Unlocking High-Current Performance in Silicon Anode: Synergistic Phosphorus Doping and Nitrogen-Doped Carbon Encapsulation to Enhance Lithium Diffusivity.

The silicon (Si) offers enormous theoretical capacity as a lithium-ion battery (LIB) anode. However, the low charge mobility in Si particles hinders its application for high current loading. In this study, ball-milled phosphorus-doped Si nanoparticles encapsulated with nitrogen-doped carbon (P-Si@N-C) are employed as an anode for LIBs. P-doped Si nanoparticles are first obtained via ball-milling and calcination of Si with phosphoric acid. N-doped carbon encapsulation is then introduced via carbonization of the surfactant-assisted polymerization of pyrrole monomer on P-doped Si. While P dopant is required to support the stability at high current density, the encapsulation of Si particles with N-doped carbon is influential in enhancing the overall Li+ diffusivity of the Si anode. The combined approaches improve the anode's Li+ diffusivity up to tenfold compared to the untreated anode. It leads to exceptional anode stability at a high current, retaining 87 % of its initial capacity under a large current rate of 4000 mA g-1. The full-cell comprising P-Si@N-C anode and LiFePO4 cathode demonstrates 94 % capacity retention of its initial capacity after 100 cycles at 1 C. This study explores the effective strategies to improve Li+ diffusivity for high-rate Si-based anode.

Trifunctional electrocatalysts based on a bimetallic nanoalloy and nitrogen-doped carbon with brush-like heterostructure.

Trifunctional ORR/OER/HER catalysts are emerging for various sustainable energy storage and conversion technologies. For this function, employing materials with 1D structures leads to catalysts having limited surface area and structural robustness. Instead of 1D catalysts, heterostructured catalysts (i.e., catalysts consisting of interfaces created by combining diverse structural components) have attracted much attention due to their high efficiency. We have fabricated a directly grown 1D-1D heterostructured bimetallic N-doped carbon trifunctional catalyst based on Fe/Co bimetallic-organic frameworks, forming nanobrushes (FeCoNC-NB) with improved resistance to collapsing and substantial numbers of exposed active sites. The secondary 1D structure of this design contributes to creating interparticle conductive networks. By combining the brush-like heterostructure, FeCo alloy active sites, and N-doped carbon as support and for encapsulation of the metal, the catalyst features a high ORR Eonset value (1.046 V), low OER overpotential (363 mV), and comparable HER overpotential (254 mV) in alkaline electrolyte. Zn-air batteries with FeCoNC-NB demonstrate a power density of 195 mW cm-2 and a superior battery life of up to 350 h. Self-powered FeCoNC-NB-based water electrolyzers as energy conversion devices are also demonstrated. This work drives the progress of trifunctional catalysts based on heterostructured nonprecious metal N-doped carbon for energy storage and conversion developments.

Effect of the oxygen vacancy electronic state on Ni migration in Li0.5(Ni0.8Mn0.1Co0.1)O2 cathode material.

Cation migration coupled with oxygen vacancy formation is known to drive the layered to disordered spinel/rock-salt phase transformation in the high-Ni layered oxide cathodes of Li-ion batteries. However, the effect of different electronic states of oxygen vacancies on the cation migration still remains elusive. Here, we investigate Ni migration in delithiated Ni-rich Li0.5Ni0.8Mn0.1Co0.1O2 (hence Li0.5NMC811) in the presence of neutral and charged oxygen vacancies by means of first-principles density functional theory (DFT) calculations coupled with the nudged elastic band (NEB) method. We find that oxygen vacancies with neutral or +2 charge favor the Ni migration to Li tetrahedral and/or octahedral sites, both thermodynamically and kinetically. As for the case of +1 charged oxygen vacancies, while they thermodynamicaly favor the Ni migration to the Li site, the relatively high migration barrier suggests that they kinetically prohibit the Ni migration. Our results suggest that controlling the formation of oxygen vacancies is the key to enhancing the Ni-rich NMC structural stability in particular in their charged states.

