In Situ Defect Engineering in Carbon by Atomic Self-Activation to Boost the Accessible Low-Voltage Insertion for Advanced Potassium-Ion Full-Cells.

Enhancing the low-potential capacity of anode materials is significant in boosting the operating voltage of full-cells and constructing high energy-density energy storage devices. Graphitic carbons exhibit outstanding low-potential potassium storage performance, but show a low K+ diffusion kinetics. Herein, in situ defect engineering in graphitic nanocarbon is achieved by an atomic self-activation strategy to boost the accessible low-voltage insertion. Graphitic carbon layers grow on nanoscale-nickel to form the graphitic nanosphere with short-range ordered microcrystalline due to nickel graphitization catalyst. Meanwhile, the widely distributed K+ in the precursor induces the activation of surrounding carbon atoms to in situ generate carbon vacancies as channels. The graphite microcrystals with defect channels realize reversible K+ intercalation at low-potential and accessible ion diffusion kinetics, contributing to high reversible capacity (209 mAh g-1 at 0.05 A g-1 under 0.8 V) and rate capacity (103.2 mAh g-1 at 1 A g-1). The full-cell with Prussian blue cathode and graphitic nanocarbon anode maintains an obvious working platform at ca. 3.0 V. This work provides a strategy for the in situ design of carbon anode materials and gives insights into the potassium storage mechanism at low-potential for high-performance full-cells.

Recent advances in in situ and operando characterization techniques for Li7La3Zr2O12-based solid-state lithium batteries.

Li7La3Zr2O12 (LLZO)-based solid-state Li batteries (SSLBs) have emerged as one of the most promising energy storage systems due to the potential advantages of solid-state electrolytes (SSEs), such as ionic conductivity, mechanical strength, chemical stability and electrochemical stability. However, there remain several scientific and technical obstacles that need to be tackled before they can be commercialised. The main issues include the degradation and deterioration of SSEs and electrode materials, ambiguity in the Li+ migration routes in SSEs, and interface compatibility between SSEs and electrodes during the charging and discharging processes. Using conventional ex situ characterization techniques to unravel the reasons that lead to these adverse results often requires disassembly of the battery after operation. The sample may be contaminated during the disassembly process, resulting in changes in the material properties within the battery. In contrast, in situ/operando characterization techniques can capture dynamic information during cycling, enabling real-time monitoring of batteries. Therefore, in this review, we briefly illustrate the key challenges currently faced by LLZO-based SSLBs, review recent efforts to study LLZO-based SSLBs using various in situ/operando microscopy and spectroscopy techniques, and elaborate on the capabilities and limitations of these in situ/operando techniques. This review paper not only presents the current challenges but also outlines future developmental prospects for the practical implementation of LLZO-based SSLBs. By identifying and addressing the remaining challenges, this review aims to enhance the comprehensive understanding of LLZO-based SSLBs. Additionally, in situ/operando characterization techniques are highlighted as a promising avenue for future research. The findings presented here can serve as a reference for battery research and provide valuable insights for the development of different types of solid-state batteries.

Ion Transport and Electrochemical Reaction in LiNi0.5Co0.2Mn0.3O2-Based High Energy/Power Lithium-Ion Batteries.

The high energy/power lithium-ion battery using LiNi0.5Co0.2Mn0.3O2 (NCM523 HEP LIB) has an excellent trade-off between specific capacity, cost, and stable thermal characteristics. However, it still brings a massive challenge for power improvement under low temperatures. Deeply understanding the electrode interface reaction mechanism is crucial to solving this problem. This work studies the impedance spectrum characteristics of commercial symmetric batteries under different states of charge (SOCs) and temperatures. The changing tendencies of the Li+ diffusion resistance Rion and charge transfer resistance Rct with temperature and SOC are explored. Moreover, one quantitative parameter, § ≡ Rct/Rion, is introduced to identify the boundary conditions of the rate control step inside the porous electrode. This work points out the direction to design and improve performance for commercial HEP LIB with common temperature and charging range of users.

Dual stabilization in potassium Prussian blue and cathode/electrolyte interface enables advanced potassium-ion full-cells.

