ABSTRACT
Considerable attention has been by far paid to stabilizing metallic Zn anodes, where side reactions and dendrite formation still remain detrimental to their practical advancement. Electrolyte modification or protected layer design is widely reported; nonetheless, an effective maneuver to synergize both tactics has been rarely explored. Herein, we propose a localized electrolyte optimization via the introduction of a dual-functional biomass modificator over the Zn anode. Instrumental characterization in conjunction with molecular dynamics simulation indicates local solvation structure transformation owing to the limitation of bound water with intermolecular hydrogen bonds, effectively suppressing hydrogen evolutions. Meanwhile, the optimized nucleation throughout the protein membrane allows uniform Zn deposition. Accordingly, the symmetric cell exhibits an elongated lifespan of 3280 h at 1.0 mA cm-2/1.0 mAh cm-2, while the capacity retention of the full cell sustains 91.1% after 2000 cycles at 5.0 A g-1. The localized electrolyte tailoring via protein membrane introduction might offer insights into operational metal anode protection.
ABSTRACT
Potassium metal battery is an appealing candidate for future energy storage. However, its application is plagued by the notorious dendrite proliferation at the anode side, which entails the formation of vulnerable solid electrolyte interphase (SEI) and non-uniform potassium deposition on the current collector. Here, this work reports a dual-modification design of aluminum current collector to render dendrite-free potassium anodes with favorable reversibility. This work achieves to modulate the electronic structure of the designed current collector and accordingly attain an SEI architecture with robust inorganic-rich constituents, which is evidenced by detailed cryo-EM inspection and X-ray depth profiling. The thus-produced SEI manages to expedite ionic conductivity and guide homogeneous potassium deposition. Compared to the potassium metal cells assembled using typical aluminum current collector, cells based on the designed current collector realize improved rate capability (maintaining 400 h under 50 mA cm-2 ) and low-temperature durability (stable operation at -50 °C). Moreover, scalable production of the current collector allows for the sustainable construction of high-safety potassium metal batteries, with the potential for reducing the manufacturing cost.
ABSTRACT
The rechargeable aqueous Zn ion battery (AZIB) is considered a promising candidate for future energy storage applications due to its intrinsic safety features and low cost. However, Zn dendrites and side reactions (e.g., corrosion, hydrogen evolution reaction, and inactive side product (Zn hydroxide sulfate) formation) at the Zn metal anode have been serious obstacles to realizing a satisfactory AZIB performance. The application of gel electrolytes is a common strategy for suppressing these problems, but the normally used highly cross-linked polymer matrix (e.g., polyacrylamide (PAM)) brings additional difficulties for battery assembly and recycling. Herein, we have developed a gel electrolyte for Zn metal anode stabilization, where a peptide matrix, a highly biocompatible material, is used for gel construction. Various experiments and simulations elucidate the sulfate anion-assisted self-assembly gel formation and its effect in stabilizing Zn metal anodes. Unlike polymer gel electrolytes, the peptide gel electrolyte can reversibly transform between gel and liquid states, thus facilitating the gel-involved battery assembly and recycling. Furthermore, the peptide gel electrolyte provides fast Zn ion diffusion (comparable to conventional liquid electrolyte) while suppressing side reactions and dendrite growth, thus achieving highly stable Zn metal anodes as validated in various cell configurations. We believe that our concept of gel electrolyte design will inspire more future directions for Zn metal anode protection based on gel electrolyte design.
ABSTRACT
Proton activity in electrolytes plays a crucial role in deciding the electrochemical performance of aqueous batteries. On the one hand, it can influence the capacity and rate performance of host materials because of the high redox activity of protons. On the other hand, it can also cause a severe hydrogen evolution reaction (HER) when the protons are aggregated near the electrode/electrolyte interface. The HER dramatically limits the potential window and the cycling stability of the electrodes. Therefore, it is critical to clarify the impact of electrolyte proton activity on the battery macro-electrochemical performance. In this work, using an aza-based covalent organic framework (COF) as a representative host material, we studied the effect of electrolyte proton activity on the potential window, storage capacity, rate performance, and cycle stability in various electrolytes. A tradeoff relationship between proton redox reactions and the HER in the COF host is revealed by utilizing various in situ and ex situ characterizations. Moreover, the origin of proton activity in near-neutral electrolytes is discussed in detail and is confirmed to be related to the hydrated water molecules in the first solvation shell. A detailed analysis of the charge storage process in the COFs is presented. These understandings can be of importance for utilizing the electrolyte proton activity to build high-energy aqueous batteries.