Coordination engineering of atomically dispersed zirconium on graphene for the oxygen reduction reaction.

We study the effect of boron and sulfur doping on graphene with atomically dispersed zirconium as an electrocatalyst for the oxygen reduction reaction (ORR) by using density functional theory (DFT). The use of Zr as a metal center offers a highly stable catalyst due to the high electronegativity difference between Zr and its ligand. The origin of the ORR activity improvement has been investigated thoroughly. Here, we proposed a novel geometric descriptor for an atomically dispersed zirconium on a nitrogen-doped graphene catalyst with an axial oxygen ligand, which is the fractional coordination number of the Zr atom. We found that the fractional coordination number can successfully describe the shift of the dz2 band center in the doped compound, which is related to the binding energy of the Zr to the O ligand. We also found that the oxygen ligand is mobile during the adsorption process of ORR intermediates, and hence it is imperative for the axial oxygen ligand to bind neither too strongly nor too weakly to the Zr atom. The coordination engineering strategy can successfully enhance the ORR activity, shifting the ORR overpotential from 0.75 V and 0.92 V to 0.33 V and 0.32 V. This study provides new insights into the origin of ORR activity by connecting the novel geometric descriptor to the electronic structure and finally it is connected to the ORR activity.

Understanding SEI evolution during the cycling test of anode-free lithium-metal batteries with LiDFOB salt.

Anode-free lithium-metal batteries (AFLMBs) have the potential to double the energy density of Li-ion batteries, but face the challenges of mossy dendritic lithium plating and an unstable solid electrolyte interphase (SEI). Previous studies have shown that the AFLMBs with an electrolyte containing lithium difluoro(oxalato)borate (LiDFOB) salt outperform those with lithium hexafluorophosphate (LiPF6), but the mechanism behind this improvement is not fully understood. In this study, X-ray photoelectron spectroscopy (XPS) depth profile analysis and electrochemical impedance spectroscopy (EIS) were conducted to investigate the SEI on plated Li from the two conducting salts and their evolution in Cu‖NMC full cells during cycling. XPS results revealed that an inorganic-rich SEI layer is formed in the cell with LiDFOB-based electrolyte, with a low carbon/oxygen ratio of 0.56 compared to 1.42 in the LiPF6-based cell. With the inorganic-rich SEI, a dense electroplated Li with a shining surface on the Cu substrate can be retained after ten cycles. The inorganic-rich SEI enhances the reversibility of Li plating and stripping, with a high average CE of ∼98% and a stable charge/discharge voltage profile. The changes in SEI resistance and cathode electrolyte interphase resistance are more prominent compared to the changes in solution and charge transfer resistances, which further validate the role of the passivation films on Li deposits and NMC cathode surfaces in stabilizing AFLMB cycling performance.

A Free-Standing Polyaniline/Silicon Nanowire Forest as the Anode for Lithium-ion Batteries.

Despite its high theoretical capacity, silicon anode has limited intrinsic conductivity and experiences significant volume changes during charge-discharge. To overcome these issues, facile metal-assisted chemical etching and in-situ polymerization of aniline are employed to produce a dense 1D polyaniline/silicon nanowire forest without noticeable agglomeration as a free-standing anode for lithium-ion batteries. This hybrid electrode possesses high cycling performance, delivering a stable capacity capped at 2 mAh cm-2 for 346 cycles of charge-discharge. Maximum capacity of 2 mAh cm-2 is also achievable at high-rate cell testing of 2 mA cm-2 , which cannot be obtained by the anode with plain silicon wafer and silicon nanowire only. The introduction of polyaniline on the silicon nanowire is shown to reduce the solid electrolyte interface (SEI) resistance, stabilize the SEI layer, further alleviate the effect of volume changes, and boost the conductivity of the hybrid anode, resulting in the high electrochemical performance of the anode.

Vertically Aligned n-Type Silicon Nanowire Array as a Free-Standing Anode for Lithium-Ion Batteries.