Potassium Prussian Blue (KPB) have been investigated as promising cathode materials for potassium-ion batteries. However, numerous structure defects and side reactions at electrode/electrolyte interface will deteriorate the electrochemical properties. Herein, dual stabilization strategy of structure of KPB particles and cathode/electrolyte interface is reported to enhance the capacity and electrochemical stability. The structure of KPB is stabilized through inhibiting nucleation and growth by addition of ethylenediaminetetraacetic acid dipotassium salt during co-precipitation, which can enlarge the particle size. Meanwhile, stabilizing the cathode/electrolyte interface via changing potassium hexafluorophosphate to potassium bis (fluorosulfonyl) imide (KFSI) electrolyte can further reduce side reactions to boost the coulombic efficiency of KPB cathode. Benefiting from dual engineering in structure of KPB and cathode/electrolyte interface, the half-cell in KFSI electrolyte possesses two discharge potential plateaus at 3.4 and 4.0 V with reversible capacity of 92.7 mAh g-1 at 0.03 A g-1. To demonstrate its practical use, KPB//graphite full-cell device is successfully constructed, exhibiting the capacity up to 102.4 mAh g-1 at 0.1 A g-1, high-rate (40.4 mAh g-1 at 1.5 A g-1) and superior cyclic stability (88% capacity retention from cycle 25 to 400 at 1 A g-1). This work provides a synergetic engineering strategy to realize the powerful application of high-performance potassium-ion full-cell devices in energy storage.

Morphology control and interface characteristics of well-dispersed nanomaterials in K-ion batteries.

Potassium ion batteries (KIBs), the working mechanism of which is similar to that of lithium-ion batteries (LIBs), have drawn much interest as power sources for large-scale grid energy storage because of their low cost and abundant resources. In this paper, the feasibility of KMnF3 as a cathode material for KIBs, the optimization of synthesis conditions and the interface characteristics of the charge and discharge process have been studied in detail. The study of interface characteristics is mainly done through the non-destructive test of electrochemical impedance spectroscopy (EIS).

Enhancing the Cycling Stability by Tuning the Chemical Bonding between Phosphorus and Carbon Nanotubes for Potassium-Ion Battery Anodes.

Phosphorus/carbon (P/C) composites as promising potassium-ion storage materials have been extensively investigated for its compound superiorities of high specific capacity and favorable electronic conductivity. However, the effects of different chemical bonding states between P and the carbon matrix for potassium-ion storage and cycling performance still need to be investigated. Herein, three P/C composites with different chemical bonding states were successfully fabricated through simply ball-milling red P with carboxylic group carbon nanotubes (CGCNTs), carbon nanotubes (CNTs), and reduced carboxylic group carbon nanotubes (RCGCNTs), respectively. When used as potassium-ion battery (PIB) anodes, the red P and CGCNT (P-CGCNT) composite deliver the most outstanding cycling stability (402.6 mAh g-1 over 110 cycles) with a favorable capacity retention of 68.26% at a current density of 0.1 A g-1, much higher than that of the phosphorus-CNT (P-CNT) composite (297.5 mAh g-1 and 50.40%). Based on the results of X-ray photoelectron spectroscopy and electrochemical performance, we propose that the existence of a carboxyl functional group will be instrumental for the formation of the P-O-C bond. More importantly, when compared with the P-C bond, the P-O-C bond can lead to a higher reversible capacity and a better long-term cycling stability as a result of the more robust bonding energy of the P-O-C bond (585 KJ mol-1) than that of the P-C bond (264 kJ mol-1). This work provides some insights into designing high-performance P anodes for PIBs.

Undercooling-directed NaCl crystallization: an approach towards nanocavity-linked graphene networks for fast lithium and sodium storage.

Despite the crystallization of inorganic salt is being technologically related to the fabrication of salt-templated materials, the two key steps, nucleation and crystal growth, still lack the kinetic control to enable precise design of salt scaffolds. Here, we study how the undercooling degree controls the construction of salt scaffolds by kinetically manipulating the nucleation and growth rates in a NaCl-F127-rhodanine system. An effective approach based on undercooling-directed NaCl crystallization is further proposed to tailor the morphology and structure of the carbon materials. Under different undercooling conditions (liquid nitrogen, -55 °C and -25 °C freezing), the salt scaffold can be tuned as spheroidal particles, ellipsoidal nanocrystal aggregates and cubic nanocrystals with round corners, respectively. Correspondingly, hollow carbon nanospheres, nanocavity-linked graphene networks (CGN) and graphene nanosheets (GNS) can be fabricated through a salt template method, respectively. The Li+ and Na+ storage mechanisms of 3D CGN and 2D GNS are discussed, focusing on the ion diffusion kinetics. The enhanced Li+ diffusion kinetics in the 3D interconnected network endows CGN with better rate performance than GNS as lithium-ion battery anode material, and Na+ adsorption dominates the Na+ storage in CGN as sodium-ion battery anode material. Our findings provide a general idea for the construction crystallization-induced architectures and offer valuable insights to achieve fast Li+/Na+ storage by boosting the ion diffusion kinetics.

