High-performance Batteries Research Articles

Dry carbothermal reaction-enabled ultra-dense nanoparticle coatings for high-performance Li-S batteries

Electrocatalysts are crucial for facilitating the sluggish conversion between S and sulfide in Li-S batteries. Despite recent exploration of advanced materials, there remains a significant gap in the morphology design rationale oriented towards practical operation conditions. In this study, we introduce a dry process based on the carbothermal reaction of oxides to achieve nanoparticle (NP) electrocatalyst coatings. This process enables us to produce ultra-high-density NPs with several tens of particles per 100 nm x 100 nm area. We unveil that this high coating density boosts the conversion kinetics by dominating a solution-phase disproportionation reaction, thereby promoting the growth of non-passivating particulate sulfide. With this NP-coated cathode, we achieve excellent kinetic performance, maintaining 53 % of cell capacity retention even with a 50-fold increase in C-rate, and exhibiting only a 0.04 % capacity decay per cycle over 300 cycles at 10C. Remarkably, our cathode achieves an initial areal capacity of 7.51 mAh cm−2 in a full cell, significantly outperforming cells reported in previous studies as well as conventional Li-ion batteries.

Rhombohedral Li1-xZr2-xSbx(PO4)3 electrolytes with improved Li+ conductivity for high-performance solid-state Li-metal battery

Recent studies on solid electrolytes have promoted the development of solid-state Li-metal batteries (SSLBs). The NASICON-type LiZr2(PO4)3 (LZP) electrolyte has received less attention due to its low conductivity and the existence of several crystal forms, which have impeded the development of LZP-based materials for SSLBs. Herein, Li1-xZr2-xSbx(PO4)3 (LZSP) ceramics were synthesized by solid-state method, and the cycle performances of symmetrical cell and Li-metal battery using LZSP electrolyte were characterized for the first time. The Sb5+ doping stabilizes the rhombohedral phase at room temperature and results in distortions in the ZrO6 octahedron and PO4 tetrahedron, which lead to variations of bond length and bond angle. The room temperature total conductivity of Li0.94Zr1.94Sb0.06(PO4)3 (LZSP-0.06) increased to 6.53 × 10−5 S·cm−1. This rise can be attributed to a reduction of the Li+ ions transport barrier originated from variations of bond length, bond angle and Raman vibrations mode. The Li/LZSP-0.06/Li symmetrical cell maintains a stable cycle duration of 670 h at a current density of 0.12 mA cm−2. The specific capacity of Li/LZSP-0.06/LiFePO4 battery reaches 140.1 mAh g−1 at 0.5C and the coulombic efficiency is 99.8 %. This battery maintains 80 % capacity after 105 cycles. These results provide reference significance for the research on SSLBs using LZP-based electrolytes. In general, the Li0.94Zr1.94Sb0.06(PO4)3 ceramic appears to be a promising solid electrolyte for SSLBs.

Bifunctionally Electrocatalytic Bromine Redox Reaction by Single-Atom Catalysts for High-Performance Zinc Batteries.

Aqueous zinc-bromine (Zn||Br2) batteries are regarded as one of the most promising energy storage devices due to their high safety, theoretical energy density, and low cost. However, the sluggish bromine redox kinetics and the formation of a soluble tribromide (Br3 -) hinder their practical applications. Here, it is proposed dispersed single iron atom coordinated with nitrogen atoms (FeN5) in a mesoporous carbon framework (FeSAC-CMK) as a conductive catalytic bromine host, which possesses porous structure and electrocatalytic functionality of FeN5 species for enhanced confinement and electrocatalytic effect. The active FeN5 species can fix the bromine (Br0) species to suppress the formation of Br3 - effectively and bifunctionally catalyze the bromide (Br-)/Br° conversion. These free up 1/3 Br- locked by Br3 - complexing agent for enhanced bromine utilization efficiency and conversion reversibility. Accordingly, the Zn||Br2 battery with FeSAC-CMK delivers an impressive specific capacity of 344 mAh g-1 at 0.2 A g-1 and superior rate capability with 164 mAh g-1 achieved even at 20 A g-1, much higher than that of inactive CMK (262 mAh g-1 at 0.2 A g-1; 6 mAh g-1 at only 8 A g-1). Furthermore, the battery demonstrates excellent cycling performance of 88% capacity retention after 2000 cycles.

