Recently, Kovalenko and co‐workers and Li and co‐workers developed CsPbX3 (X = Cl, Br, I) inorganic perovskite quantum dots (IPQDs), which exhibited ultrahigh photoluminescence (PL) quantum yields (QYs), low‐threshold lasing, and multicolor electroluminescence. However, the usual synthesis needs high temperature, inert gas protection, and localized injection operation, which are severely against applications. Moreover, the so unexpectedly high QYs are very confusing. Here, for the first time, the IPQDs' room‐temperature (RT) synthesis, superior PL, underlying origins and potentials in lighting and displays are reported. The synthesis is designed according to supersaturated recrystallization (SR), which is operated at RT, within few seconds, free from inert gas and injection operation. Although formed at RT, IPQDs' PLs have QYs of 80%, 95%, 70%, and FWHMs of 35, 20, and 18 nm for red, green, and blue emissions. As to the origins, the observed 40 meV exciton binding energy, halogen self‐passivation effect, and CsPbX3@X quantum‐well band alignment are proposed to guarantee the excitons generation and high‐rate radiative recombination at RT. Moreover, such superior optical merits endow them with promising potentials in lighting and displays, which are primarily demonstrated by the white light‐emitting diodes with tunable color temperature and wide color gamut. A room‐temperature supersaturated recrystallization method is developed to rapidly synthesize all‐inorganic halide perovskite QDs with blue, green, and red luminescent quantum yields of 70%–95% and line‐widths less than 35 nm. The origins of the optical superiority are proposed to be the observed 40 meV exciton binding energy, surface self‐passivation effect, and quantum‐well band alignment. Such superior optical merits endow them with promising potentials in healthy lighting and wide‐color‐gamut displays, which are primarily demonstrated by the color‐temperature‐tunable white light‐emitting diodes.
There is a growing demand for flexible and soft electronic devices. In particular, stretchable, skin‐mountable, and wearable strain sensors are needed for several potential applications including personalized health‐monitoring, human motion detection, human‐machine interfaces, soft robotics, and so forth. This Feature Article presents recent advancements in the development of flexible and stretchable strain sensors. The article shows that highly stretchable strain sensors are successfully being developed by new mechanisms such as disconnection between overlapped nanomaterials, crack propagation in thin films, and tunneling effect, different from traditional strain sensing mechanisms. Strain sensing performances of recently reported strain sensors are comprehensively studied and discussed, showing that appropriate choice of composite structures as well as suitable interaction between functional nanomaterials and polymers are essential for the high performance strain sensing. Next, simulation results of piezoresistivity of stretchable strain sensors by computational models are reported. Finally, potential applications of flexible strain sensors are described. This survey reveals that flexible, skin‐mountable, and wearable strain sensors have potential in diverse applications while several grand challenges have to be still overcome. Stretchable and sensitive strain sensors can potentially function for biomedical applications, human–machine interfaces, and emerging soft robotics. Recent advancements in the development of stretchable, skin‐mountable, and wearable strain sensors and their potential applications are reviewed. High performance sensors have been developed by composites of functional nanomaterials and flexible polymer supports.
A recent approach for solar‐to‐hydrogen generation has been water electrolysis using efficient, stable, and inexpensive bifunctional electrocatalysts within strong electrolytes. Herein, the direct growth of 1D NiCo2S4 nanowire (NW) arrays on a 3D Ni foam (NF) is described. This NiCo2S4 NW/NF array functions as an efficient bifunctional electrocatalyst for overall water splitting with excellent activity and stability. The 3D‐Ni foam facilitates the directional growth, exposing more active sites of the catalyst for electrochemical reactions at the electrode–electrolyte interface. The binder‐free, self‐made NiCo2S4 NW/NF electrode delivers a hydrogen production current density of 10 mA cm–2 at an overpotential of 260 mV for the oxygen evolution reaction and at 210 mV (versus a reversible hydrogen electrode) for the hydrogen evolution reaction in 1 m KOH. This highly active and stable bifunctional electrocatalyst enables the preparation of an alkaline water electrolyzer that could deliver 10 mA cm–2 under a cell voltage of 1.63 V. Because the nonprecious‐metal NiCo2S4 NW/NF foam‐based electrodes afford the vigorous and continuous evolution of both H2 and O2 at 1.68 V, generated using a solar panel, they appear to be promising water splitting devices for large‐scale solar‐to‐hydrogen generation. Direct growth of thiospinel nanowire arrays on a nickel current collector improves overall water splitting using an efficient and durable nonprecious‐metal NiCo2S4 nanowire array on a nickel foam in an alkaline electrolyte. More exposed active sites and a higher number of electron routes decrease the overpotential and enhance the bifunctional activity for large‐scale application.