Scalable Synthesis Nano-Perovskite K(Mn0.95Ni0.05)F3 Cathode by Homogeneous Precipitation Method for Potassium-Ion Batteries.

Potassium-ion batteries (KIBs) are favored by researchers because of the unique advantages. In this work, KIB cathode material nano-perovskite K(Mn0.95Ni0.05)F3 with concentration gradient was synthesized by EDTA-assisted homogeneous precipitation method for the first time and characterized. The solid solution material was deposited on the multi-walled carbon nanotubes (MWCNTs) to form K(Mn0.95Ni0.05)F3/MWCNT nanocomposites to improve the electron conductivity of the electrode material so as to obtain the excellent electrochemical performance. As expected, the charge and discharge capacities of K(Mn0.95Ni0.05)F3/MWCNTs after the 60th cycle can still reach 106.8 and 98.5 mAh g-1 over the voltage range 4.2-1.2 V vs. K/K+ at the current density of 35 mA g-1, respectively. Electrochemical performance studies showed that solid solution K(Mn0.95Ni0.05)F3 had the potential applications as the cathode material for KIBs. Electrochemical impedance spectroscopy (EIS) was used to study the transport and reaction processes of ions at the solid-liquid interface. The main factors affecting electrochemical performance could be analyzed from the Nyquist plot of the EIS test.

Nitrogen/Oxygen Co-Doped Hierarchically Porous Carbon for High-Performance Potassium Storage.

Although the insertion of potassium ions into graphite has been proven to be realistic, the electrochemical performance of potassium-ion batteries (PIBs) is not yet satisfactory. Therefore, more effort is required to improve the specific capabilities and achieve a long cycling life. The mild carbonization process in molten salt (NaCl-KCl) is used to synthesize nitrogen/oxygen co-doped hierarchically porous carbon (NOPC) for PIBs by using cyanobacteria as the carbon source. This exhibits highly reversible capacities and ultra-long cycling stability, retaining a capacity of 266 mA h g-1 at 50 mA g-1 (100 cycles) and presents a capacity of 104.3 mA h g-1 at 1000 mA g-1 (1000 cycles). Kinetics analysis reveals that the potassium ion (K+ ) storage of NOPC is controlled by a capacitive process, which plays a crucial role in the excellent rate performance and superior reversible ability. The high proportion of capacitive behavior can be ascribed to the hierarchically porous structure and improved conductivity resulting from nitrogen and oxygen doping. Furthermore, density functional theory (DFT) calculations theoretically validate the enhanced potassium storage effect of the as-obtained NOPC. More importantly, the route to NOPC from cyanobacteria in molten salt provides a green approach to the synthesis of porous carbon materials.

Phosphorus Particles Embedded in Reduced Graphene Oxide Matrix to Enhance Capacity and Rate Capability for Capacitive Potassium-Ion Storage.

Early studies indicate that graphite is feasible as the negative electrode of a potassium-ion battery, but its electrochemical performance still cannot meet the demands of applications. More efforts should be focused on increasing the specific capacity and improving the rate capability in the meantime. Thus, stainless-steel autoclave technology has been utilized to prepare phosphorus nanoparticles encapsulated in reduced graphene oxide matrix as the electrode materials for a potassium-ion battery. As a result, the composite matrix affords high reversible capacities of 354 and 253 mA h g-1 at 100 and 500 mA g-1 , respectively. The superior electrochemical performance is mainly because the composite matrix possesses better electronic conductivity and a robust structure, which can promote the electron-transfer performance of the electrode. Furthermore, phosphorus particles can contribute to the high capacity through an alloying mechanism. In addition, the silklike, ultrathin, film composite with a high surface area is conducive to capacitive potassium-ion storage, which plays a more important role in rate performance and a high current density capability.

Fast Diffusion of O2 on Nitrogen-Doped Graphene to Enhance Oxygen Reduction and Its Application for High-Rate Zn-Air Batteries.

