Nonflammable Phosphate-Based Electrolyte for Safe and Stable Potassium Batteries Enabled by Optimized Solvation Effect.

Current potassium-ion batteries (PIBs) are limited in safety and lifetime owing to the lack of suitable electrolyte solutions. To address these issues, herein, we report an innovative non-flammable electrolyte design strategy that leverages an optimal moderate solvation phosphate-based solvent which strikes a balance between solvation capability and salt dissociation ability, leading to superior electrochemical performance. The formulated electrolyte simultaneously exhibits the advantages of low salt concentration (only 0.6 M), low viscosity, high ionic conductivity, high oxidative stability, and safety. Our electrolyte also promotes the formation of self-limiting inorganic-rich interphases at the anode surface, alongside robust cathode-electrolyte interphase on iron-based Prussian blue analogues, mitigating electrode/electrolyte side reactions and preventing Fe dissolution. Notably, the PIBs employing our electrolyte exhibit exceptional durability, with 80 % capacity retention after 2,000 cycles at high-voltage of 4.2 V in a coin cell. Impressively, in a larger scale pouch cell, it maintains over 81 % of its initial capacity after 1,400 cycles at 1 C-rate with high average Coulombic efficiency of 99.6 %. This work represents a significant advancement toward the realization of safe, sustainable, and high-performance PIBs.

Restructuring Electrolyte Solvation by a Partially and Weakly Solvating Cosolvent toward High-Performance Potassium-Ion Batteries.

Ether-based electrolytes are among the most important electrolytes for potassium-ion batteries (PIBs) due to their low polarization voltage and notable compatibility with potassium metal. However, their development is hindered by the strong binding between K+ and ether solvents, leading to [K+-solvent] cointercalation on graphite anodes. Herein, we propose a partially and weakly solvating electrolyte (PWSE) wherein the local solvation environment of the conventional 1,2-dimethoxyethane (DME)-based electrolyte is efficiently reconfigured by a partially and weakly solvating diethoxy methane (DEM) cosolvent. For the PWSE in particular, DEM partially participates in the solvation shell and weakens the chelation between K+ and DME, facilitating desolvation and suppressing cointercalation behavior. Notably, the solvation structure of the DME-based electrolyte is transformed into a more cation-anion-cluster-dominated structure, consequently promoting thin and stable solid-electrolyte interphase (SEI) generation. Benefiting from optimized solvation and SEI generation, the PWSE enables a graphite electrode with reversible K+ (de)intercalation (for over 1000 cycles) and K with reversible plating/stripping (the K||Cu cell with an average Coulombic efficiency of 98.72% over 400 cycles) and dendrite-free properties (the K||K cell operates over 1800 h). We demonstrate that rational PWSE design provides an approach to tailoring electrolytes toward stable PIBs.

Building Stable Solid-State Potassium Metal Batteries.

Solid-state potassium metal batteries (SPMBs) are promising candidates for the next generation of energy storage systems for their low cost, safety, and high energy density. However, full SPMBs are not yet reported due to the K dendrites, interfacial incompatibility, and limited availability of suitable solid-state electrolytes. Here, stable SPMBs using a new iodinated solid polymer electrolyte (ISPE) are presented. The functional ions reconstruct ion transport channels, providing efficient potassium ion transport. ISPE shows a combination of high ionic conductivity, superior interfacial compatibility, and electrochemical stability. In situ alloying and iodinated interlayer increase K metal compatibility for prolonged cycling with low polarization. Moreover, the ISPE enables SPMBs with Prussian blue cathode stable operation at a high voltage of 4.5 V, a superior rate capability, and long-term cycling over 3000 cycles (4.2 V vs K+/K) with an ultra-high coulombic efficiency of 99.94%. More importantly, a classic solid-state potassium metal pouch cell achieves 4.2 V stable cycling over 800 cycles with a high retention of 93.6%, presenting a new development strategy for secure and high-performance rechargeable solid-state potassium metal batteries.

Nonfluorinated Antisolvents for Ultrastable Potassium-Ion Batteries.

