Cathode Material For Batteries Research Articles

Stabilizing high temperature operation and calendar life of LiNi0.5Mn1.5O4

Severe capacity degradation at high operating voltages and poor interphase stability at elevated temperature have thus far precluded the practical application of LiNi0.5Mn1.5O4 (LNMO) as a cathode material for lithium-ion batteries. Addressing these challenges through a combination of experimental and theoretical methods in this work, we demonstrate how a fluorinated carbonate electrolyte enables both high-voltage and high temperature operation by mitigating the traditional interfacial reactions observed in electrolytes with conventional carbonate solvents. Computational studies confirm the exceptional oxidation stability of fluorinated carbonate electrolyte which reduces deprotonation at high voltage. The mitigated deprotonation will then minimize the formation of HF acid which corrodes the LNMO surface and leads to phase transformation and poor interphases. With fluorinated carbonate electrolyte at elevated temperature, it was found on LNMO’s subsurface a reduced amount of Mn3O4 phase which can block Li+ transfer and result in drastic cell failure. Leveraging this approach, LNMO/graphite full cells with a high loading of 3.0 mAh/cm2 achieve excellent cycling stability, retaining ∼84 % of their initial capacity at room temperature (25 °C) after 200 cycles and ∼68 % after 100 cycles at 55 °C. This advanced electrolyte also shows promise for improving calendar life, retaining >30 % more capacity than the carbonate baseline after high temperature storage. These results indicate that electrolytes based on fluorinated carbonates are a promising strategy for overcoming the remaining challenges toward practical commercial application of LNMO.

Enhanced High Voltage Stability of Spinel‐Type Structured LiNi0.5Mn1.5O4 Electrodes: Targeted Octahedral Crystal Site Modification

AbstractHigh‐voltage spinel‐type structured LiNi0.5Mn1.5O4 (LNMO) shows promise as a next‐generation high‐energy‐density lithium‐ion battery cathode material, however, capacity decay on extended cycling hinders its widespread adoption, underscoring an urgent need for further development. In this work, we introduce Zn at octahedral 16c crystal sites in LNMO with Fd m space group to improve rate capability and reduce the rapid capacity decay otherwise experienced during extended cycling. The current work resolves the detailed influence of isolated modification at octahedral 16c crystal sites, unveiling the mechanism for these performance improvements. We show that occupation of Zn at previously empty 16c sites prevents the migration of Ni/Mn to adjacent 16c sites, eliminating transformation to a rock‐salt type structured Ni0.25Mn0.75O2 phase above 4.8 V, preventing structure degradation and suppressing voltage polarization. This study provides insights into the fundamental structure‐function relationship of the LNMO battery cathode, pointing to pathways for the crystal structure engineering of materials with superior performance.

A Comprehensive Review on Reductive Recycling of Cathode Materials of Spent Lithium-Ion Batteries.

The prosperity of the lithium-ion battery market is inevitably accompanied by the depletion of corresponding resources and the accumulation of spent batteries in a dialectical manner. Spent lithium-ion batteries are harboring the characteristics of hazardous waste and high-value resources, so efficient recycling is of great significance. The cathode material is considered as an interesting target for repurposing. Despite some important reviews give commendable emphasis to recycling technologies, there is still a dearth of exploration of recycling mechanisms. This deficiency of awareness highlights the need for further research and development in this area. This review aims to systematically review and thoroughly discuss the reduction reaction mechanism of each method regarding different cathode materials. And systematically digest the selection of reducing agent and the effect of reduction reaction on material regeneration are systematically digested, as well as the impact of the reduction reaction on the regeneration of materials. This review emphasizes the importance of balancing efficiency, economic and environmental benefits in reuse technologies. Finally, the review proposes an outlook on the opportunities and challenges facing the reuse of key materials for next-generation spent batteries aimed at promoting the green and sustainable development of lithium-ion batteries, circular economy and ecological balance.

