The past decade has witnessed substantial advances in the synthesis of various electrode materials with three-dimensional (3D) ordered macroporous or mesoporous structures (the so-called “inverse ...opals”) for applications in electrochemical energy storage devices. This review summarizes recent advancements in 3D ordered porous (3DOP) electrode materials and their unusual electrochemical properties endowed by their intrinsic and geometric structures. The 3DOP electrode materials discussed here mainly include carbon materials, transition metal oxides (such as TiO2, SnO2, Co3O4, NiO, Fe2O3, V2O5, Cu2O, MnO2, and GeO2), transition metal dichalcogenides (such as MoS2 and WS2), elementary substances (such as Si, Ge, and Au), intercalation compounds (such as Li4Ti5O12, LiCoO2, LiMn2O4, LiFePO4), and conductive polymers (polypyrrole and polyaniline). Representative applications of these materials in Li ion batteries, aqueous rechargeable lithium batteries, Li-S batteries, Li-O2 batteries, and supercapacitors are presented. Particular focus is placed on how ordered porous structures influence the electrochemical performance of electrode materials. Additionally, we discuss research opportunities as well as the current challenges to facilitate further contributions to this emerging research frontier.Energy devices: Porous materials for better storageThree-dimensional ordered porous materials can improve the electrochemical storage of energy. Jing Wang and Yuping Wu from Nanjing Tech University, China and co-workers review the development of these materials for use as electrodes in devices such as batteries and supercapacitors. Three-dimensional ordered porous materials are created by inserting the desired raw material into a template made from an array of spheres. The spheres are removed to leave a hole-filled material ideal for storage. The authors describe how this ordered porous structure influences the electrochemical performance of electrodes made from elementary materials, transition metal oxides, conductive polymers, or carbon-based materials, among others. The challenges for the future are discussed, including developing a better fundamental understanding of charge transport, improving efficiency, scaling-up production, and lowering production costs.
Zinc–iodine aqueous batteries (ZIABs) are highly attractive for grid‐scale energy storage due to their high theoretical capacities, environmental friendliness, and intrinsic non‐flammability. ...However, because of the close redox potential of Zn stripping/platting and hydrogen evolution, slight overcharge of ZIABs would induce drastic side reactions, serious safety concerns, and battery failure. A novel type of stimulus‐responsive zinc–iodine aqueous battery (SR‐ZIAB) with fast overcharge self‐protection ability is demonstrated by employing a smart pH‐responsive electrolyte. Operando spectroelectrochemical characterizations reveal that the battery failure mechanism of ZIABs during overcharge arises from the increase of electrolyte pH induced by hydrogen evolution as well as the consequent irreversible formation of insulating ZnO at anode and soluble Zn(IO3)2 at cathode. Under overcharge conditions, the designed SR‐ZIABs can be rapidly switched off with capacity degrading to 6% of the initial capacity, thereby avoiding continuous battery damage. Importantly, SR‐ZIABs can be switched on with nearly 100% of capacity recovery by re‐adjusting the electrolyte pH. This work will inspire the development of aqueous Zn batteries with smart self‐protection ability in the overcharge state.
Integrating stimulus responses into rechargeable batteries shows potential to revolutionize energy storage for smart devices. A stimulus‐responsive Zn–I2 battery can be rapidly switched off with capacity degrading to 6% of the initial capacity under overcharge conditions, thereby preventing irreversible side reactions (including hydrogen generation and electrode degradation), battery failure, and relevant safety issues.
Conventional electric double-layer capacitors are energy storage devices with a high specific power and extended cycle life. However, the low energy content of this class of devices acts as a ...stumbling block to widespread adoption in the energy storage field. To circumvent the low-energy drawback of electric double-layer capacitors, here we report the assembly and testing of a hybrid device called electrocatalytic hydrogen gas capacitor containing a hydrogen gas negative electrode and a carbon-based positive electrode. This device operates using pH-universal aqueous electrolyte solutions (i.e., from 0 to 14) in a wide temperature range (i.e., from - 70 °C to 60 °C). In particular, we report specific energy and power of 45 Wh kg
and 458 W kg
(both values based on the electrodes' active materials mass), respectively, at 1 A g
and 25 °C with 9 M H
PO
electrolyte solution. The device also enables capacitance retention of 85% (final capacitance of about 114 F g
) after 100,000 cycles at 10 A g
and 25 °C with 1 M phosphate buffer electrolyte solution.