A robust interface between the electrode and electrolyte is essential for the long-term cyclability of potassium-ion batteries (PIBs). An effective strategy for achieving this objective is to enhance the formation of an anion-derived, robust, and stable solid-electrolyte interphase (SEI) via electrolyte structure engineering. Herein, inspired by the application of antisolvents in recrystallization, we propose a nonfluorinated antisolvent strategy to optimize the electrolyte solvation structure. In contrast to the conventional localized superconcentrated electrolyte introducing high-fluorinated ether solvent, the anion-cation interaction is considerably enhanced by introducing a certain amount of nonfluorinated antisolvent into a phosphate-based electrolyte, thereby promoting the formation of a thin and stable SEI to ensure excellent cycling performance of PIBs. Consequently, the nonfluorinated antisolvent electrolyte exhibits superior stability in the K||graphite cell (negligible capacity degradation after 1000 cycles) and long-term cycling in the K||K symmetric cell (>2200 h), as well as considerably improved oxidation stability. This study demonstrates the feasibility of optimized electrolyte engineering with a nonfluorinated antisolvent, providing an approach to realizing superior electrochemical energy storage systems in PIBs.

Superstable potassium metal batteries with a controllable internal electric field.

Stable potassium metal batteries (PMBs) are promising candidates for electrical energy storage due to their ability to reversibly store electrical energy at a low cost. However, dendritic growth and large volume changes hinder their practical application. Here, referring to the morphology and structure of a virus, a bionic virus-like-carbon microsphere (BVC) was designed as the anode host for a PMB. A BVC with a three-dimensional structure can not only control the electric field, which can suppress dendrite formation, but can also provide a larger space to accommodate the volume change during the cycle progress. The designed potassium (K) metal anode exhibits excellent cycle life and stability (during 1800 h of repeated plating/stripping of K at a current density of 0.1 mA cm-2, K-BVC can realize a very stable K metal anode with low voltage hysteresis). Stable cyclability and improved rate capability can be realized in a full cell using Prussian blue over 400 cycles. This research provides a new idea for the development of stable K metal anodes and may pave the way for the practical application of next-generation metal batteries.

DEM Study of the Motion Characteristics of Rice Particles in the Indented Cylinder Separator.

The precise separation of rice particles is an important step in rice processing. In this paper, discrete element simulations of the motion of rice particles of different integrity in an indented cylinder separator were carried out using numerical simulation methods. The effects of single factors (cylinder rotation rate, cylinder axial inclination angle, and collection trough inclination angle) on the motion trajectories of particles are investigated and the probability distribution functions of particles are obtained. The statistical method of Kullback-Leibler divergence is used to quantitatively evaluate the differences in the probability distribution functions of the escape angles of particles of different degrees of integrity. The purpose of this paper is to determine the optimum parameters for an indent cylinder separator by understanding the material cylinder separating process from particle scale and to provide a basis for the numerical design of a grain particle cylinder separators.

Facilitating Phase Evolution for a High-Energy-Efficiency, Low-Cost O3-Type NaxCu0.18Fe0.3Mn0.52O2 Sodium Ion Battery Cathode.

The phase transition and lattice parameter evolution of O3 structure commonly occurs in O3-type sodium ion battery (SIB) cathodes, which might enlarge the voltage hysteresis and lower the energy efficiency. Given that the cost is one of the issues discouraging the application of SIBs in large-scale energy storage, here we focus on Co/Ni-free NaxCu0.18Fe0.3Mn0.52O2 (x = 0.8, 0.85, 0.9) and propose a convenient strategy to reduce the voltage hysteresis. It is found that when the Na content is 0.8, the highest energy efficiency of 95.4% after activation is achieved (2.5-4.0 V, 50 mA g-1, the 50th cycle), in addition to a satisfactory capacity retention (about 0.056% decay per cycle). The further characterizations reveal that Na0.8Cu0.18Fe0.3Mn0.52O2 owns a gentle O3-P3 phase transition process and does not undergo O3 phase lattice parameter evolution. The key point lies in the attainability of the O3/P3 composite of the material. This work will provide a simple strategy for the rational design of O3-type cathodes with a high energy efficiency and might offer inspiration to search for layered oxides with a higher O3/P3 critical Na content through element adjustments.

Carbon Dots@rGO Paper as Freestanding and Flexible Potassium-Ion Batteries Anode.