Ultrahigh‐Ni Cathode with Superior Structure Stability Enabled by a Covalent Bonding Strategy

AbstractUltrahigh‐nickel layered oxide cathodes are the most promising cathode materials for high‐energy lithium‐ion batteries. However, the rapid structural degradation during cycling charge‐discharge process limits its commercial application. Herein, we report a covalent pinning strategy to enhance structure stability of ultrahigh‐Ni cathode LiNi0.9Co0.06Mn0.04O2 (NCM90). Zr is gradient diffused into the lattice of NCM90 and forms Zr−O bonds during the sintering process, which can effectively alleviate the lattice distortion like introducing pinning centers due to the stronger bond energy, enhancing its structure stability during charge‐discharge process. In the meanwhile, the Zr−O on the surface of NCM90 powder forms LixZryOz coating layer due to the reaction with lithium residue, which prevents from the edge reconstruction and mitigates the occurrence of side reactions, as well as ensuring a fast Li+ diffusion pathway crossing the interface. As a result, the Zr−O modified NCM90 (Zr‐NCM) achieves 88.8 % remarkable capacity retention at 1 C after 200 cycles over 2.8–4.3 V, which is superior to the pristine NCM90 with 71.2 % retention. This work demonstrates that the Zr−O bonding can provide an effective structure pinning for the ultrahigh‐Ni cathode, which will largely guide the development of high‐performance lithium‐ion battery cathode materials.

Intercalation-Induced Localized Conversion Reaction in h-CuSe for Ultrafast-Rechargeable and Long-Cycling Sodium Metal Battery.

Cathode materials of sodium-based batteries with high specific capacity and fast charge-discharge mode, as well as ultralong reversible cycles at wide applied temperatures, are essential for future development of advanced energy storage system. Developing transition metal selenides with intercalation features provides a new strategy for realizing the above cathode materials. Herein, this work reports a storage mechanism of sodium ion in hexagonal CuSe (h-CuSe) based on the density functional theory (DFT) guidance. This work reveals that the two-dimensional ion intercalation triggers localized redox reaction in the h-CuSe bulk phase, termed intercalation-induced localized conversion (ILC) mechanism, to stabilize the sodium storage structure by forming localized Cu7Se4 transition phase and adjusting the near-edge coordination state of the Cu sites to achieve high reversible capacity and ultra-long cycling life, while allowing rapid charge-discharge cycling over a wide temperature range.

Inhibiting the Jahn-Teller Effect of Manganese Hexacyanoferrate via Ni and Cu Codoping for Advanced Sodium-Ion Batteries.

Manganese (Mn)-based Prussian blue analogs (PBAs) are of great interest as a prospective cathode material for sodium-ion batteries (SIBs) due to their high redox potential, easy synthesis, and low cost. However, the Jahn-Teller effect and low electrical conductivity of Mn-based PBA cause poor structure stability and unsatisfactory performance during the cycling. Herein, a novel nickel- and copper-codoped K2Mn[Fe(CN)6] cathode is developed via a simple coprecipitation strategy. The doping elements improve the electrical conductivity of Mn-based PBA by reducing the bandgap, as well as suppress the Jahn-Teller effect by stabilizing the framework, as verified by the density functional theory calculations. Simultaneously, the substitution of sodium with potassium in the lattice is beneficial for filling vacancies in the PBA framework, leading to higher average operating voltages and superior structural stability. As a result, the as-prepared Mn-based cathode exhibits excellent reversible capacity (116.0 mAh g-1 at 0.01 A g-1) and superior cycling stability (81.8% capacity retention over 500 cycles at 0.1 A g-1). This work provides a profitable doping strategy to inhibit the Jahn-Teller structural deformation for designing stable cathode material of SIBs.

A Cu/MnOx Composite with Copper-Doping-Induced Oxygen Vacancies as a Cathode for Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries are anticipated to be the next generation of important energy storage devices to replace lithium-ion batteries due to the ongoing use of lithium resources and the safety hazards associated with organic electrolytes in lithium-ion batteries. Manganese-based compounds, including MnOx materials, have prominent places among the many zinc-ion battery cathode materials. Additionally, Cu doping can cause the creation of an oxygen vacancy, which increases the material's internal electric field and enhances cycle stability. MnOx also has great cyclic stability and promotes ion transport. At a current density of 0.2 A g-1, the Cu/MnOx nanocomposite obtained a high specific capacitance of 304.4 mAh g-1. In addition, Cu/MnOx nanocomposites showed A high specific capacity of 198.9 mAh g-1 after 1000 cycles at a current density of 0.5 A g-1. Therefore, Cu/MnOx nanocomposites are expected to be a strong contender for the next generation of zinc-ion battery cathode materials in high energy density storage systems.

Approaching Ultimate Synthesis Reaction Rate of Ni-Rich Layered Cathodes for Lithium-Ion Batteries

HighlightsA series of layered oxide cathode materials were synthesized by high-temperature shock strategy for the first time.The approaching ultimate solid reaction rate of the layered nickel-rich layered oxide LiNixCoyMnzO2 was investigated for the first time. Ultrafast average reaction rate of phase transition from Ni0.6Co0.2Mn0.2(OH)2 to Li-containing oxides is 66.7 (% s-1), that is, taking only 1.5 s.

