategy, provide a universal platform to fabricate desired 3D multifunctional nanomaterials that can be used in a broad range of catalysis, environmental protection, energy storage and conversation, drug delivery, chemical and biological sensing, and so forth.Keywords: carbon nanotube; catalysis; graphene hydrogel; one-pot self-assembly; p-nitrophenol; palladium nanoparticles

Freestanding paper-like electrode materials have trigged significant research interest for their practical application in flexible and lightweight energy storage devices. In this work, we reported a new type of flexible nanohybrid paper electrode based on full inkjet printing synthesis of a freestanding graphene paper (GP) supported three-dimensional (3D) porous graphene hydrogel (GH)–polyaniline (PANI) nanocomposite, and explored its practical application in flexible all-solid-state supercapacitor (SC). The utilization of 3D porous GH scaffold to load nanostructured PANI dramatically enhances the electrical conductivity, the specific capacitance and the cycle stability of the GH–PANI nanocomposite. Additionally, GP can intimately interact with GH–PANI through π–π stacking to form a unique freestanding GP supported GH–PANI nanocomposite (GH–PANI/GP) with distinguishing mechanical, electrochemical and capacitive properties. These exceptional attributes, coupled with the merits of full inkjet printing strategy, lead to the formation of a high-performance binder-free paper electrode for flexible and lightweight SC application. The flexible all-solid-state symmetric SC based on GH–PANI/GP electrode and gel electrolyte exhibits remarkable mechanical flexibility, high cycling performance and acceptable energy density of 24.02 Wh kg–1 at a power density of 400.33 W kg–1. More importantly, the proposed simple and scale-up full inkjet printing procedure for the preparation of freestanding GP supported 3D porous GH-PANI nanocomposite is a modular approach to fabricate other graphene-based nanohybrid papers with tailorable properties and optimal components.Keywords: all-solid-state supercapacitor; flexible electrode; freestanding graphene paper; full inkjet printing synthesis; three-dimensional porous graphene−polyaniline nanocomposite

A three-dimensional graphene wrapped nickel foam (Ni/GF) architecture has been prepared by a facile yet effective and scalable interfacial reduction method. Inspired by the porous and conductive network structures of Ni/GF, we have deposited manganese dioxide (MnO2) and polypyrrole (PPy) nanostructures on the Ni/GF substrates and successfully fabricated a flexible solid-state asymmetric supercapacitor assembled with Ni/GF/MnO2 as the positive electrode and Ni/GF/PPy as the negative electrode in a gel electrolyte. Benefiting from the high capacitance and fast ion transport properties of our hierarchically porous electrodes, the optimized asymmetric supercapacitor exhibits an excellent stability in a high-voltage region of 1.8 V and remarkable cycling stability with only 9.8% decrease of capacitance after 10000 cycles. Moreover, the device can deliver a high energy density of 1.23 mW h cm−3, which is substantially enhanced compared to most of the reported solid-state supercapacitors. The impressive results presented here may pave the way for promising applications in future energy storage systems.

Fiber based supercapacitors are promising energy storage devices for flexible electronics because of their integration of lightweight, high flexibility and tiny volume. Here, a facile yet effective method is developed to synthesize two types of functionalized carbonaceous fibers, i.e., carbon fiber@reduced graphene oxide@manganese dioxide (CF@RGO@MnO2) and CF@thick RGO (CF@TRGO), by dip coating and subsequent electrochemical strategies. The assembled asymmetric supercapacitor device using CF@RGO@MnO2 as the positive electrode and CF@TRGO as the negative electrode can be operated with a high voltage region of 1.6 V and exhibits a high volumetric energy density of 1.23 mW h cm−3. Additionally, our device has an excellent long-term cycling stability with more than 91% retention after 10000 cycles. To demonstrate potential applications of our prepared fiber based all-solid-state asymmetric supercapacitors, we successfully use them to power a flexible integrated copper phthalocyanine (CuPc) photodetector and a light-emitting diode.