Anion and cation substitution is an effective way in modulating electrochemical properties of electrode materials to achieve enhanced performance. Herein, we report our finding in the fabrication of ...advanced binder-free supercapacitor electrodes of hierarchical anion- (phosphorus-) and cation- (zinc- and nickel-) substituted cobalt oxides (denoted as ZnNiCo-P) architectures assembled from nanosheets grown directly on Ni foam. In contrast to the reference Co-P systems, the as-prepared electrode manifests a markedly improved electrochemical performance with a high specific capacity of ~ 958 C g−1 at 1 A g−1 and an outstanding rate capability (787 C g−1 at 20 A g−1) due to its compositional and structural advantages. Density functional theory calculations confirm that the Co species partially replaced by Zn/Ni and O species by P can simultaneously improve the charge transfer behavior and facilitate the OH- adsorption and deprotonation/protonation reaction process. Moreover, an aqueous hybrid supercapacitor based on self-supported ZnNiCo-P nanosheet electrode demonstrates a high energy density of 60.1 Wh kg−1 at a power density of 960 W kg−1, along with a superior cycling performance (89% of initial specific capacitance after 8000 cycles at 10 A g−1 is retained). These findings offer insights into the rational design of transition metal compounds with multi-components and favorable architectures by manipulating the cations and anions of metal compounds for high-performance supercapacitors.
A high-performance mix-metal phosphide nanosheet electrode enables excellent capacity, rate capability, and cycle stability of hybrid supercapacitors. The electrode is composed of hierarchical Zn and Ni co-substituted Co phosphide nanosheet arrays grown on porous Ni foam. Display omitted
•Hierarchical ZnNiCo-P nanosheet arrays grown directly on Ni foam are constructed for the first time.•The resultant binder-free electrodes manifest outstanding electrochemical performances.•The synergetic contribution and structural features together contribute to outstanding electrochemical performance.•The assembled ZnNiCo-P//PPD-rGOs hybrid supercapacitor achieved a high energy density of 60.1 W h kg−1 at a power density of 960 W kg−1.
N-doped carbon hollow microspheres have been synthesized by a facile interfacial sol-gel coating process using resorcinol/formaldehyde as the carbon precursor and ethylenediamine (EDA) as both the ...base catalyst and nitrogen precursor. They possessed uniform size of ~ 120nm in diameter with porous shells as thin as ~ 10nm. The BET specific surface area and pore volume were measured to be 267m2g−1 and 1.2cm3g−1, respectively. The nitrogen doping of 8.23wt% in carbon matrix could be achieved without sacrificing the hollow spherical morphology. Density functional theory (DFT) calculation results clearly reveal that N-doping could significantly change the interaction sites and enhance the adsorption of PF6- ions towards carbon framework. Quasi-solid-state full sodium-ion capacitors employing the nanoporous disordered carbon nanoparticles and N-doped carbon hollow microspheres as the battery-type negative and supercapacitor-type positive electrodes with a Na+-conducting gel polymer electrolyte were demonstrated. The devices exhibit a comprehensive and superior electrochemical performance in terms of ultrahigh operating voltage of 4.4V, high energy density of 157Whkg−1 at 620Wkg−1, and prolonged cycling stability over 1000 cycles with ~ 70% of capacitance retention. Such outstanding performances suggest that the quasi-solid-state full sodium-ion capacitors could be potential safe and flexible electrochemical energy storage devices in the near future.