New Insight into Bulk Structural Degradation of High-Voltage LiCoO2 at 4.55 V.

The aggravated mechanical and structural degradation of layered oxide cathode materials upon high-voltage charging invariably causes fast capacity fading, but the underlying degradation mechanisms remain elusive. Here we report a new type of mechanical degradation through the formation of a kink band in a Mg and Ti co-doped LiCoO2 cathode charged to 4.55 V (vs Li/Li+). The local stress accommodated by the kink band can impede crack propagation, improving the structural integrity in a highly delithiated state. Additionally, machine-learning-aided atomic-resolution imaging reveals that the formation of kink bands is often accompanied by the transformation from the O3 to O1 phase, which is energetically favorable as demonstrated by first-principles calculations. Our results provide new insights into the mechanical degradation mechanism of high-voltage LiCoO2 and the coupling between electrochemically triggered mechanical failures and structural transition, which may provide valuable guidance for enhancing the electrochemical performance of high-voltage layered oxide cathode materials for lithium-ion batteries.

Boosting the Electrochemical Performance of Primary and Secondary Lithium Batteries with Mn-Doped All-Fluoride Cathodes.

Transition metal fluorides are potentially high specific energy cathode materials of next-generation lithium batteries, and strategies to address their low conductivity typically involve a large amount of carbon coating, which reduces the specific energy of the electrode. In this study, MnyFe1-yF3@CFx was generated by the all-fluoride strategy, converting most of the carbon in MnyFe1-yF3@C into electrochemical active CFx through a controllable NF3 gas phase fluorination method, while still retaining a tightly bound graphite layer to provide initial conductivity, which greatly improved the energy density of the composite. This synergistic effect of nonfluorinated residual carbon (∼11%) and Mn doping ensures the electrochemical kinetics of the composite. The loading mass of the active substance had been increased to 86%. The theoretical and actual discharge capacity of MnyFe1-yF3@CFx composite was up to 765 mAh g-1 (pure FeF3 is 712 mAh g-1) and 728 mAh g-1, respectively. The discharge capacity at the high-voltage (3.0 V) platform was more than three times higher than that of the non-Mn-doped composite (FeF3@CFx).

Promoted production of aromatic hydrocarbons in biomass catalytic pyrolysis over the coupled catalysts of carbon-reduced waste lithium battery cathode materials and HZSM-5

Inexpensive catalyst sources are of great importance in the conversion of biomass to economically valuable monocyclic aromatic hydrocarbons, and transition metals (Co, Ni, Fe and Mn) rich in catalytic effects in massive waste lithium battery cathode materials are not effectively reutilized currently. For this reason, the feasibility of employing the valuable metal oxides in the carbon-reduced waste lithium battery cathode materials (waste LiFePO4 batteries, LFP, and waste LiNixCoyMn1–x–yO2 batteries, NCM) with HZSM-5 as coupled catalysts in the rape straw catalytic pyrolysis to produce aromatic hydrocarbons was explored. The carbon-reduced waste lithium battery cathode materials performed well at 5 wt% carbon loading, and the content of active components Fe2O3 (SLFPC-5) and NiO (SNCMC-5) used for the reduction of large molecular oxygenates in biomass pyrolysis gas was increased by water leaching treatment. SLFPC-5 demonstrated superior bond-cutting performance, while SNCMC-5 exhibited strong deoxygenation performance. The selectivity of monocyclic aromatic hydrocarbons (MAHs) catalyzed by SLFPC-5/HZSM-5 and SNCMC-5/HZSM-5 was as high as 63.69 % and 79.19 %, with BTX yields of 14.58 wt% and 16.68 wt% respectively. This coupled catalytic system offers a low-cost source of catalysts for biomass catalytic pyrolysis and broadens the possibility of high-value recycling of wasted lithium batteries.