Electrochemical behavior and reaction mechanism of nano-BiOBr/rGO composite micro flower with strong interface coupling as potassium-ion battery anodes

To explore the potential of bismuth oxybromide (BiOBr) as anodes for high-performance potassium (K)-ion batteries and understand its potassium storage mechanism, a novel nano-BiOBr/reduced graphene oxide (rGO) composite micro flower (labelled as SI-coupled nano-BiOBr/rGO micro flower), where nano-BiOBr slices are firmly anchored on rGO by strong interface coupling, is constructed. Unique microstructure accompanied by C-Bi bonds at the interface between BiOBr and rGO endows it with abundant high-speed charge transfer channels and excellent structural stability. As a result, it exhibits an excellent rate performance (a high reversible capacity of 278 mAh/g at 5 A/g) and a remarkable long-term cycling stability maintaining 95.4 % after 1000 cycles at 2.5 A/g. Furthermore, it is also found that SI-coupled nano-BiOBr/rGO micro flower anode undergoes intercalation, conversion, and alloying (BiOBr → KzBiOBr → Bi → KBi2 → K3Bi2 → K3Bi) at the initial discharge process, and the subsequent charge process is only reversible dealloying and conversion reaction (K3Bi → K3Bi2 → KBi2 → Bi → BiOxBry). This work not only demonstrates the large potential of BiOBr as high-performance K-ion battery anodes, but also elucidates for the first time its K storage mechanism.

Designing a Refined Multi-Structural Polymer Electrolyte Framework for Highly Stable Lithium-Metal Batteries.

Rational structural designs of solid polymer electrolytes featuring rich interface-phase morphologies can improve electrolyte connection and rapid ion transport. However, these rigid interfacial structures commonly result in diminished or entirely inert ionic conductivity within their bulk phase, compromising overall electrolyte performance. Herein, a multi-component ion-conductive electrolyte was successfully designed based on a refined multi-structural polymer electrolyte (RMSPE) framework with uniform Li+ solvation chemistry and rapid Li+ transporting kinetics. The RMSPEis constructed via polymerization-induced phase separation based on a rational combination of lithiophilic components and rigid/flexible chain units with significant hydrophobic/hydrophilic contrasts. Further refined by coating a robust polymer network, this all-organic design endows a homogenous micro-nano porous structure, providing a novel framework favorable for rapid ion transport in both its soft interfacial and bulk phases. The RMSPE exhibited excellent ion conductivity of 1.91 mS cm-1 at room temperature and a high Li+ transference number of 0.7. Assembled symmetrical Li cells realized stable cycling for over 2400 h at 3.0 mA cm-2. LiFePO4 full batteries demonstrated a long lifespan of 3300 cycles with a capacity retention of 93.5% and stable cycling performance at -35 °C. This innovative design concept offers a promising perspective for achieving high-performance polymer-based Li metal batteries.

WN-CoS2 nanoparticles encapsulated into carbon nanotubes enable a stable and high-performance rechargeable zinc air battery

The battery performance associated with longevity are the priorities for the industrialization of rechargeable zinc air battery (ZAB). Herein, we have reported the construction of WN-CoS2 heterostructure enveloped by nitrogen and phosphorus co-doped carbon nanotubes (WN-CoS2@NPCNT). WN-CoS2@NPCNT performs a superior oxygen evolution reaction (OER) catalytic activity of 279 mV overpotential to reach 10 mA cm−2, lowered by 85 mV with relative to CoS2@NCNT attributing to the heterostructure efficiently modulating the electronic structure of active sites. Besides, the half-wave potential reaches 0.875 V vs. RHE for WN-CoS2@NPCNT under oxygen reduction reaction (ORR) condition, corresponding to a 3.2-time higher kinetic current density compared to commercial Pt/C. Due to the exceptional bifunctionality, the battery performance is 205 mW cm−2 for WN-CoS2@NPCNT, 1.54 times higher than commercial counterpart, Pt/C + IrO2. Impressively, the battery performance sustains for 1000 h for WN-CoS2@NPCNT stemming from the confinement effect caused by NPCNT. In addition, the all-solid-state ZAB shows a high-power density of 55 mW cm−2.