N-doped graphene (NDG) was investigated for oxygen reduction reaction (ORR) and used as air-electrode catalyst for Zn-air batteries. Electrochemical results revealed a slightly lower kinetic activity but a much larger rate capability for the NDG than commercial 20% Pt/C catalyst. The maximum power density for a Zn-air cell with NDG air cathode reached up to 218 mW cm-2, which is nearly 1.5 times that of its counterpart with the Pt/C (155 mW cm-2). The equivalent diffusion coefficient (DE) of oxygen from electrolyte solution to the reactive sites of NDG was evaluated as about 1.5 times the liquid-phase diffusion coefficient (DL) of oxygen within bulk electrolyte solution. Combined with experiments and ab initio calculations, this seems counterintuitive reverse ORR of NDG versus Pt/C can be rationalized by a spontaneous adsorption and fast solid-state diffusion of O2 on ultralarge graphene surface of NDG to enhance effective ORR on N-doped-catalytic-centers and to achieve high-rate performance for Zn-air batteries.

Cascading Boost Effect on the Capacity of Nitrogen-Doped Graphene Sheets for Li- and Na-Ion Batteries.

Specific capacity and cyclic performance are critically important for the electrode materials of rechargeable batteries. Herein, a capacity boost effect of Li- and Na-ion batteries was presented and clarified by nitrogen-doped graphene sheets. The reversible capacities progressively increased from 637.4 to 1050.4 mAh g-1 (164.8% increase) in Li-ion cell tests from 20 to 185 cycles, and from 187.3 to 247.5 mAh g-1 (132.1% increase) in Na-ion cell tests from 50 to 500 cycles. The mechanism of the capacity boost is proposed as an electrochemical induced cascading evolution of graphitic N to pyridinic and/or pyrrolic N, during which only these graphitic N adjacent pyridinic or pyrrolic structures can be taken precedence. The original and new generated pyridinic and pyrrolic N have strengthened binding energies to Li/Na atoms, thus increased the Li/Na coverage and delivered a progressive capacity boost with cycles until the entire favorable graphitic N transform into pyridinic and pyrrolic N.

Direct Synthesis of Few-Layer F-Doped Graphene Foam and Its Lithium/Potassium Storage Properties.

Heteroatom-doped graphene is considered a potential electrode materials for lithium-ion batteries (LIBs). However, potassium-ion batteries (PIBs) systems are possible alternatives due to the comparatively higher abundance. Here, a practical solid-state method is described for the preparation of few-layer F-doped graphene foam (FFGF) with thickness of about 4 nm and high surface area (874 m(2)g(-1)). As anode material for LIBs, FFGF exhibits 800 mAh·g(-1) after 50 cycles at a current density of 100 mA·g(-1) and 555 mAh·g(-1) after 100 cycles at 200 mA·g(-1) as well as remarkable rate capability. FFGF also shows 165.9 mAh·g(-1) at 500 mA·g(-1) for 200 cycles for PIBs. Research suggests that the multiple synergistic effects of the F-modification, high surface area, and mesoporous membrane structures endow the ions and electrons throughout the electrode matrix with fast transportation as well as offering sufficient active sites for lithium and potassium storage, resulting in excellent electrochemical performance. Furthermore, the insights obtained will be of benefit to the design of reasonable electrode materials for alkali metal ion batteries.

γ-Fe2O3 Nanocrystalline Microspheres with Hybrid Behavior of Battery-Supercapacitor for Superior Lithium Storage.

Maghemite (γ-Fe2O3) nanocrystalline microspheres (MNMs) self-assembled with 52 nm nanocrystals bridged with FeOOH around grain boundaries were formed by solvothermal reaction and thermal oxidation. The unique architecture endows the MNMs with the lithium storage behavior of a hybrid battery-supercapacitor electrode: initial charge capacity of 1060 mAh g(-1) at the 100 mA g(-1) rate, stable cyclic capacity of 1077.9 mAh g(-1) at the same rate after 140 cycles, and rate capability of 538.8 mAh g(-1) at 2400 mA g(-1). This outstanding performance was attributed to the nanocrystal superiority, which shortens the Li(+) diffusion paths. The mechanism of this hybrid anode material was investigated with experimental measurements and structural analysis. The results indicate that at the first discharge, the MNM nanocrystal microsphere, whose structure can buffer the volume change that occurs during lithiation/delithiation, goes through four stages: Li(+) insertion in cation vacancies, spinel-to-rocksalt transformation, Li(+) intercalation of Li(1.75+x)Fe2O3 nanocrystals, and interfacial Li storage around nanocrystal boundaries. Only the latter two stages were reversible at and after the second charging/discharging cycle, exhibiting the hybrid behavior of a battery-supercapacitor with superior lithium storage.