ABSTRACT
Carbonaceous materials are promising anodes for practical potassium-ion batteries, but fail to meet the requirements for durability and high capacities at low potentials. Herein, we constructed a durable carbon anode for high-energy-density K-ion full cells by a preferential pyrolysis strategy. Utilizing S and N volatilization from a π-π stacked supermolecule, the preferential pyrolysis process introduces low-potential active sites of sp2 hybridized carbon and carbon vacancies, endowing a low-potential "vacancy-adsorption/intercalation" mechanism. The as-prepared carbon anode exhibits a high capacity of 384.2â mAh g-1 (90 % capacity locates below 1â V vs. K/K+ ), which contributes to a high energy density of 163â Wh kg-1 of K-ion full battery. Moreover, abundant vacancies of carbon alleviate volume variation, boosting the cycling stability over 14 000â cycles (8400â h). Our work provides a new synthesis approach for durable carbon anodes of K-ion full cells with high energy densities.
ABSTRACT
Electrolyte design has become ever more important to enhance the performance of lithium-ion batteries (LIBs). However, the flammability issue and high reactivity of the conventional electrolytes remain a major problem, especially when the LIBs are operated at high voltage and extreme temperatures. Herein, we design a novel non-flammable fluorinated ester electrolyte that enables high cycling stability in wide-temperature variations (e.g., -50 °C-60 °C) and superior power capability (fast charge rates up to 5.0â C) for the graphite||LiNi0.8 Co0.1 Mn0.1 O2 (NCM811) battery at high voltage (i.e., >4.3â V vs. Li/Li+ ). Moreover, this work sheds new light on the dynamic evolution and interaction among the Li+ , solvent, and anion at the molecular level. By elucidating the fundamental relationship between the Li+ solvation structure and electrochemical performance, we can facilitate the development of high-safety and high-energy-density batteries operating in harsh conditions.
ABSTRACT
Metal-based anodes (Li, Zn, etc.) are regarded as promising solutions for next-generation advanced batteries due to their high theoretical specific capacities. However, most of these metal anodes suffer from dendrite growth, which severely restricts their practical applications. Recently, epitaxial anode metal deposition by choosing a suitable substrate has received tremendous attention as an effective strategy to suppress dendrites. However, the epitaxial relationship between plated metal and the substrate has been a subject of debate. Herein, large-area, mono-orientated 2D material (MoS2 ) is used, for the first time, to electrodeposit truly epitaxial Zn anodes. The continuous (without edges) mono-orientated MoS2 films are shown to be an effective strategy for suppressing metal dendrites. In addition, the epitaxial nature of the electrodeposited Zn anode is proven by pole figure analysis, which provides the first demonstration of truly epitaxial Zn anode growth over large area as metal anode protection strategy through epitaxy.
ABSTRACT
The popular metal-ion batteries (MIBs) suffer from environmental and economic issues because of their heavy dependency on nonrenewable metals. Here, we propose a metal-free ammonium (NH4 + )-based dual-ion battery with a record-breaking operation voltage of 2.75â V. The working mechanism of this sustainable battery involves the reversible anion (PF6 - ) intercalation chemistry in graphite cathode and NH4 + intercalation behavior in PTCDI (3,4,9,10-perylenetetracarboxylic diimide) anode. This new battery configuration successfully circumvented the reduction susceptibility of NH4 + and the lack of mature NH4 + -rich cathodes for NH4 + ion batteries (AIBs). The customized organic NH4 + electrolyte endows the graphite||PTCDI full battery with durable longevity (over 1000â cycles) and a high energy density (200â Wh kg-1 ). We show that the development of AIBs should be high-voltage-oriented while circumventing low operation potential to avoid NH4 + reduction.
ABSTRACT
Aqueous ammonium ion battery is a promising sustainable energy storage system. However, the side reactions originating from electrolytes (the water decomposition and host material dissolution) preclude its practical applications. Unlike the metal-based aqueous batteries, the idea of "ultrahigh concentrated electrolyte" is not feasible due to the strong hydrolysis of ammonium ions. Therefore, we propose an effective and sustainable strategy for the water hydrogen bond network modulation by adding sucrose into the electrolytes. The sucrose can form sucrose-water hydrogen bond networks to break the continuous water hydrogen bond network, thereby inhibiting water decomposition significantly. Moreover, the weak hydrogen bond interaction between ammonium and sucrose facilitates rapid ion migration, leading to an improved ionic conductivity. This work presents a new electrolyte modulating strategy for the practical application of aqueous ammonium ion batteries.
ABSTRACT
Sodium ion batteries (SIBs) are considered the most promising battery technology in the post-lithium era due to the abundant sodium reserves. In the past two decades, exploring new electrolytes for SIBs has generally relied on the "solid electrolyte interphase (SEI)" theory to optimize the electrolyte components. However, many observed phenomena cannot be fully explained by the SEI theory. Therefore, electrolyte solvation structure and electrode-electrolyte interface behavior have recently received tremendous research interest to explain the improved performance. Considering there is currently no review paper focusing on the solvation structure of electrolytes in SIBs, a systematic survey on SIBs is provided, in which the specific solvation structure design guidelines and their consequent impact on the electrochemical performance are elucidated. The key driving force of solvation structure formation, and the recent advances in adjusting SIB solvation structures are discussed in detail. It is believed that this review can provide new insights into the electrolyte optimization strategies of high-performance SIBs and even other emerging battery systems.