Polyacrylonitrile-blended polyethersulfone separator with greatly improved interface compatibility for lithium-oxygen battery

A novel polyacrylonitrile-blended/polyethersulfone (PES/PAN) separator was developed using the nonsolvent-induced phase separation (NIPS) method to improve the poor interfacial compatibility of Li-O2 batteries. Batteries assembled with the represented PES/PAN-2 separator exhibits significantly enhanced stability compared to the pristine PES separator. Its interfacial impedance (425.1 Ω) is one-fifth that of the pure PES separator (2018.1 Ω), while its ionic conductivity (0.70 mS cm−1) is nearly double that of the pristine PES (0.38 mS cm−1). With all these merits, the battery utilizing the PES/PAN-2 separator achieved excellent cycling performance of up to 80 cycles at 1000 mAh g−1, making it a superior choice for high-performance lithium-oxygen batteries.

Anion-Anchored Polymer-in-Salt Solid Electrolyte for High-Performance Zinc Batteries.

Solid polymer electrolytes hold promise for addressing key challenges in rechargeable zinc batteries (ZBs) utilizing aqueous electrolytes. However, achieving simultaneous high ionic conductivity, excellent mechanical strength, and a high cation transference number while effectively suppressing Zn dendrites remains challenging. Herein, we design a novel polymer-in-salt solid electrolyte (PISSE) composed of polyacrylonitrile (PAN), zinc chloride (ZnCl2), and niobium pentoxide with oxygen vacancies (Nb2O5-x) with high ionic conductivity. PAN polymer matrix provides the electrolyte good mechanical properties and solubility of Zn salt. The high concentration of ZnCl2 effectively decouples the Zn2+ from polymer chain segments and provides more ionic conduction amorphous region. Moreover, incorporating Nb2O5-x filler accelerates Zn2+ desolvation by anchoring (ZnxCly)2x-y clusters and enhances the system's mechanical properties, achieving a superior Zn2+ transference number (~0.93) and interfacial stability. Consequently, the optimized PISSE demonstrates exceptional stability during prolonged cycling periods, wide temperature range operation (-40 ℃ to 60 ℃), remarkable flexibility, and compatibility with diverse electrode materials. This study provides valuable insights into the design of solid-state electrolytes based on ZBs and elucidates their multifunctional prospects.

Constructing Donor–Acceptor-Linked COFs Electrolytes to Regulate Electron Density and Accelerate the Li+ Migration in Quasi-Solid-State Battery

HighlightsDonor–acceptor-linked covalent organic framework (COF)-based electrolyte can not only fulfill highly-selective Li+ conduction, but also offer a crucial opportunity to understand the role of electronic density in quasi-solid-state Li metal batteries.Donor–acceptor-linked COF electrolyte results in Li+ transference number 0.83, high ionic conductivity 6.7 × 10–4 S cm−1 and excellent cyclic ability in Li metal batteries.In situ characterizations, density functional theory calculation and time-of-flight secondary ion mass spectrometry are adopted to expound the mechanism of the rapid migration of Li+ in the “donor–acceptor” electrolyte system.