Unlocking the potential of spinel MnV2O4 for highly durable aqueous zinc-ion batteries

Aqueous zinc-ion batteries (AZIBs) have received comprehensive attention as promising candidates for large-scale energy storage owing to high security, low cost, and environmental friendliness. Developing appropriate cathode materials is of great significance for high-efficiency Zn2+ storage. Herein, we proposed an efficient in-situ electrochemical pretreatment strategy to unlock the potential of non-electrochemically active spinel MnV2O4via an irreversible phase reconstruction from crystalline structure to short-range ordered amorphous state. Specifically, the reconstructed electrodes not only deliver abundant active sites for Zn2+ ions accommodation, but also shorten diffusion paths for rapid reaction kinetics, thus achieving superior electrochemical properties. As revealed, the optimized electrodes present a prominent specific capacity of 445 mA h g−1 at 0.1 A g−1, a high capacity retention of 73.1 % over 2000 cycles at 5 A g−1, as well as exceptional energy density of 335 W h kg−1 and power density of 176 W kg−1 based on the mass of cathode. In addition, the reaction mechanism during Zn2+ ions storage process is systematically investigated by ex-situ X-ray diffraction and X-ray photoelectron spectroscopy. This in-situ electrochemical conversion mechanism sheds light on a new methodology of designing desirable cathode materials for aqueous ion batteries.

Exploring the Effect of TiO2 Coating on Na0.85Li0.12Ni0.22Mn0.66O2 Cathode Materials for Na-Ion Batteries

Layered transition metal oxides have great potential as cathode materials for sodium ion batteries, but some limitations like structural instability and poor rate performance restricts its further application. To overcome the above issues, a simultaneously modified P2-type cathode of Na0.85Li0.12Ni0.22Mn0.66O2 with 1% weight TiO2 coating (NLNMO-1%wt TiO2) based on doping and coating approaches was prepared by high-temperature solid-state reaction and liquid phase coating. This new strategy reduces the relative content of Mn3+, which suppresses the Jahn-Teller effect and enhanes the structural stability. The as-prepared cathode shows improved rate capability, with a high reversible capacity of 111.4 mAh g−1 at 1 C and a capacity retention of 94.5% after 100 cycles. At 5 C, it maintains a capacity of 87.1 mAh g−1 at 5 C with capacity retention of 81.8% after 400 cycles. Additionally, it provides a stable CEI film, reducing side reactions and electrode pulverization. which could be confirmed by scanning electron microscopy and high-resolution transmission electron microscopy. Overall, this synergistic modification strategy provides a pathway for improving the electrochemical performance of layered oxide cathode materials for sodium-ion batteries.

Boosting interface compatibility of high-voltage LiNi0.5Mn1.5O4 cathode materials with an ionic-conductive Li0.33La0.56TiO3 coating

High voltage LiNi0.5Mn1.5O4 (LNMO) is a crucial cathode material for lithium-ion batteries (LIBs) aiming at high energy densities. However, its performance is hindered by the dissolution of transition metal ions and the instability of the cathode electrolyte interface (CEI) film at elevated voltages. To address these issues, we report a solvothermal method to prepare LNMO coated with Li+-conductor Li0.33La0.56TiO3 (LNMO@LLTO). Our study reveals that the LLTO coating not only enhances ion diffusion at the interface, minimizing the Li+ concentration gradient, and acts as a barrier against Mn-ion dissolution. This coating minimizes side reactions, mitigates structural degradation, and promotes the formation of a stable and balanced CEI film that incorporates LLTO, thus ensuring the long-term cycle stability. When compared to bulk LNMO, the LNMO@LLTO cathode demonstrates superior performance, maintaining reversible capacities of 111.4 and 102.2 mAh·g−1 after 500 cycles at 2 and 5C at 25 °C, respectively. Even at 60 °C, the LNMO@LLTO maintains a high capacity of 94.3 mAh·g−1 with minimal electrochemical polarization after 200 cycles at 2C. This simple preparation technique, together with its performance promotion, offers new insights into the development of high voltage cathode materials for high energy density LIBs.

High performance phenothiazine-based battery materials achieved by synergistic steric blocking and extended conjugation

Phenothiazine derivatives, as sustainable cathode materials for batteries, show significant promise for large-scale electrical energy storage applications. However, the irreversibility of the sulfur redox active center severely limits their energy density and discharge voltage in rechargeable organic batteries. This study concentrates on identifying the potential side reactions that contribute to the irreversibility of phenothiazine-based materials. We propose a molecular design strategy that synergistically blocks the active site and extends the conjugation, markedly improving the electrochemical reversibility of these materials. Our findings reveal that phenothiazine derivatives can undergo two successive, one-electron redox reactions without interference from chemical bond rearrangement and reactive radicals. The assembled cells, utilizing lithium (Li) and sodium (Na) as anodes, display two distinct discharge plateaus at 3.3/3.9 V vs. Li+/Li and 3.1/3.7 V vs. Na+/Na, respectively, with nearly identical contributions from the nitrogen (N) and sulfur (S) redox centers. The phenothiazine derivatives designed via this strategy rank among the few phenothiazine-based organic electrode materials capable of achieving highly reversible, two-electron transfer redox reactions in organic batteries.