Organometal trihalide perovskite based solar cells have exhibited the highest efficiencies to‐date when incorporated into mesostructured composites. However, thin solid films of a perovskite absorber should be capable of operating at the highest efficiency in a simple planar heterojunction configuration. Here, it is shown that film morphology is a critical issue in planar heterojunction CH3NH3PbI3‐xClx solar cells. The morphology is carefully controlled by varying processing conditions, and it is demonstrated that the highest photocurrents are attainable only with the highest perovskite surface coverages. With optimized solution based film formation, power conversion efficiencies of up to 11.4% are achieved, the first report of efficiencies above 10% in fully thin‐film solution processed perovskite solar cells with no mesoporous layer. The critical role of perovskite morphology in planar heterojunction perovskite solar cells is probed and understood. Dewetting of perovskite films is minimized, to achieve uniform 100% coverage perovskite layers. Solution cast planar heterojunction solar cells with efficiencies of up to 11.4% are fabricated, a new record for such cells with no mesoporous layer.
The status of ambient temperature sodium ion batteries is reviewed in light of recent developments in anode, electrolyte and cathode materials. These devices, although early in their stage of development, are promising for large‐scale grid storage applications due to the abundance and very low cost of sodium‐containing precursors used to make the components. The engineering knowledge developed recently for highly successful Li ion batteries can be leveraged to ensure rapid progress in this area, although different electrode materials and electrolytes will be required for dual intercalation systems based on sodium. In particular, new anode materials need to be identified, since the graphite anode, commonly used in lithium systems, does not intercalate sodium to any appreciable extent. A wider array of choices is available for cathodes, including high performance layered transition metal oxides and polyanionic compounds. Recent developments in electrodes are encouraging, but a great deal of research is necessary, particularly in new electrolytes, and the understanding of the SEI films. The engineering modeling calculations of Na‐ion battery energy density indicate that 210 Wh kg−1 in gravimetric energy is possible for Na‐ion batteries compared to existing Li‐ion technology if a cathode capacity of 200 mAh g−1 and a 500 mAh g−1 anode can be discovered with an average cell potential of 3.3 V. The research and development of ambient temperature Na‐ion batteries is progressing quickly and is now poised to penetrate the energy storage landscape. The combination of new electrode materials, electrochemical couples, and engineering advances coupled with a potential for low‐cost and long‐life make them attractive candidates for grid storage.
Development of easy‐to‐make, highly active, and stable bifunctional electrocatalysts for water splitting is important for future renewable energy systems. Three‐dimension (3D) porous Ni/Ni8P3 and Ni/Ni9S8 electrodes are prepared by sequential treatment of commercial Ni‐foam with acid activation, followed by phosphorization or sulfurization. The resultant materials can act as self‐supported bifunctional electrocatalytic electrodes for direct water splitting with excellent activity toward oxygen evolution reaction and hydrogen evolution reaction in alkaline media. Stable performance can be maintained for at least 24 h, illustrating their versatile and practical nature for clean energy generation. Furthermore, an advanced water electrolyzer through exploiting Ni/Ni8P3 as both anode and cathode is fabricated, which requires a cell voltage of 1.61 V to deliver a 10 mA cm−2 water splitting current density in 1.0 m KOH solution. This performance is significantly better than that of the noble metal benchmark—integrated Ni/IrO2 and Ni/Pt–C electrodes. Therefore, these bifunctional electrodes have significant potential for realistic large‐scale production of hydrogen as a replacement clean fuel to polluting and limited fossil‐fuels. Three‐dimension nickel‐based electrocatalytic electrodes (Ni/Ni8P3 and Ni/Ni9S8) are developed for application in water splitting. The as‐obtained Ni/Ni8P3 catalytic electrode, particularly exhibiting excellent electrocatalytic activity and stability due to its advanced structure effects, can serve as a highly efficient and stable bifunctional catalyst for overall water splitting.