Carbonaceous materials, especially with graphite-layers structure, as anode for potassium-ion batteries (PIBs), are the footstone for industrialization of PIBs. However, carbonaceous materials with graphite-layers structure usually suffer from poor cycle life and inferior stability, not to mention freestanding and flexible PIBs. Here, a freestanding and flexible 3D hybrid architecture by introducing carbon dots on the reduced graphene oxide surface (CDs@rGO) is synthesized as high performance PIBs anode. The CDs@rGO paper has efficient electron and ion transfer channels due to its unique structure, thus enhancing reaction kinetics. In addition, the CDs provide abundant defects and oxygen-containing functional groups, which can improve the electrochemical performance. This freestanding and flexible anode exhibits the high capacity of 310 mAh g-1 at 100 mA g-1, ultra-long cycle life (840 cycles with a capacity of 244 mAh g-1 at 200 mA g-1), and excellent rate performance (undergo six consecutive currents changing from 100 to 500 mA g-1, high capacity 185 mAh g-1 at 500 mA g-1), outperforming many existing carbonaceous PIB anodes. The results may provide a starting point for high-performance freestanding and flexible PIBs and promote the rapid development of next-generation flexible batteries.

Accessible COF-Based Functional Materials for Potassium-Ion Batteries and Aluminum Batteries.

The porous structure composed of non-metal elements of covalent organic frameworks (COFs) contributes to a large surface area and multifunction, rendering COFs a brilliant material for energy storage. Unfortunately, the low conductivity of most COFs limits their application in batteries. Herein, we fabricate COF-derived nitrogen-doped porous carbon (NPC) using nitrogen-rich COF-JLU2 as precursors by a simple carbonization for potassium-ion batteries (PIBs) and aluminum (Al) batteries for the first time. The computational results suggest that NPC has an enhanced conductivity and optimized electron density distribution. NPC could overcome the low conductivity of COF and thus further optimize its electrochemical performance in PIBs and Al batteries. It displays an excellent stability even after 2500 cycles (as the anode for PIBs) and 30000 cycles (as the cathode for Al batteries) with a high Coulombic efficiency. This fascinating study may be extended in other COFs for energy storage applications.

Rational Design of a Polyimide Cathode for a Stable and High-Rate Potassium-Ion Battery.

Potassium has similar chemical characteristics compared with lithium while it is more abundant and of low cost, resulting in widespread research attention on potassium-ion batteries (PIBs). Developing organic polymer cathodes has garnered extensive attention because of their merits of environmental friendship and structure diversity, while confronted with inferior cycle stability and low rate performance. In this paper, we utilize the low-cost graphite nanosheets to stabilize polyimide (PI@G) for PIBs. Additionally, the potassium storage mechanism of PI@G was further evaluated; the highly reversible chemical bonds (C═O) of PI@G are responsible to its long-term stability. Consequently, the PI@G exhibits a maximal capacity of 142 mA h g-1 at the current density of 100 mA g-1 and maintains a capacity of 118 mA h g-1 after 500 cycles (corresponding to a capacity fade of 0.034% per cycle). Moreover, the full battery based on the PI@G cathode also reveals promisingly electrochemical performance. This study may have great significance to the application prospect of the organic cathode for PIBs.

Sb-MOFs derived Sb nanoparticles@porous carbon for high performance potassium-ion batteries anode.

Reasonable design of Sb-based nanomaterials, which can alleviate volume expansion, agglomeration and pulverization, is meaningful for PIBs. We used Sb-MOFs as precursors to perfectly and controllably embed uniform Sb nanoparticles (∼19 nm) into porous carbon networks through simple carbonization strategies and achieved excellent electrochemical performance for PIBs.

Nature of Bimetallic Oxide Sb2MoO6/rGO Anode for High-Performance Potassium-Ion Batteries.