ABSTRACT
Energy harvesting modules play an increasingly important role in the development of autonomous self-powered microelectronic devices. MXenes (i.e., 2D transition metal carbide/nitride) have recently emerged as promising candidates for energy applications due to their excellent electronic conductivity, large specific surface area, and tunable properties. Herein, a perspective on using MXenes to harvest energy from various sources in the environment is presented. First, the characteristics of MXenes that facilitate energy capturing are systematically introduced and the preparation strategies of MXenes and their derived nanostructures tailored toward such applications are summarized. Subsequently, the harvesting mechanism of different energy sources (e.g., solar energy, thermoelectric energy, triboelectric energy, piezoelectric energy, salinity-gradient energy, electrokinetic energy, ultrasound energy, and humidity energy) are discussed. Then, the recent progress of MXene-based nanostructures in energy harvesting, as well as their applications, is introduced. Finally, opinions on the existing challenges and future directions of MXene-based nanostructure for energy harvesting are presented.
ABSTRACT
Aqueous zinc-ion batteries are regarded as ideal candidates for stationary energy-storage systems due to their low cost and high safety. However, zinc can readily grow into dendrites, leading to limited cycling performance and quick failure of the batteries. Herein, a novel strategy is proposed to mitigate this dendrite problem, in which a selectively polarized ferroelectric polymer material (poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE))) is employed as a surface protective layer on zinc anodes. Such a polarized ferroelectric polymer layer can enable a locally concentrated zinc-ion distribution along the coated surface and thus enable the horizontal growth of zinc plates. As a result, symmetrical zinc batteries using such anodes exhibit long cycling lifespan at 0.2 mA cm-2 , 0.2 mAh cm-2 for 2000 h, and a high rate performance up to 15 mA cm-2 . Also, the full cell (including a Zn-MnO2 battery and a zinc-ion capacitor) based on this anode is demonstrated. This work provides a novel strategy to protect the zinc anode and even other metal anodes exploiting polymer ferroelectricity.
ABSTRACT
Ammonium ions (NH4+), as non-metallic charge carriers, have spurred great research interest in the realm of aqueous batteries. Unfortunately, most inorganic host materials used in these batteries are still limited by the sluggish diffusion kinetics. Here, we report a unique hydrogen bond chemistry to employ covalent organic frameworks (COFs) for NH4+ ion storage, which achieves a high capacity of 220.4 mAh g-1 at a current density of 0.5 A g-1. Combining the theoretical simulation and materials analysis, a universal mechanism for the reaction of nitrogen and oxygen bridged by hydrogen bonds is revealed. In addition, we explain the solvation behavior of NH4+, leading to a relationship between redox potential and desolvation energy barrier. This work provides a new insight into NH4+ ion storage in host materials based on hydrogen bond chemistry. This mechanism can be leveraged to design and develop COFs for electrochemical energy storage.
ABSTRACT
Zinc metal anode has garnered a great deal of scientific and technological interest. Nevertheless, major bottlenecks restricting its large-scale utilization lie in the poor electrochemical stability and unsatisfactory cycling life. Herein, a Janus separator is developed via directly growing vertical graphene (VG) carpet on one side of commercial glass fiber separator throughout chemical vapor deposition. A simple air plasma treatment further renders the successful incorporation of oxygen and nitrogen heteroatoms on bare graphene. Thus-derived 3D VG scaffold affording large surface area and porous structure can be viewed as a continuation of planar zinc anode. In turn, the Janus separator harvests homogenous electric field distribution and lowered local current density at the interface of the anode/electrolyte, as well as harnesses favorable zincophilic feature for building-up uniform Zn ionic flux. Such a separator engineering enables an impressive rate and cycle performance (93% over 5000 cycles at 5 A g-1 ) for Zn-ion hybrid capacitors and outstanding energy density (182 Wh kg-1 ) for V2 O5 //Zn batteries, respectively. This strategy with large scalability and cost-effectiveness represents a universal route to protect prevailing metal anodes (Zn, Na, K) in rechargeable batteries.