Display omitted
•N-doped carbon hollow microspheres were synthesized by a facile interfacial sol-gel coating process.•Quasi-solid-state full sodium-ion capacitors with a Na+-conducting gel polymer electrolyte were demonstrated.•The devices exhibit a comprehensive and superior electrochemical performance.
The development of Zn-free anodes to inhibit Zn dendrite formation and modulate high-capacity Zn batteries is highly applauded yet very challenging. Here, we design a robust two-dimensional ...antimony/antimony-zinc alloy heterostructured interface to regulate Zn plating. Benefiting from the stronger adsorption and homogeneous electric field distribution of the Sb/Sb
Zn
-heterostructured interface in Zn plating, the Zn anode enables an ultrahigh areal capacity of 200 mAh cm
with an overpotential of 112 mV and a Coulombic efficiency of 98.5%. An anode-free Zn-Br
battery using the Sb/Sb
Zn
-heterostructured interface@Cu anode shows an attractive energy density of 274 Wh kg
with a practical pouch cell energy density of 62 Wh kg
. The scaled-up Zn-Br
battery in a capacity of 500 mAh exhibits over 400 stable cycles. Further, the Zn-Br
battery module in an energy of 9 Wh (6 V, 1.5 Ah) is integrated with a photovoltaic panel to demonstrate the practical renewable energy storage capabilities. Our superior anode-free Zn batteries enabled by the heterostructured interface enlighten an arena towards large-scale energy storage applications.
Electrolytic MnO2/Zn batteries have attracted extensive attention for use in large-scale energy storage applications due to their low cost, high output voltage, safety, and environmental ...friendliness. However, the poor electrical conductivity of MnO2 limits its deposition and dissolution at large capacities, which leads to sluggish reaction kinetics and drastic capacity decay. Here, we report a theory-guided design principle for an electrolytic MnO2/Zn battery co-regulated with transition metal ions that has improved electrochemical performance in terms of deposition and stripping chemistries. We start with first-principles calculations to predict the electrolytic effects of regulating transition metal ions in the deposition/stripping chemistry of the MnO2 cathode. The results indicate that with the simultaneous incorporation of strongly electronegative Co and Ni, the MnO2 cathode tends to possess more active electron states, faster charge-transfer kinetics, and better electrical conductivity than either MnO2 regulated with Co or Ni on their own, or pristine MnO2; hence, this co-regulation is beneficial for the cathode solid/liquid MnO2/Mn2+ reactions. We then fabricate and demonstrate a novel Co2+ and Ni2+ co-regulated MnO2/Zn (Co–Ni–MnO2/Zn) battery that yields significantly better electrochemical performance, finding that the synergistic regulation of Co and Ni on MnO2 can significantly increase its intrinsic conductivity and achieve high rates and Coulombic efficiencies at large capacities. The aqueous Co–Ni–MnO2/Zn battery exhibits a high rate (10C, 100 mA cm–2), high Coulombic efficiency (91.89%), and excellent cycling stability (600 cycles without decay) at a large areal capacity of 10 mAh cm–2. Our proposed strategy of co-regulation with transition metal ions offers a versatile approach for improving the electrochemical performance of aqueous electrolytic MnO2/Zn batteries in large-scale energy storage applications.
An aqueous electrolytic MnO2/Zn battery is regulated by Ni2+ and Co2+ ions on the cathode Mn2+/MnO2 chemistry. The co-regulation of Ni2+ and Co2+ on the MnO2 cathode is able to improve the electrolytic effects and thus its deposition and stripping performance Display omitted
•Developing a transition metal ions co-regulated electrolytic MnO2/Zn battery.•The multi-active electron states and fast charge-transfer kinetics of Co-Ni-MnO2 are beneficial to MnO2/Mn2+ reactions.•The Co-Ni-MnO2/Zn battery exhibits a high Coulombic efficiency and excellent cycling stability at 10 mAh cm–2.•Providing new approaches toward high performance aqueous batteries for large-scale energy storage applications.