NiO nanosheets constructing honeycomb porous catalyst as an effective oxygen adsorption interlayer support for high performance lithium-oxygen batteries

Lithium-oxygen (LiO2) batteries are considered as a novel energy storage system as a result of its outstanding energy density. However, the challenge of oxygen corrosion is still restricting the practical application in LiO2 batteries. Here, we successfully acquire the NiO nanosheets constructing honeycomb porous catalysts as an effective oxygen adsorption interlayer support for high-performance LiO2 batteries. Honeycomb porous structures can store more oxygen and the defects in the exterior of NiO nanosheets can furnish more Lewis acid sites and catalytic sites to bind more O2− as a Lewis base for absorbing O2. Consequently, NiO nanosheets constructing honeycomb porous catalysts as interlayer is loading on the glass fiber membrane separator for LiO2 batteries in order to protect the anode from oxygen corrosion. The interlayer with 1.0 mg/cm2 NiO loading rate per unit area shows the outstanding electrochemical performance at a fixed 500 mAh/g specific discharge capacity and 0.1 mA/cm2 current density for 106 cycles in the LiO2 battery. This work provides an effective strategy to protect the Li metal anode in LiO2 batteries, at the same time, proposes a novel view for the efficient modification of separator.

Synergistic Regulation of Anode and Cathode Interphases via an Alum Electrolyte Additive for High-performance Aqueous Zinc-Vanadium Batteries.

A zinc (Zn) metal anode paired with a vanadium oxide (VOx) cathode is a promising system for aqueous Zn-ion batteries (AZIBs); however, side reactions proliferating on the Zn anode surface and the infinite dissolution of the VOx cathode destabilise the battery system. Here, we introduce a multi-functional additive into the ZnSO4 (ZS) electrolyte, KAl(SO4)2 (KASO), to synchronise the in-situ construction of the protective layer on the surface of the Zn anode and the VOx cathode. Theoretical calculations and synchrotron radiation have verified that the high-valence Al3+plays multifunctionalroles of competing with Zn2+for solvation and forming a Zn-Al alloy layer with a homogeneous electricfield to mitigate the side reactions and dendrite generation. The Al-containing cathode-electrolyte interface considerably alleviates the irreversible dissolution of the VOx cathode and the accumulation of byproducts. Consequently, the Zn || Zn cell with KASO exhibits an ultra-long cycle of 6000 h at 2 mA cm-2. Importantly, the VOx cathodes (VO2, V2O5 and NH4V4O10) in the ZS-KASO electrolyte showed excellent cycling stability, even at a low negative/positive (N/P) ratio of 2.83 and high mass loading (~16 mg cm-2). This study offers a practical reference for concurrently addressing challenges at the anode and cathode of AZIBs.

Emulating "Curvature-Enhanced Adsorbate Coverage" for Superconformal and Orientated Zn Electrodeposition in Zinc-ion-Batteries.

Uneven Zn deposition and unfavorable side reactions have prevented the reversibility of the Zn anode. Herein, we design a rearranged (002) textured Zn anode inspired by a traditional curvature-enhanced adsorbate coverage (CEAC) process to realize the highly reversible Zn anode. The rearranged (002) textured structure orientates the superconformal Zn deposition owing to the spatial deposition rate of the rearranged crystal planes, promoting bottom-up "superfilling" of the 3D Zn skeletons. Meanwhile, our designed anode also induces the epitaxial Zn deposition, alleviating the parasitic reactions owing to the lowest surface energy of the (002) plane. Attributed to these superiorities, uniform and oriented Zn deposition can be obtained, exhibiting an ultra-long lifespan over 479 hrs at an ultrahigh depth of discharge (DOD) of 82.12%. The Zn|Na2V6O16·3H2O battery delivers an improved cycling performance, even at a high area capacity of 5.15 mAh/cm2 with a low negative/positive (N/P) capacity ratio of 1.63. The superconformal deposition approach for Zn anodes paves the way for the practical application of high-performance zinc-ion batteries.

Modulating the Inner Helmholtz Plane towards Stable Solid Electrolyte Interphase by Anion-π Interactions for High-Performance Anode-Free Lithium Metal Batteries.