As new members of carbon material family, carbon and graphene quantum dots (CDs, GQDs) have attracted tremendous attentions for their potentials for biological, optoelectronic, and energy related applications. Among these applications, bio‐imaging has been intensively studied, but optoelectronic and energy devices are rapidly rising. In this Feature Article, recent exciting progresses on CD‐ and GQD‐based optoelectronic and energy devices, such as light emitting diodes (LEDs), solar cells (SCs), photodetctors (PDs), photocatalysis, batteries, and supercapacitors are highlighted. The recent understanding on their microstructure and optical properties are briefly introduced in the first part. Some important progresses on optoelectronic and energy devices are then addressed as the main part of this Feature Article. Finally, a brief outlook is given, pointing out that CDs and GQDs could play more important roles in communication‐ and energy‐functional devices in the near future. Carbon dots and graphene quantum dots have been investigated for several years and researchers' interest is moving from photoluminescence towards device applications. In this Feature Article, applications in optoelectronic and energy devices of carbon dots and graphene quantum dots are summarized, as well as their optical properties. Future directions, challenges, and other possible applications are also put forward.
Lithium (Li) metal has been considered as an important substitute for the graphite anode to further boost the energy density of Li‐ion batteries. However, Li dendrite growth during Li plating/stripping causes safety concern and poor lifespan of Li metal batteries (LMB). Herein, fluoroethylene carbonate (FEC) additives are used to form a LiF‐rich solid electrolyte interphase (SEI). The FEC‐induced SEI layer is compact and stable, and thus beneficial to obtain a uniform morphology of Li deposits. This uniform and dendrite‐free morphology renders a significantly improved Coulombic efficiency of 98% within 100 cycles in a Li | Cu half‐cell. When the FEC‐protected Li metal anode matches a high‐loading LiNi0.5Co0.2Mn0.3O2 (NMC) cathode (12 mg cm−2), a high initial capacity of 154 mAh g−1 (1.9 mAh cm−2) at 180.0 mA g−1 is obtained. This LMB with conversion‐type Li metal anode and intercalation‐type NMC cathode affords an emerging energy storage system to probe the energy chemistry of Li metal protection and demonstrates the material engineering of batteries with very high energy density. Fluoroethylene carbonate (FEC) additive is used to form a LiF‐rich solid electrolyte interphase (SEI). The FEC‐induced SEI layer is compact and stable, and therefore beneficial to obtain a uniform morphology of Li deposits. When the FEC‐protected Li metal anode matches a high‐loading oxide cathode, a high initial capacity and stable cycling are achieved.
A facile and novel one‐step method of growing nickel‐cobalt layered double hydroxide (Ni‐Co LDH) hybrid films with ultrathin nanosheets and porous nanostructures on nickel foam is presented using cetyltrimethylammonium bromide as nanostructure growth assisting agent but without any adscititious alkali sources and oxidants. As pseudocapacitors, the as‐obtained Ni‐Co LDH hybrid film‐based electrodes display a significantly enhanced specific capacitance (2682 F g−1 at 3 A g−1, based on active materials) and energy density (77.3 Wh kg−1 at 623 W kg−1), compared to most previously reported electrodes based on nickel‐cobalt oxides/hydroxides. Moreover, the asymmetric supercapacitor, with the Ni‐Co LDH hybrid film as the positive electrode material and porous freeze‐dried reduced graphene oxide (RGO) as the negative electrode material, exhibits an ultrahigh energy density (188 Wh kg−1) at an average power density of 1499 W kg−1 based on the mass of active material, which greatly exceeds the energy densities of most previously reported nickel or cobalt oxide/hydroxide‐based asymmetric supercapacitors. Ni–Co LDH electrode materials with ultrahigh capacitive performance are prepared. The capacitive performances of as‐obtained Ni–Co LDHs for pseudocapacitors and asymmetric supercapacitors significantly exceed those of most similar reported materials. This synthesis method can also be extended to synthesize other bimetallic LDHs with high electrochemical activity.
Water splitting for the production of hydrogen and oxygen is an appealing solution to advance many sustainable and renewable energy conversion and storage systems, while the key fact depends on the innovative exploration regarding the design of efficient electrocatalysts. Reported herein is the growth of CoP mesoporous nanorod arrays on conductive Ni foam through an electrodeposition strategy. The resulting material of well‐defined mesoporosity and a high specific surface area (148 m2 g−1) can be directly employed as a bifunctional and flexible working electrode for both hydrogen and oxygen evolution reactions, showing superior activities as compared with noble metal benchmarks and state‐of‐the‐art transition‐metal‐based catalysts. This is intimately related to the unique nanorod array electrode configuration, leading to excellent electric interconnection and improved mass transport. A further step is taken toward an alkaline electrolyzer that can achieve a current density of 10 mA cm−2 at a voltage around 1.62 V over a long‐term operation, better than the combination of Pt and IrO2. This development is suggested to be readily extended to obtain other electrocatalysis systems for scale‐up water‐splitting technology. Flexible, bifunctional electrodes with self‐supported CoP mesoporous nanorod arrays are fabricated through an electrodeposition strategy. The electrodes possess well‐structured mesoporosity and a high specific surface area, exhibiting high activities toward both electrochemical hydrogen and oxygen evolution reactions. In a further step, an alkaline electrolyzer with a current density of 10 mA cm−2 at 1.62 V in a long‐term operation is realized.