Severe dendrite growth and high‐level activity of the lithium metal anode lead to a short life span and poor safety, seriously hindering the practical applications of lithium metal batteries. With a ...trisalt electrolyte design, an F‐/N‐containing inorganics–rich solid electrolyte interphase on a lithium anode is constructed, which is electrochemically and thermally stable over long‐term cycles and safety abuse conditions. As a result, its Coulombic efficiency can be maintained over 98.98% for 400 cycles. An 85.0% capacity can be retained for coin‐type full cells with a 3.14 mAh cm−2 LiNi0.5Co0.2Mn0.3O2 cathode after 200 cycles and 1.0 Ah pouch‐type full cells with a 4.0 mAh cm−2 cathode after 72 cycles. During the thermal runaway tests of a cycled 1.0 Ah pouch cell, the onset and triggering temperatures were increased from 70.8 °C and 117.4 °C to 100.6 °C and 153.1 °C, respectively, indicating a greatly enhanced safety performance. This work gives novel insights into electrolyte and interface design, potentially paving the way for high‐energy‐density, long‐life‐span, and thermally safe lithium metal batteries.
An F‐/N‐containing inorganics‐rich solid electrolyte interphase is constructed, which is electrochemically and thermally stable during the long‐term cycles and safety abuse conditions. More than 6 times longer cycles compared with routine cells are achieved in 1.0 Ah pouch‐type cells. The onset and triggering temperatures during the thermal runaway are increased from 70.8 and 117.4 to 100.6 and 153.1 °C, respectively.
Sodium (Na)-ion capacitors possess higher energy density than supercapacitors and higher power density than Na-ion batteries. However, kinetic mismatches between fast capacitive charge storage on the ...cathode and sluggish battery-type reactions on the anode lead to a poor charge/discharge rate capability and insufficient power output of Na-ion capacitors. Thus, developing suitable anode materials for Na-ion capacitors is urgently desirable. This work demonstrates an electrochemically exfoliated graphite (EEG) anode with enhanced capacitive charge storage, greatly boosting the Na-ion reaction kinetics of co-intercalation. The EEG anode shows a high reversible capacity of 109 mAh g–1 and maintains a good capacity retention of 90% after 1000 cycles. The assembled Na-ion capacitor using the EEG anode can finish the charge/discharge process in less than 10 s, which achieves an ultrahigh power density of 17,500 W kg–1 with an energy density of 17 Wh kg–1. The high capacitive contributions at both the anode and cathode contribute to the fast rate capability and high power output of the fabricated Na-ion capacitors. This work will promote the development of ultrafast charging sodium-ion storage devices.
Electrochemical nitrogen reduction reaction is considered as an energy‐saving technology for artificial N2 fixation at ambient conditions. Here, the single Mo atom supported by the P‐vacancy defected ...BP monolayer is proved to be a promising single‐atom electrocatalyst for N2 fixation with a considerably small overpotential.
Catalytic reduction of molecular dinitrogen (N2) to ammonia (NH3) is one of the most important and challenging industrial reactions. Electrochemical reduction is considered as an energy‐saving technology for artificial ambient nitrogen fixation, which is emerging as an optimal potential sustainable strategy to substitute for the Haber–Bosch process. However, this process demands efficient catalysts for the N2 reduction reaction (NRR). Here, by means of first‐principles calculations, we systematically explored the potential electrocatalytic performance of single transition metal atoms (Pd, Ag, Rh, Cu, Ti, Mo, Mn, Zn, Fe, Co, Ru, and Pt) embedded in monolayer defective boron phosphide (TMs/BP) monolayer with a phosphorus monovacancy for ambient NH3 production. Among them, the Mo/BP exhibits the best catalytic performance for ambient reduction of N2 through the typical enzymatic and consecutive reaction pathways with an activation barrier of 0.68 eV, indicating that Mo/BP is an efficient catalyst for N2 fixation. We believe that this work could provide a new avenue of ambient NH3 synthesis by using the designed single‐atom electrocatalysts.
PDF