Due to its high theoretical specific capacity, a silicon anode is one of the candidates for realizing high energy density lithium-ion batteries (LIBs). However, problems related to bulk silicon (e.g., low intrinsic conductivity and massive volume expansion) limit the performance of silicon anodes. In this work, to improve the performance of silicon anodes, a vertically aligned n-type silicon nanowire array (n-SiNW) was fabricated using a well-controlled, top-down nano-machining technique by combining photolithography and inductively coupled plasma reactive ion etching (ICP-RIE) at a cryogenic temperature. The array of nanowires ~1 µm in diameter and with the aspect ratio of ~10 was successfully prepared from commercial n-type silicon wafer. The half-cell LIB with free-standing n-SiNW electrode exhibited an initial Coulombic efficiency of 91.1%, which was higher than the battery with a blank n-silicon wafer electrode (i.e., 67.5%). Upon 100 cycles of stability testing at 0.06 mA cm-2, the battery with the n-SiNW electrode retained 85.9% of its 0.50 mAh cm-2 capacity after the pre-lithiation step, whereas its counterpart, the blank n-silicon wafer electrode, only maintained 61.4% of 0.21 mAh cm-2 capacity. Furthermore, 76.7% capacity retention can be obtained at a current density of 0.2 mA cm-2, showing the potential of n-SiNW anodes for high current density applications. This work presents an alternative method for facile, high precision, and high throughput patterning on a wafer-scale to obtain a high aspect ratio n-SiNW, and its application in LIBs.

Versatilely tuned vertical silicon nanowire arrays by cryogenic reactive ion etching as a lithium-ion battery anode.

Production of high-aspect-ratio silicon (Si) nanowire-based anode for lithium ion batteries is challenging particularly in terms of controlling wire property and geometry to improve the battery performance. This report demonstrates tunable optimization of inductively coupled plasma reactive ion etching (ICP-RIE) at cryogenic temperature to fabricate vertically-aligned silicon nanowire array anodes with high verticality, controllable morphology, and good homogeneity. Three different materials [i.e., photoresist, chromium (Cr), and silicon dioxide (SiO2)] were employed as masks during the subsequent photolithography and cryogenic ICP-RIE processes to investigate their effects on the resulting nanowire structures. Silicon nanowire arrays with a high aspect ratio of up to 22 can be achieved by tuning several etching parameters [i.e., temperature, oxygen/sulfur hexafluoride (O2/SF6) gas mixture ratio, chamber pressure, plasma density, and ion energy]. Higher compressive stress was revealed for longer Si wires by means of Raman spectroscopy. Moreover, an anisotropy of lattice stress was found at the top and sidewall of Si nanowire, indicating compressive and tensile stresses, respectively. From electrochemical characterization, half-cell battery integrating ICP-RIE-based silicon nanowire anode exhibits a capacity of 0.25 mAh cm-2 with 16.67% capacity fading until 20 cycles, which has to be improved for application in future energy storage devices.

Red Bean Pod Derived Heterostructure Carbon Decorated with Hollow Mixed Transition Metals as a Bifunctional Catalyst in Zn-Air Batteries.

Design and synthesis of low-cost and efficient bifunctional catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in Zn-air batteries are essential and challenging. We report a facile method to synthesize heterostructure carbon consisting of graphitic and amorphous carbon derived from the agricultural waste of red bean pods. The heterostructure carbon possesses a large surface area of 625.5 m2 g-1 , showing ORR onset potential of 0.89 V vs. RHE and OER overpotential of 470 mV at 5 mA cm-2 . Introducing hollow FeCo nanoparticles and nitrogen dopant improves the bifunctional catalytic activity of the carbon, delivering ORR onset potential of 0.93 V vs. RHE and OER overpotential of 360 mV. Electron energy-loss spectroscopy (EELS) O K-edge map suggests the presence of localized oxygen on the FeCo nanoparticles, suggesting the oxidation of the nanoparticles. Zn-air battery with these carbon-based catalysts exhibits a peak power density as high as 116.2 mW cm-2 and stable cycling performance over 210 discharge/charge cycles. This work contributes to the advancement of bifunctional oxygen electrocatalysts while converting agricultural waste into value-added material.