Anode-freelithium (Li) metal batteries (AFLBs) featured high energy density are viewed as the viable future energy storage technology. However, the irregular Li deposition and unstable solid electrolyte interphase (SEI) on anode current collectors reduce their cycling performance. Here, we propose a concept of anion-recognition electrodes enabled by anion-π interactions to regulate the inner Helmholtz plane (IHP) and electrolyte solvation chemistry for high-performance AFLBs. By engineering the electrodes with electron-deficient aromatic-π systems that possess high permanent quadrupole moment (Qzz),the anion-π interactions can be generated to concentrate the anions on the electrode surface and tune the IHP structure to construct a stable anion-derived SEI layer, thus achieving highly reversible Li plating/stripping process. Through designing various current collectors with different Qzz values, the intimate correlations among the surface charge of the electrode, competitive adsorption of the IHP, and SEI structures are demonstrated. Particularly, the modified carbon cloth current collector with a high Qzz value (+35.1) delivers a high average Li stripping/plating Coulombic efficiency of 99.1% over 230 cycles in the carbonated electrolyte, enabling a long lifespan and high capacity retention of LiNi0.8Co0.1Mn0.1O2-based AFLBs with a commercial-level areal capacity (4.1 mA h cm-2).

Compositional Engineering of Lithium Metal Anode for High-Performance Garnet-Type Solid-State Lithium Battery.

Garnet-type solid-state lithium batteries (SSLBs) possess excellent potential owing to their safety and high energy density. However, fundamental barriers are deficient cycling stability and poor rate capability. The main concern lies in generating voids at the Li|garnet interface during Li stripping, stemming from the sluggish diffusion of Li atoms inside the bulk Li metal. Herein, a composite anode (AN@Li) containing Li-Al alloy, Li3N, and LiNO2 is designed by introducing aluminum nitrate into molten Li. The lower interfacial formation energies exhibited by Li-Al alloy, Li3N, and LiNO2 with garnet solid-state electrolyte (SSE) enhance the wettability of AN@Li toward SSE. Meanwhile, it affords efficient conductive pathways that facilitate Li+ diffusion in the bulk anode (not just on the surface). Impressively, the resulting symmetric cell with AN@Li electrodes achieves high critical current density (1.95mA cm-2) and long cycle life (6000h at 0.3mA cm-2). The SSLB coupled with LiFePO4 cathode and AN@Li anode enables stable cycling for 200 cycles at a high rate of 1 C with a retention of 96% and exhibiting outstanding rate capability (145.9 mAh g-1 at 2 C). This work provides practical insights for producing high-performance lithium metal anode for advanced garnet-type SSLBs.

The Design of Transition Metal Sulfide Cathodes for High-Performance Magnesium-Ion Batteries

The Design of Transition Metal Sulfide Cathodes for High-Performance Magnesium-Ion Batteries

A Bio-Inspired Multifunctional Hydrogel Network with Toughly Interfacial Chemistry for Dendrite-Free Flexible Zinc Ion Battery.

Flexible and high-performance aqueous zinc-ion batteries (ZIBs), coupled with low cost and safe, are considered as one of the most promising energy storage candidates for wearable electronics. Hydrogel electrolytes present a compelling alternative to liquid electrolytes due to their remarkable flexibility and clear advantages in mitigating parasitic side reactions. However, hydrogel electrolytes suffer from poor mechanical properties and interfacial chemistry, which limits them to suppressed performance levels in flexible ZIBs, especially under harsh mechanical strains. Herein, a bio-inspired multifunctional hydrogel electrolyte network (polyacrylamide (PAM)/trehalose) with improved mechanical and adhesive properties was developed via a simple trehalose network-repairing strategy to stabilize the interfacial chemistry for dendrite-free and long-life flexible ZIBs. As a result, the trehalose-modified PAM hydrogel exhibits a superior strength and stretchability up to 100 kPa and 5338 %, respectively, as well as strong adhesive properties to various substrates. Also, the PAM/trehalose hydrogel electrolyte provides superior anti-corrosion capability for Zn anode and regulates Zn nucleation/growth, resulting in achieving a high Coulombic efficiency of 98.8 %, and long-term stability over 2400 h. Importantly, the flexible Zn//MnO2 pouch cell exhibits excellent cycling performance under different bending conditions, which offers a great potential in flexible energy-related applications and beyond.