“Graphitic” (g)‐C3N4 with a layered structure has the potential of forming graphene‐like nanosheets with unusual physicochemical properties due to weak van der Waals forces between layers. Herein is shown that g‐C3N4 nanosheets with a thickness of around 2 nm can be easily obtained by a simple top‐down strategy, namely, thermal oxidation etching of bulk g‐C3N4 in air. Compared to the bulk g‐C3N4, the highly anisotropic 2D‐nanosheets possess a high specific surface area of 306 m2 g−1, a larger bandgap (by 0.2 eV), improved electron transport ability along the in‐plane direction, and increased lifetime of photoexcited charge carriers because of the quantum confinement effect. As a consequence, the photocatalytic activities of g‐C3N4 nanosheets have been remarkably improved in terms of •OH radical generation and photocatalytic hydrogen evolution. Graphene‐like C3N4 nanosheets produced by direct thermal oxidative etching of bulk “graphitic”‐C3N4 show superior photocatalytic activities compared to the bulk due to a high specific surface area, a larger bandgap (by 0.2 eV), increased lifetimes of photoexcited charge carriers, and improved electron transport ability.
The formation of semiconductor composites comprising multicomponent or multiphase heterojunctions is a very effective strategy to design highly active photocatalyst systems. This review summarizes the recent strategies to develop such composites, and highlights the most recent developments in the field. After a general introduction into the different strategies to improve photocatalytic activity through formation of heterojunctions, the three different types of heterojunctions are introduced in detail, followed by a historical introduction to semiconductor heterojunction systems and a thorough literature overview. Special chapters describe the highly‐investigated carbon nitride heterojunctions as well as very recent developments in terms of multiphase heterojunction formation, including the latest insights into the anatase‐rutile system. When carefully designed, semiconductor composites comprising two or three different materials or phases very effectively facilitate charge separation and charge carrier transfer, substantially improving photocatalytic and photoelectrochemical efficiency. The formation of semiconductor composites, leading to multicomponent and multiphase heterojunctions, is herein reviewed. Highly active photocatalyst systems with improved charge carrier separation and charge transfer are the result, leading to significantly enhanced efficiencies. Particular interest is given to recent developments in multiphase composites
Organic–inorganic hybrid perovskites have attracted attention as successful light harvesting materials for mesoscopic solid‐state solar cells and led to record breaking efficiencies. The photovoltaic performance of these devices is greatly dependent on the film morphology, which in turn is dependent on the deposition techniques and subsequent treatments employed. In this work the perovskite film is deposited by spin‐coating a precursor solution of PbCl2 and CH3NH3I (1 to 3 molar ratio) in dimethylformamide. Here, the role of the temperature used in the annealing process required to convert the as deposited solution into the perovskite material is investigated. It is found that the conversion requires sufficiently high temperatures to ensure the vaporization of solvent and the crystallization of the perovskite material. However, increasing the annealing temperature too high leads to the additional formation of PbI2, which is detrimental to the photovoltaic performance. Furthermore, the effect of the annealing temperature on the film formation, morphology, and composition is examined and correlated with the photovoltaic performance and device working mechanisms. The effect of the annealing temperature on the formation of the perovskite film is investigated. The temperature determines the rate of solvent vaporization and perovskite crystallization thus controlling the film morphology and composition, leading to the formation of PbI2 at very high temperatures. This is correlated with the device performance and working mechanisms.