Facile synthesis of battery waste-derived graphene for transparent and conductive film application by an electrochemical exfoliation method.

One of the emerging challenges in tackling environmental issues is to treat electronic waste, with fast-growing battery waste as a notable threat to the environment. Proper recycling processes, particularly the conversion of waste to useful & value-added materials, are of great importance but not readily available. In this work, we report a facile and fast production of graphene from graphite extracted from spent Zn-C batteries. The graphene flakes are produced by electrochemically exfoliating graphite under varying DC voltages in poly(sodium 4-styrenesulfonate) (PSS) solution of different concentrations. The exfoliation takes place via the insertion of PSS into the interlayers of graphite to form C-S bonds as confirmed by FTIR and XPS studies. Under an applied voltage of 5 V and in 0.5 M PSS, high quality graphene flakes are obtained in a good yield, giving an I D/I G ratio of about 0.86 in Raman spectroscopy. The transparent conductive film prepared from the dispersion of high quality graphene flakes shows great promise due to its low sheet resistance (R s) of 1.1 kΩ sq-1 and high transmittance of 89%. This work illustrates an effective and low-cost method to realize large scale production of graphene from electronic waste.

Enhancing bifunctional catalytic activity of cobalt-nickel sulfide spinel nanocatalysts through transition metal doping and its application in secondary zinc-air batteries.

Developing large-scale and high-performance OER (oxygen evolution reaction) and ORR (oxygen reduction reaction) catalysts have been a challenge for commercializing secondary zinc-air batteries. In this work, transition metal-doped cobalt-nickel sulfide spinels are directly produced via a continuous hydrothermal flow synthesis (CHFS) approach. The nanosized cobalt-nickel sulfides are doped with Ag, Fe, Mn, Cr, V, and Ti and evaluated as bifunctional OER and ORR catalyst for Zn-air battery application. Among the doped spinel catalysts, Mn-doped cobalt-nickel sulfides (Ni1.29Co1.49Mn0.22S4) exhibit the most promising OER and ORR performance, showing an ORR onset potential of 0.9 V vs. RHE and an OER overpotential of 348 mV measured at 10 mA cm-2, which is attributed to their high surface area, electronic structure of the dopant species, and the synergistic coupling of the dopant species with the active host cations. The dopant ions primarily alter the host cation composition, with the Mn(iii) cation linked to the introduction of active sites by its favourable electronic structure. A power density of 75 mW cm-2 is achieved at a current density of 140 mA cm-2 for the zinc-air battery using the manganese-doped catalyst, a 12% improvement over the undoped cobalt-nickel sulfide and superior to that of the battery with a commercial RuO2 catalyst.

Flexible and Wearable All-Solid-State Al-Air Battery Based on Iron Carbide Encapsulated in Electrospun Porous Carbon Nanofibers.

In this work, electrospinning N-doped carbon nanofibers containing iron carbide (Fe3C@N-CFs) are synthesized and employed as the cathode in the flexible Al-air battery. Benefiting from the excellent catalytic activity of the iron carbide which is uniformly encapsulated in the N-doped carbon matrix, as well as the large specific surface area of the cross-linked network nanostructure, the as-prepared Fe3C@N-CFs show outstanding catalytic activity and stability toward oxygen reduction reaction. The as-fabricated all-solid-state Al-air batteries with Fe3C@N-CF catalyst show a stable discharge voltage (1.61 V) for 8 h, giving a capacity of 1287.3 mA h g-1.

Electrochemical energy storage devices for wearable technology: a rationale for materials selection and cell design.