Potassium-ion batteries (KIBs) are one of the most appealing alternatives to lithium-ion batteries, particularly attractive in large-scale energy storage devices considering the more sufficient and lower cost supply of potassium resources in comparison with lithium. To achieve more competitive KIBs, it is necessary to search for anode materials with a high performance. Herein, the bimetallic oxide Sb2MoO6, with the presence of reduced graphene oxide, is reported as a high-performance anode material for KIBs in this study, achieving discharge capacities as high as 402 mAh g-1 at 100 mA g-1 and 381 mAh g-1 at 200 mA g-1, and reserving a capacity of 247 mAh g-1 after 100 cycles at a current density of 500 mA g-1. Meanwhile, the potassiation/depotassiation mechanism of this material is probed in-depth through the electrochemical characterization, operando X-ray diffraction, transmission electron microscope, and density functional theory calculation, successfully unraveling the nature of the high-performance anode and the functions of Sb and Mo in Sb2MoO6. More importantly, the phase development and bond breaking sequence of Sb2MoO6 are successfully identified, which is meaningful for the fundamental study of metal-oxide based electrode materials for KIBs.

Graphene Armored with a Crystal Carbon Shell for Ultrahigh-Performance Potassium Ion Batteries and Aluminum Batteries.

Graphene is of great significance in energy storage devices. However, a graphene-based electrode is difficult to use in direct applications due to the large surface area and flexibility, which leads to the excessive consumption of electrolyte, low Coulombic efficiency, and electrode shedding behaviors. Herein, a special crystal carbon@graphene microsphere (CCGM) composite was successfully synthesized. The scalable carbonaceous microsphere composite displays a small specific surface area and a superior structure stability. As a potassium ion battery electrode in a half-cell, CCGM delivers an initial capacity of 297.89 mAh g-1 with a high Coulombic efficiency of about 99%. It achieves an excellent cyclic stability with no capacity loss after 1250 cycles at the low current density of 100 mA g-1 with a long performing period of more than one year. As the cathode for an aluminum battery, a reversible specific capacity of 99.1 mAh g-1 at 1000 mA g-1 is obtained. CCGM delivers a long cycle performance of about 10 000 cycles at 4000 mA g-1 with a capacity retention of nearly 100%. Our design provides a fresh thought for the improvement of graphene-based materials, and it will greatly facilitate the application of graphene in the field of energy storage.

In Situ Alloying Strategy for Exceptional Potassium Ion Batteries.

We report an in situ alloying strategy for obtaining homogeneous (Bi,Sb) alloy nanoparticles from (Bi,Sb)2S3 nanotubes for the exceptional anode of potassium ion batteries (KIBs). The operando X-ray diffraction results, along with transmission electron microscopy and energy-dispersive X-ray spectroscopy mappings, successfully reveal the phase evolution of this material, which is (Bi,Sb)2S3 → (Bi,Sb) → K(Bi,Sb) → K3(Bi,Sb) during the initial discharge and K3(Bi,Sb) → K(Bi,Sb) → (Bi,Sb) in the charging process. The in situ alloying strategy produces a synergistic effect and brings an outstanding electrochemical performance. It achieves ultrahigh discharge capacities of 611 mAh g-1 at 100 mA g-1 (0.135C) and 300 mAh g-1 at 1000 mA g-1 (1.35C) and retains a capacity as high as 353 mAh g-1 after 1000 cycles at 500 mA g-1 (0.675C) with a Coulombic efficiency close to 100%. In addition, the KIBs full cell, which is composed of this anode and a perylenetetracarboxylic dianhydride cathode, reaches an initial discharge capacity as high as 276 mAh g-1 at 500 mA g-1 and maintains 207 mAh g-1 after 100 cycles.

Super long-life potassium-ion batteries based on an antimony@carbon composite anode.

A highly stable Sb based anode material of well-confined Sb@graphene@carbon (Sb@G@C) was developed for high performance PIBs. The Sb@G@C electrode exhibits a reversible capacity of 474 mA h g-1 at 100 mA g-1 (second charge), an outstanding long cycle stability over 800 cycles with a capacity retention as high as 72.3% and an excellent rate performance.

Carbon Nanoscrolls for Aluminum Battery.