The photoluminescence, transmittance, charge‐carrier recombination dynamics, mobility, and diffusion length of CH3NH3PbI3 are investigated in the temperature range from 8 to 370 K. Profound changes in the optoelectronic properties of this prototypical photovoltaic material are observed across the two structural phase transitions occurring at 160 and 310 K. Drude‐like terahertz photoconductivity spectra at all temperatures above 80 K suggest that charge localization effects are absent in this range. The monomolecular charge‐carrier recombination rate generally increases with rising temperature, indicating a mechanism dominated by ionized impurity mediated recombination. Deduced activation energies Ea associated with ionization are found to increase markedly from the room‐temperature tetragonal (Ea ≈ 20 meV) to the higher‐temperature cubic (Ea ≈ 200 meV) phase adopted above 310 K. Conversely, the bimolecular rate constant decreases with rising temperature as charge‐carrier mobility declines, while the Auger rate constant is highly phase specific, suggesting a strong dependence on electronic band structure. The charge‐carrier diffusion length gradually decreases with rising temperature from about 3 μm at −93 °C to 1.2 μm at 67 °C but remains well above the optical absorption depth in the visible spectrum. These results demonstrate that there are no fundamental obstacles to the operation of cells based on CH3NH3PbI3 under typical field conditions. The photoconductivity in CH3NH3PbI3 thin films is investigated from 8 to 370 K across three structural phases. Analysis of the charge‐carrier recombination dynamics reveals a variety of starkly differing recombination mechanisms. Evidence of charge‐carrier localization is observed only at low temperature. High charge mobility and diffusion length are maintained at high temperature beyond the tetragonal‐to‐cubic phase transition at ≈310 K.
Although phosphorene has attracted much attention in electronics and optoelectronics as a new type of two‐dimensional material, in‐depth investigations and applications have been limited by the current synthesis techniques. Herein, a basic N‐methyl‐2‐pyrrolidone (NMP) liquid exfoliation method is described to produce phosphorene with excellent water stability, controllable size and layer number, as well as in high yield. Phosphorene samples composed of one to four layers exhibit layer‐dependent Raman scattering characteristics thus providing a fast and efficient means for the in situ determination of the thickness (layer number) of phosphorene. The linear and nonlinear ultrafast absorption behavior of the as‐exfoliated phosphorene is investigated systematically by UV–vis–NIR absorption and Z‐scan measurements. By taking advantage of their unique nonlinear absorption, ultrashort pulse generation applicable to optical saturable absorbers is demonstrated. In addition to a unique fabrication technique, our work also reveals the large potential of phosphorene in ultrafast photonics. A basic N‐methyl‐2‐pyrrolidone liquid exfoliation method is described to produce phosphorene with an excellent water stability, controllable size and layer number, as well as in a high yield. Phosphorene with one to four layers exhibits layer‐dependent Raman scattering characteristics thus providing a fast and efficient means for the in situ determination of the thickness of phosphorene.
A strategy to prepare flexible and conductive MXene/graphene (reduced graphene oxide, rGO) supercapacitor electrodes by using electrostatic self‐assembly between positively charged rGO modified with poly(diallyldimethylammonium chloride) and negatively charged titanium carbide MXene nanosheets is presented. After electrostatic assembly, rGO nanosheets are inserted in‐between MXene layers. As a result, the self‐restacking of MXene nanosheets is effectively prevented, leading to a considerably increased interlayer spacing. Accelerated diffusion of electrolyte ions enables more electroactive sites to become accessible. The freestanding MXene/rGO‐5 wt% electrode displays a volumetric capacitance of 1040 F cm−3 at a scan rate of 2 mV s−1 , an impressive rate capability with 61% capacitance retention at 1 V s−1 and long cycle life. Moreover, the fabricated binder‐free symmetric supercapacitor shows an ultrahigh volumetric energy density of 32.6 Wh L−1, which is among the highest values reported for carbon and MXene based materials in aqueous electrolytes. This work provides fundamental insight into the effect of interlayer spacing on the electrochemical performance of 2D hybrid materials and sheds light on the design of next‐generation flexible, portable and highly integrated supercapacitors with high volumetric and rate performances. MXene/reduced graphene oxide (rGO) hybrid films are prepared through electrostatic self‐assembly of negatively charged MXene nanosheets and positively charged rGO nanosheets. rGO nanosheets are inserted in between MXene layers as conductive spacers, efficiently alleviating the self‐restacking of both rGO and MXene. As a result, the hybrid films exhibit ultrahigh volumetric capacitance and an impressive rate capability.