Compatible energy storage devices that are able to withstand various mechanical deformations, while delivering their intended functions, are required in wearable technologies. This imposes constraints on the structural designs, materials selection, and miniaturization of the cells. To date, extensive efforts have been dedicated towards developing electrochemical energy storage devices for wearables, with a focus on incorporation of shape-conformable materials into mechanically robust designs that can be worn on the human body. In this review, we highlight the quantified performances of reported wearable electrochemical energy storage devices, as well as their micro-sized counterparts under specific mechanical deformations, which can be used as the benchmark for future studies in this field. A general introduction to the wearable technology, the development of the selection and synthesis of active materials, cell design approaches and device fabrications are discussed. It is followed by challenges and outlook toward the practical use of electrochemical energy storage devices for wearable applications.

One-Step Facile Synthesis of Cobalt Phosphides for Hydrogen Evolution Reaction Catalysts in Acidic and Alkaline Medium.

Catalysts for hydrogen evolution reaction are in demand to realize the efficient conversion of hydrogen via water electrolysis. In this work, cobalt phosphides were prepared using a one-step, scalable, and direct gas-solid phosphidation of commercially available cobalt salts. It was found that the effectiveness of the phosphidation reaction was closely related to the state of cobalt precursors at the reaction temperature. For instance, a high yield of cobalt phosphides obtained from the phosphidation of cobalt(II) acetate was related to the good stability of cobalt salt at the phosphidation temperature. On the other hand, easily oxidizable salts (e.g., cobalt(II) acetylacetonate) tended to produce a low amount of cobalt phosphides and a large content of metallic cobalt. The as-synthesized cobalt phosphides were in nanostructures with large catalytic surface areas. The catalyst prepared from phosphidation of cobalt(II) acetate exhibited an improved catalytic activity as compared to its counterpart derived from phosphidation of cobalt(II) acetylacetonate, showing an overpotential of 160 and 175 mV in acidic and alkaline electrolytes, respectively. Both catalysts also displayed an enhanced long-term stability, especially in the alkaline electrolyte. This study illustrates the direct phosphidation behavior of cobalt salts, which serve as a good vantage point in realizing the large-scale synthesis of transition-metal phosphides for high-performance electrocatalysts.

Hollow Co3 O4 Nanosphere Embedded in Carbon Arrays for Stable and Flexible Solid-State Zinc-Air Batteries.

Highly active and durable air cathodes to catalyze both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are urgently required for rechargeable metal-air batteries. In this work, an efficient bifunctional oxygen catalyst comprising hollow Co3 O4 nanospheres embedded in nitrogen-doped carbon nanowall arrays on flexible carbon cloth (NC-Co3 O4 /CC) is reported. The hierarchical structure is facilely derived from a metal-organic framework precursor. A carbon onion coating constrains the Kirkendall effect to promote the conversion of the Co nanoparticles into irregular hollow oxide nanospheres with a fine scale nanograin structure, which enables promising catalytic properties toward both OER and ORR. The integrated NC-Co3 O4 /CC can be used as an additive-free air cathode for flexible all-solid-state zinc-air batteries, which present high open circuit potential (1.44 V), high capacity (387.2 mAh g-1 , based on the total mass of Zn and catalysts), excellent cycling stability and mechanical flexibility, significantly outperforming Pt- and Ir-based zinc-air batteries.

NiMn layered double hydroxides as efficient electrocatalysts for the oxygen evolution reaction and their application in rechargeable Zn-air batteries.

High performance catalysts for the oxygen evolution reaction (OER) are in demand to improve the re-chargeability of Zn-air batteries. In this work, atomically dispersed NiMn layered double hydroxides are prepared via simple hydrothermal synthesis and tested as the OER catalyst in rechargeable Zn-air batteries. NiMn layered double hydroxides with the optimized Ni : Mn molar feeding ratio have good crystallinity, big interlayer spacing, and large surface area, which are beneficial to enhance their catalytic activity. They are highly active and stable during the OER, showing an overpotential of 0.35 V, a Tafel slope of 40 mV dec-1, and remarkable stability during 16 h of a chronopotentiometry test. Rechargeable Zn-air batteries with NiMn layered double hydroxides as the OER catalyst exhibit a low charge voltage of ≈2 V which is stable for up to 200 cycles. This study illustrates a platform to enhance the catalytic activity of the OER catalyst via fine-tuning the composition and physical properties of the materials and their application for rechargeable metal-air batteries.