This design provides a scalable route for in situ synthesizing of special carbon nanoscrolls as the cathode for an aluminum battery. The frizzy architectures are generated by a few graphene layers convoluting into the hollow carbon scroll, possessing rapid electronic transportation channels, superior anion storage capability, and outstanding ability of accommodating a large volume expansion during the cycling process. The electrochemical performance of the carbon nanoscroll cathode is fully tapped, displaying an excellent reversible discharge capacity of 104 mAh g-1 at 1000 mA g-1. After 55 000 cycles, this cathode retains a superior reversible specific capacity of 101.24 mAh g-1 at an ultrafast rate of 50 000 mA g-1, around 100% of the initial capacity, which demonstrates a superior electrochemical performance. In addition, anionic storage capability and structural stability are discussed in detail. The battery capacity under a wide temperature range from -80 to 120 °C is examined. At a low temperature of -25 °C, the battery delivers a discharge capacity of 62.83 mAh g-1 after 10 000 cycles, obtaining a capacity retention near 100%. In addition, it achieves a capacity of 99.5 mAh g-1 after 4000 cycles at a high temperature of 80 °C, with a capacity retention close to 100%. The carbon nanoscrolls possess an outstanding ultrafast charging/variable discharging rate performance surpassing all the batteries previously reported, which are highly promising for being applied in energy storage fields.

Graphene Nanoribbons on Highly Porous 3D Graphene for High-Capacity and Ultrastable Al-Ion Batteries.

Graphene nanoribbons on highly porous 3D graphene foam as the binder-free cathode for flexible Al-ion batteries exhibit low charge voltage, high capacity, excellent cycling ability (even after 10 000 cycles there is no capacity decay), and fast charging and slow discharging performance (the battery can be fully charged in 80 s and discharged in more than 3100 s).

Effect of pyrolysis temperature on the chemical oxidation stability of bamboo biochar.

Biochar produced by biomass pyrolysis has the advantage of carbon sequestration. However, some of the carbon atoms in biochar are not very stable. In this study, the effect of pyrolysis temperature on the chemical oxidation stability of bamboo biochar was investigated using the atomic ratios of H/C and O/C, Fourier transform infrared spectroscopy, and potassium dichromate (K2Cr2O7) oxidation spectrophotometric method. The results show that the carbon yield and ratios of H/C and O/C decreased from 71.72%, 0.71, and 0.32 to 38.48%, 0.22, and 0.06, respectively, as the temperature was increased from 300°C to 700°C. Moreover, the main oxygen-containing functional groups gradually decreased, while the degree of aromatization increased accordingly. The biochar showed a better stability at a higher pyrolysis temperature. The proportion of carbon loss, i.e., the amount of oxidized carbon with respect to the total carbon of the biochar, decreased from 16.52% to 6.69% with increasing temperature.

Super long-life supercapacitors based on the construction of nanohoneycomb-like strongly coupled CoMoO(4)-3D graphene hybrid electrodes.

Nanohoneycomb-like strongly coupled CoMoO4 -3D graphene hybird electrodes are synthesized for supercapacitors which exhibit excellent specific capacitance and superior long-term cycle stability. The supercapacitor device can power a 5 mm-diameter LED efficiently for more than 3 min with a charging time of only 2 s, and shows high energy densities and good cycle stability.

Synthesis of bacteria promoted reduced graphene oxide-nickel sulfide networks for advanced supercapacitors.

Supercapacitors with potential high power are useful and have attracted much attention recently. Graphene-based composites have been demonstrated to be promising electrode materials for supercapacitors with enhanced properties. To improve the performance of graphene-based composites further and realize their synthesis with large scale, we report a green approach to synthesize bacteria-reduced graphene oxide-nickel sulfide (BGNS) networks. By using Bacillus subtilis as spacers, we deposited reduced graphene oxide/Ni3S2 nanoparticle composites with submillimeter pores directly onto substrate by a binder-free electrostatic spray approach to form BGNS networks. Their electrochemical capacitor performance was evaluated. Compared with stacked reduced graphene oxide-nickel sulfide (GNS) prepared without the aid of bacteria, BGNS with unique nm-µm structure exhibited a higher specific capacitance of about 1424 F g(-1) at a current density of 0.75 A g(-1). About 67.5% of the capacitance was retained as the current density increased from 0.75 to 15 A g(-1). At a current density of 75 A g(-1), a specific capacitance of 406 F g(-1) could still remain. The results indicate that the reduced graphene oxide-nickel sulfide network promoted by bacteria is a promising electrode material for supercapacitors.