One-Pot Hydrothermal Synthesis of FeMoO4 Nanocubes as an Anode Material for Lithium-Ion Batteries with Excellent Electrochemical Performance.

Metal molybdates nanostructures hold great promise as high-performance electrode materials for next-generation lithium-ion batteries. In this work, the facial design and synthesis of monodisperse FeMoO4 nanocubes with the edge lengths of about 100 nm have been successfully prepared and present as a novel anode material for highly efficient and reversible lithium storage. Well-defined single-crystalline FeMoO4 with high uniformity are first obtained as nanosheets and then self-aggregated into nanocubes. The morphology of the product is largely controlled by the experimental parameters, such as the reaction temperature and time, the ratio of reactant, the solution viscosity, etc. The molybdate nanostructure would effectively promote the insertion of lithium ions and withstand volume variation upon prolonged charge/discharge cycling. As a result, the FeMoO4 nanocubes exhibit high reversible capacities of 926 mAh g(-1) after 80 cycles at a current density of 100 mA g(-1) and remarkable rate performance, which indicate that the FeMoO4 nanocubes are promising materials for high-power lithium-ion battery applications.

Bottom-up synthesis of nitrogen-doped graphene sheets for ultrafast lithium storage.

A facile bottom-up strategy was developed to fabricate nitrogen-doped graphene sheets (NGSs) from glucose using a sacrificial template synthesis method. Three main types of nitrogen dopants (pyridinic, pyrrolic and graphitic nitrogens) were introduced into the graphene lattice, and an inimitable microporous structure of NGS with a high specific surface area of 504 m(2) g(-1) was obtained. Particularly, with hybrid features of lithium ion batteries and Faradic capacitors at a low rate and features of Faradic capacitors at a high rate, the NGS presents a superior lithium storage performance. During electrochemical cycling, the NGS electrode afforded an enhanced reversible capacity of 832.4 mA h g(-1) at 100 mA g(-1) and an excellent cycling stability of 750.7 mA h g(-1) after 108 discharge-charge cycles. Furthermore, an astonishing rate capability of 333 mA h g(-1) at 10,000 mA g(-1) and a high rate cycle performance of 280.6 mA h g(-1) even after 1200 cycles were also achieved, highlighting the significance of nitrogen doping on the maximum utilization of graphene-based materials for advanced lithium storage.

Electrochemical and electronic properties of LiCoO2 cathode investigated by galvanostatic cycling and EIS.

The processes of extraction and insertion of lithium ions in LiCoO(2) cathode are investigated by galvanostatic cycling and electrochemical impedance spectroscopy (EIS) at different potentials during the first charge/discharge cycle and at different temperatures after 10 charge/discharge cycles. The spectra exhibit three semicircles and a slightly inclined line that appear successively as the frequency decreases. An appropriate equivalent circuit is proposed to fit the experimental EIS data. Based on detailed analysis of the change in kinetic parameters obtained from simulating the experimental EIS data as functions of potential and temperature, the high-frequency, the middle-frequency, and the low-frequency semicircles can be attributed to the migration of the lithium ions through the SEI film, the electronic properties of the material and the charge transfer step, respectively. The slightly inclined line arises from the solid state diffusion process. The electrical conductivity of the layered LiCoO(2) changes dramatically at early delithiation as a result of a polaron-to-metal transition. In an electrolyte solution of 1 mol L(-1) LiPF(6)-EC (ethylene carbonate) :DMC (dimethyl carbonate), the activation energy of the ion jump (which is related to the migration of the lithium ions through the SEI film), the thermal activation energy of the electrical conductivity and the activation energy of the intercalation/deintercalation reaction are 37.7, 39.1 and 69.0 kJ mol(-1), respectively.

[Ion-conducting mechanism of composite polymer electrolyte: an emission FTIR spectroscopy study].

Solvent-free, composite electrolytes based on poly(ethylene oxide) (PEO) were prepared by using mesoporous silica SBA-15 with surface modification of (trimethylchlorosilane) as the filler. The samples were explored by emission FTIR spectroscopy at elevated temperatures. The results of emission FTIR spectra illustrated the dependence of crystalline PEO phase on temperature. On the basis of electrochemistry, SEM, and emission FTIR studies, the effect of inorganic filler on the ionic conductivity was analyzed, and a conclusion concerning the ion-conducting mechanism of composite polymer electrolyte was drawn. The exploratory experiments demonstrated that the emission FTIR spectroscopy is an important method to be applied in the study of lithium batteries.