Encapsulation of Sn Sub-Nanoclusters in Multichannel Carbon Matrix for High-Performance Potassium-Ion Batteries.

Sub-nanoclusters with ultra-small particle sizes are particularly significant to create advanced energy storage materials. Herein, Sn sub-nanoclusters encapsulated in nitrogen-doped multichannel carbon matrix (denoted as Sn-SCs@MCNF) are designed by a facile and controllable route as flexible anode for high-performance potassium ion batteries (PIBs). The uniformly dispersed Sn sub-nanoclusters in multichannel carbon matrix can be precisely identified, which ensure us to clarify the size influence on the electrochemical performance. The sub-nanoscale effect of Sn-SCs@MCNF restrains electrode pulverization and enhances the K+ diffusion kinetics, leading to the superior cycling stability and rate performance. As freestanding anode in PIBs, Sn-SCs@MCNF manifests superior K+ storage properties, such as exceptional cycling stability ( around 331 mAh g-1 after 150 cycles at 100 mA g-1) and rate capability. Especially, the Sn-SCs@MCNF||KFe[Fe(CN)6] full cell demonstrates impressive reversible capacity of around 167 mAh g-1 at 0.4 A g-1 even after 200 cycles. Theoretical calculations clarify that the ultrafine Sn sub-nanoclusters are beneficial for electron transfer and contribute to the lower energy barriers of the intermediates, thereby resulting in promising electrochemical performance. Comprehensive investigation for the intrinsic K+ storage process of Sn-SCs@MCNF is revealed by in situ analysis. This work provides vital guidance to design sub-nanoscale functional materials for high-performance energy-storage devices.

Tuning collective anion motion enables superionic conductivity in solid-state halide electrolytes.

Halides of the family Li3MX6 (M = Y, In, Sc and so on, X = halogen) are emerging solid electrolyte materials for all-solid-state Li-ion batteries. They show greater chemical stability and wider electrochemical stability windows than existing sulfide solid electrolytes, but have lower room-temperature ionic conductivities. Here we report the discovery that the superionic transition in Li3YCl6 is triggered by the collective motion of anions, as evidenced by synchrotron X-ray and neutron scattering characterizations and ab initio molecular dynamics simulations. Based on this finding, we used a rational design strategy to lower the transition temperature and thus improve the room-temperature ionic conductivity of this family of compounds. We accordingly synthesized Li3YClxBr6-x and Li3GdCl3Br3 and achieved very high room-temperature conductivities of 6.1 and 11 mS cm-1 for Li3YCl4.5Br1.5 and Li3GdCl3Br3, respectively. These findings open new routes to the design of room-temperature superionic conductors for high-performance solid batteries.

Activating supercooled electrolytes

Abstract While materials science research in the rechargeable battery field is usually application-oriented, the general supercooled liquid theory from glass science can drive high-performance low-temperature aqueous batteries, facilitating cross-disciplinary collaborations and simultaneous research break- throughs.

Promoting Cathodic Kinetics and Anodic Stability in Practical Room-Temperature Sodium-Sulfur Batteries with Bifunctional Electrolytes.

The development of room-temperature (RT) sodium-sulfur (Na-S) batteries is severely hindered due to the slow kinetics of the S cathode and the instability of the Na-metal anode. To overcome this, we introduced a dual-functional electrolyte cosolvent, trifluoromethanesulfonamide (TFMSA). Short-chain Na2Sx (1 ≤ x ≤ 2) can be effectively dissolved due to the strong H-S bond interaction between TFMSA and sulfides, which changes the S conversion process, thereby effectively enhancing the conversion kinetics of the cathode. Meanwhile, TFMSA can generate a stable solid electrolyte interphase on the Na-metal surface to protect it from soluble polysulfide attack. Therefore, the RT Na-S batteries using the ether electrolyte show a high initial discharge capacity of 896.6 mAh g-1 and a capacity retention rate of 73% after 150 cycles at 0.2C, and the pouch cell also demonstrates its practical performance. This work proposes a dual-functional electrolyte cosolvent selection principle to inspire the practical application of high-performance RT Na-S batteries.