Manganese Oxide Catalyst Grown on Carbon Paper as an Air Cathode for High-Performance Rechargeable Zinc-Air Batteries.

Manganese oxide is grown directly on carbon paper through a simple immersion process, and used as a catalyst-modified air cathode for rechargeable zinc-air batteries. The manganese oxide is distributed evenly within the porous carbon paper, which promotes a rapid three-phase reaction and high utilization of the active materials. Zinc-air batteries with the manganese oxide catalyst directly grown on the carbon paper exhibit improved performance compared with zinc-air batteries fabricated by using manganese oxide powder catalyst coated on carbon paper. The directly grown catalyst reduces the contact resistance and enhances the discharge/charge profile of the zinc-air batteries. Zinc-air batteries with the directly grown catalyst show a discharge voltage of 1.2 V at a current density of 15 mA cm-2 and deliver a power density as high as 108 mW cm-2 at an applied current of 168 mA cm-2 . Furthermore, good cycling stability for up to 500 cycles is achievable during continuous discharge-charge tests without the need to replace the zinc anode or replenish the electrolyte; this outperforms most currently available bifunctional catalysts for rechargeable zinc-air batteries. This study illustrates a promising platform to enhance the cycle life of rechargeable metal-air batteries.

Insights on the fundamental capacitive behavior: a case study of MnO2.

In this work, an insightful study on the fundamental capacitive behavior of MnO2 based electrodes is carried out using MnO2 hierarchical spheres (MHSs) and MnO2 nanoneedles (MNs) as examples. An overall understanding of the relationship between the capacitive performance and the electrode configuration as well as the morphology of active material, loading density, porosity of electrode, and electrolyte concentration is investigated comprehensively. Our analyses show that MnO2 with thin structure is of advantage to increase the utility of active material and to deliver higher specific capacitance, as the faradic reaction happens at/near the surface. Creation of an efficient path for the transport of electrons and ions is crucial to achieve high rate capabilities. Cycling stability could be improved by suppressing the side reaction. It is also important to shed light on the charge contribution from a graphite paper (GP) substrate since it may cause a misinterpretation of the capacitive behavior. This study provides a comprehensive understanding on the fundamental capacitive behavior of MnO2 based electrodes and gives useful clues for designing high performance supercapacitors.

Nickel cobalt oxide nanowire-reduced graphite oxide composite material and its application for high performance supercapacitor electrode material.

In this paper, we report a facile synthesis method of mesoporous nickel cobalt oxide (NiCo2O4) nanowire-reduced graphite oxide (rGO) composite material by urea induced hydrolysis reaction, followed by sintering at 300 degrees C. P123 was used to stabilize the GO during synthesis, which resulted in a uniform coating of NiCo2O4 nanowire on rGO sheet. The growth mechanism of the composite material is discussed in detail. The NiCo2O4-rGO composite material showed an outstanding electrochemical performance of 873 F g(-1) at 0.5 A g(-1) and 512 F g(-1) at 40 A g(-1). This method provides a promising approach towards low cost and large scale production of supercapacitor electrode material.

Large areal mass, flexible and free-standing reduced graphene oxide/manganese dioxide paper for asymmetric supercapacitor device.

Well-separated RGO sheets decorated with MnO2 nanoparticles facilitate easy access of the electrolyte ions to the high surface area of the paper electrode, enabling the fabrication of a thicker electrode with heavier areal mass and higher areal capacitance (up to 897 mF cm(-2) ). The electrochemical performance of the bent asymmetric device with a total active mass of 15 mg remains similar to the one in the flat configuration, demonstrating good mechanical robustness of the device.