As one important component of sulfur cathodes, the carbon host plays a key role in the electrochemical performance of lithium‐sulfur (Li‐S) batteries. In this paper, a mesoporous nitrogen‐doped carbon (MPNC)‐sulfur nanocomposite is reported as a novel cathode for advanced Li‐S batteries. The nitrogen doping in the MPNC material can effectively promote chemical adsorption between sulfur atoms and oxygen functional groups on the carbon, as verified by X‐ray absorption near edge structure spectroscopy, and the mechanism by which nitrogen enables the behavior is further revealed by density functional theory calculations. Based on the advantages of the porous structure and nitrogen doping, the MPNC‐sulfur cathodes show excellent cycling stability (95% retention within 100 cycles) at a high current density of 0.7 mAh cm‐2 with a high sulfur loading (4.2 mg S cm‐2) and a sulfur content (70 wt%). A high areal capacity (≈3.3 mAh cm‐2) is demonstrated by using the novel cathode, which is crucial for the practical application of Li‐S batteries. It is believed that the important role of nitrogen doping promoted chemical adsorption can be extended for development of other high performance carbon‐sulfur composite cathodes for Li‐S batteries. The nitrogen‐doped mesoporous carbon material is found to chemically adsorb sulfur, and the related mechanism is revealed by experimental survey and density functional theory calculation. Taking full advantages of chemical adsorption of sulfur, MPNC‐S cathode delivered an excellent capacity retention (95% within 100 cycles), high Coulombic efficiency (>96%), as well as high areal capacity of above 3 mAh cm‐2.
2D graphitic carbon nitride (GCN) nanosheets have attracted tremendous attention in photocatalysis due to their many intriguing properties. However, the photocatalytic performance of GCN nanosheets is still restricted by the limited active sites and the serious aggregation during the photocatalytic process. Herein, a simple approach to produce holey GCN (HGCN) nanosheets with abundant in‐plane holes by thermally treating bulk GCN (BGCN) under an NH3 atmosphere is reported. These formed in‐plane holes not only endow GCN nanosheets with more exposed active edges and cross‐plane diffusion channels that greatly speed up mass and photogenerated charge transfer, but also provide numerous boundaries and thus decrease the aggregation. Compared to BGCN, the resultant HGCN has a much higher specific surface area of 196 m2 g−1, together with an enlarged bandgap of 2.95 eV. In addition, the HGCN is demonstrated to be self‐modified with carbon vacancies that make HGCN show much broader light absorption extending to the near‐infrared region, a higher donor density, and remarkably longer lifetime of charge carriers. As such, HGCN has a much higher photocatalytic hydrogen production rate of nearly 20 times the rate of BGCN. An efficient etching process, thermal treatment of bulk graphitic carbon nitride under NH3 atmosphere, has been developed to synthesize holey graphitic carbon nitride (HGCN) nanosheets. The resultant HGCN exhibits significantly improved photocatalytic hydrogen production performance under visible light.
Self‐supported electrodes comprising carbon fiber paper (CP) integrated with bifunctional nickel phosphide (Ni‐P) electrocatalysts are fabricated by electrodeposition of Ni on functionalized CP, followed by a convenient one‐step phosphorization treatment in phosphorus vapor at 500 °C. The as‐fabricated CP@Ni‐P electrode exhibits excellent electrocatalytic performance toward hydrogen evolution in both acidic and alkaline solutions, with only small overpotentials of 162 and 250 mV, respectively, attaining a cathodic current density of 100 mA cm−2. Furthermore, the CP@Ni‐P electrode also exhibits superior catalytic performance toward oxygen evolution reaction (OER). An exceptionally high OER current of 50.4 mA cm−2 is achieved at an overpotential of 0.3 V in 1.0 m KOH. The electrode can sustain 10 mA cm−2 for 180 h with only negligible degradation, showing outstanding durability. Detailed microstructural and compositional studies reveal that upon OER in alkaline solution the surface Ni‐P is transformed to NiO covered with a thin Ni(OH)x layer, forming a Ni‐P/NiO/Ni(OH)x heterojunction, which presumably enhances the electrocatalytic performance for OER. Given the well‐defined bifunctionality, a full alkaline electrolyzer is constructed using two identical CP@Ni‐P electrodes as cathode and anode, respectively, which can realize overall water splitting with efficiency as high as 91.0% at 10 mA cm−2 for 100 h. Overall water splitting is realized at a high efficiency (91.0% at 10 mA cm−2) with excellent stability and durability by an alkaline electrolyzer made from self‐supported carbon fiber paper electrodes integrated with bifunctional nickel phosphide catalysts. The self‐supported electrode exhibits superior electrocatalytic performance toward both hydrogen evolution and oxygen evolution reactions in alkaline medium.