Construction of a bi-continuous charge transport network towards high-performance vanadium-based phosphate cathode materials for potassium ion batteries

As one class of most promising cathode materials for potassium ion batteries (KIBs), polyanionic compounds still suffer from unsatisfactory effective capacity and rate performance due to their poor intrinsic electronic conductivity. In this paper, nanoscale K3V3(PO4)4 (KVP) particles with a bi-continuous charge transport network (denote as KVP-S) are designed and prepared. Carbon nanotubes (CNTs) play a crucial role in this design, not only effectively inhibiting the aggregation and growth of particles, but also providing a three-dimensional (3D) electron conductive network. Benefiting from the advantages of nanoscale particle size and bi-continuous charge transport network, the KVP-S electrode exhibits a high capacity (118mAh g−1 at 20 mA g−1), outstanding rate performance (102 mAh g−1 at 0.5 C; 66 mAh g−1 at 5 C) and excellent cycling stability (94 % retention after 50 cycles at 1 C). Even at a higher rate of 5 C, it still maintains a high capacity retention of 92 % after 300 cycles. More importantly, the capacity can maintain 80 mAh g−1 at 1 C when the mass loading is extended to 4 mg cm−2, In addition, in-situ X-ray diffraction (XRD) and ex-situ X-ray photoelectron spectroscopy (XPS) analyses reveal that the potassium storage mechanism of KVP-S is two single-phase solid solution reactions, involving V2+/V3+/V4+ three-electron redox conversions with a total volume change of 5.5 %. This study provides a new way to rationally design nanoscale particle electrodes with highly conductive charge transport networks.

Mo-Doped Na4Fe3(PO4)2P2O7/C Composites for High-Rate and Long-Life Sodium-Ion Batteries.

Na4Fe3(PO4)2P2O7/C (NFPP) is a promising cathode material for sodium-ion batteries, but its electrochemical performance is heavily impeded by its low electronic conductivity. To address this, pure-phase Mo6+-doped Na4Fe3-xMox(PO4)2P2O7/C (Mox-NFPP, x = 0, 0.05, 0.10, 0.15) with the Pn21a space group is successfully synthesized through spray drying and annealing methods. Density functional theory (DFT) calculations reveal that Mo6+ doping facilitates the transition of electrons from the valence to the conduction band, thus enhancing the intrinsic electron conductivity of Mox-NFPP. With an optimal Mo6+ doping level of x = 0.10, Mo0.10-NFPP exhibits lower charge transfer resistance, higher sodium-ion diffusion coefficients, and superior rate performance. As a result, the Mo0.10-NFPP cathode offers an initial discharge capacity of up to 123.9 mAh g-1 at 0.1 C, nearly reaching its theoretical capacity. Even at a high rate of 10 C, it delivers a high discharge capacity of 86.09 mAh g-1, maintaining 96.18% of its capacity after 500 cycles. This research presents a new and straightforward strategy to enhance the electrochemical performance of NFPP cathode materials for sodium-ion batteries.

Cu doping in TM ordered and disordered layered oxides for Sodium-Ion Batteries: Electrochemical Properties, structure evolution and Cu-Ion migration

The ordered/disordered distribution of transition metal (TM) plays a significant role in determining electrochemical properties including lattice oxygen redox, ion kinetics and structure evolution. From a novel perspective, this work demonstrates how the TM distributions influence the doping effect by means of introducing Cu element into ordered/disordered O3-Nax(NiySb1-y)O2. What’s more, the irreversible Cu migration from TM sites to Na layers upon electrochemical process is found. This migration which would deteriorate electrochemical stability only occurs in honeycomb-ordered compounds, instead of in disordered one. Theoretical calculations reveal that the TM disordered distribution promotes the formation of antibonding orbitals between Cu 3d and O 2p, thereby increasing the barrier of Cu migration to maintain well Na diffusion kinetics. Our discovery rolls out a new guidance for designing advanced cathode materials for sodium-ion batteries and speeds up the research on transition metal migration.

The emerging high-entropy strategy: a booster to the development of cathode materials for power batteries

The emerging high-entropy strategy: a booster to the development of cathode materials for power batteries

Recent advances of cobalt-free and nickel-rich cathode materials for lithium-ion batteries

Recent advances of cobalt-free and nickel-rich cathode materials for lithium-ion batteries