ABSTRACT
3D printing technology has stimulated a burgeoning interest to fabricate customized architectures in a facile and scalable manner targeting wide ranged energy storage applications. Nevertheless, 3D-printed hybrid capacitor devices synergizing favorable energy/power density have not yet been explored thus far. Herein, we demonstrate a 3D-printed sodium-ion hybrid capacitor (SIC) based on nitrogen-doped MXene (N-Ti3C2Tx) anode and activated carbon cathode. N-Ti3C2Tx affording a well-defined porous structure and uniform nitrogen doping can be obtained via a sacrificial template method. Thus-formulated ink can be directly printed to form electrode architecture without the request of a conventional current collector. The 3D-printed SICs, with a large areal mass loading up to 15.2 mg cm-2, can harvest an areal energy/power density of 1.18 mWh cm-2/40.15 mW cm-2, outperforming the state-of-the-art 3D-printed energy storage devices. Furthermore, our SIC also achieves a gravimetric energy/power density of 101.6 Wh kg-1/3269 W kg-1. This work demonstrates that the 3D printing technology is versatile enough to construct emerging energy storage systems reconciling high energy and power density.
ABSTRACT
The template-confined synthesis strategy is a simple and effective methodology to prepare two-dimensional nanomaterials. It has multiple advantages including green process, controllable morphology and adjustable crystal structure, and therefore, it is promising in the energy storage realm to synthesize high-performance electrode materials. In this review, we summarize the recent advances in the template-confined synthesis of two-dimensional nanostructures for aqueous energy storage applications. The material design is discussed in detail to accommodate target usage in aqueous supercapacitors and zinc metal batteries. The remaining challenges and future prospective are also covered.
ABSTRACT
Wearable and portable self-powered units have stimulated considerable attention in both the scientific and technological realms. However, their innovative development is still limited by inefficient bulky connections between functional modules, incompatible energy storage systems with poor cycling stability, and real safety concerns. Herein, we demonstrate a flexible solar-charging integrated unit based on the design of printed magnesium ion aqueous asymmetric supercapacitors. This power unit exhibits excellent mechanical robustness, high photo-charging cycling stability (98.7% capacitance retention after 100 cycles), excellent overall energy conversion and storage efficiency (ηoverall = 17.57%), and outstanding input current tolerance. In addition, the Mg ion quasi-solid-state asymmetric supercapacitors show high energy density up to 13.1 mWh cm-3 via pseudocapacitive ion storage as investigated by an operando X-ray diffraction technique. The findings pave a practical route toward the design of future self-powered systems affording favorable safety, long life, and high energy.
ABSTRACT
Lithium-sulfur (Li-S) batteries are recognized as one of the most promising energy storage systems due to the high energy density and cost effectiveness. However, their practical implementation has still been handicapped due to notorious lithium polysulfide (LiPS) shuttle and depressed sulfur redox kinetics. It is therefore desirable to exploit key mediators synergizing electrical conductivity and electrocatalytic activity for the cathode. Herein, we report the employment of atmospheric pressure chemical vapor deposition to harness the efficient and controllable synthesis of metallic VTe2 over particulated MgO substrates, which has scarcely been demonstrated by conventional wet-chemical synthetic routes thus far. The thus-derived VTe2@MgO heterostructure as an efficient promotor enables effective regulation of LiPSs with respect to polysulfide capture/conversion and Li2S decomposition. As a result, a S/VTe2@MgO cathode with a sulfur loading of 1.6 mg cm-2 harvests long-term cyclability with a negligible capacity decay of 0.055% per cycle over 1000 cycles at 1.0 C. Even at a sulfur loading of 6.9 mg cm-2, the cathode still delivers electrochemical performances that can rival the state-of-the-art high-loading counterparts. Our work might offer a feasible solution for developing heterostructured promotors with multifunctionality and electrocatalytic activity for high-performance Li-S batteries.
ABSTRACT
Mass production of graphene powders affording high quality and environmental benignancy serves as a prerequisite for the practical usage of graphene in multiple energy storage applications. Herein, we exploit a salt-templated CVD approach to harness the direct synthesis of nitrogen-doped graphene (NG) nanosheets and related ink dispersions in a scalable, safe, efficient, and green fashion. Thus-fabricated NG accompanying large productivity, excellent electrical conductivity, and favorable solution processability possesses implications in printable energy storage devices. With the NG-based ink in hand, self-standing 3D architectures with programmable patterns can be directly printed over a myriad of substrates. Accordingly, both electrode preparation for flexible supercapacitors and separator modification in Li-S batteries can be enabled via printing by employing our NG-based composite inks. This work thus represents a practical route for mass production of graphene inks with cost-effectiveness and eco-friendliness for emerging energy storage technology.
ABSTRACT
An innovative photo-enhanced aqueous redox battery (PEARB) built upon a simple two-electrode configuration is demonstrated. The synergy of the photo-cathode and battery-anode is realized by directly growing vertically oriented SnS2 arrays on Ti mesh, manifesting advanced photo-electrocatalytic activities. The assembled PEARB achieves 2.5-fold capacity enhancement under solar illumination.