KTi2(PO4)3 with Large Ion Diffusion Channel for High‐Efficiency Sodium Storage

To accommodate the decreasing lithium resource and ensure continuous development of energy storage industry, sodium‐based batteries are widely studied to inherit the next generation of energy storage devices. In this work, a novel Na super ionic conductor type KTi₂(PO₄)₃/carbon nanocomposite is designed and fabricated as sodium storage electrode materials, which exhibits considerable reversible capacity (104 mAh g^?1 under the rate of 1 C with flat voltage plateaus at ≈2.1 V), high‐rate cycling stability (74.2% capacity retention after 5000 cycles at 20 C), and ultrahigh rate capability (76 mAh g^?1 at 100 C) in sodium ion batteries. Besides, the maximum ability for sodium storage is deeply excavated by further investigations about different voltage windows in half and full sodium ion cells. Meanwhile, as cathode material in sodium‐magnesium hybrid batteries, the KTi₂(PO₄)₃/carbon nanocomposite also displays good electrochemical performances (63 mAh g^?1 at the 230th cycle under the voltage window of 1.0–1.9 V). The results demonstrate that the KTi₂(PO₄)₃/carbon nanocomposite is a promising electrode material for sodium ion storage, and lay theoretical foundations for the development of new type of batteries.     

Realizing Three‐Electron Redox Reactions in NASICON‐Structured Na3MnTi(PO4)3 for Sodium‐Ion Batteries

Developing multielectron reaction electrode materials is essential for achieving high specific capacity and high energy density in secondary batteries; however, it remains a great challenge. Herein, Na₃MnTi(PO₄)₃/C hollow microspheres with an open and stable NASICON framework are synthesized by a spray‐drying‐assisted process. When applied as a cathode material for sodium‐ion batteries, the resultant Na₃MnTi(PO₄)₃/C microspheres demonstrate fully reversible three‐electron redox reactions, corresponding to the Ti^3+/4+ (≈2.1 V), Mn^2+/3+ (≈3.5 V), and Mn^3+/4+ (≈4.0 V vs Na⁺/Na) redox couples. In situ X‐ray diffraction results reveals that both solid‐solution and two‐phase electrochemical reactions are involved in the sodiation/desodiation processes. The high specific capacity (160 mAh g^?1 at 0.2 C), outstanding cyclability (≈92% capacity retention after 500 cycles at 2 C), and the facile synthesis make the Na₃MnTi(PO₄)₃/C a prospective cathode material for sodium‐ion batteries.     

H2V3O8 Nanowire/Graphene Electrodes for Aqueous Rechargeable Zinc Ion Batteries with High Rate Capability and Large Capacity

Aqueous rechargeable zinc ion batteries are considered a promising candidate for large‐scale energy storage owing to their low cost and high safety nature. A composite material comprised of H₂V₃O₈ nanowires (NWs) wrapped by graphene sheets and used as the cathode material for aqueous rechargeable zinc ion batteries is developed. Owing to the synergistic merits of desirable structural features of H₂V₃O₈ NWs and high conductivity of the graphene network, the H₂V₃O₈ NW/graphene composite exhibits superior zinc ion storage performance including high capacity of 394 mA h g^?1 at 1/3 C, high rate capability of 270 mA h g^?1 at 20 C and excellent cycling stability of up to 2000 cycles with a capacity retention of 87%. The battery offers a high energy density of 168 W h kg^?1 at 1/3 C and a high power density of 2215 W kg^?1 at 20 C (calculated based on the total weight of H₂V₃O₈ NW/graphene composite and the theoretically required amount of Zn). Systematic structural and elemental characterization confirm the reversible Zn²⁺ and water cointercalation electrochemical reaction mechanism. This work brings a new prospect of designing high‐performance aqueous rechargeable zinc ion batteries for grid‐scale energy storage.     

Highly Reversible Na Storage in Na3V2(PO4)3 by Optimizing Nanostructure and Rational Surface Engineering

Sodium‐ion batteries (NIBs) have attracted more and more attention as economic alternatives for lithium‐ion batteries (LIBs). Sodium super ionic conductor (NASICON) structure materials, known for high conductivity and chemical diffusion coefficient of Na⁺ (≈10^?14 cm² s^?1), are promising electrode materials for NIBs. However, NASICON structure materials often suffer from low electrical conductivity (<10^?4 S cm^?1), which hinders their electrochemical performance. Here high performance sodium storage performance in Na₃V₂(PO₄)₃ (NVP) is realized by optimizing nanostructure and rational surface engineering. A N, B codoped carbon coated three‐dimensional (3D) flower‐like Na₃V₂(PO₄)₃ composite (NVP@C‐BN) is designed to enable fast ions/electrons transport, high‐surface controlled energy storage, long‐term structural integrity, and high‐rate cycling. The conductive 3D interconnected porous structure of NVP@C‐BN greatly releases mechanical stress from Na⁺ extraction/insertion. In addition, extrinsic defects and active sites introduced by the codoping heteroatoms (N, B) both enhance Na⁺ and e^? diffusion. The NVP@C‐BN displays excellent electrochemical performance as the cathode, delivering reversible capacity of 70% theoretical capacity at 100 C after 2000 cycles. When used as anode, the NVP@C‐BN also shows super long cycle life (38 mA h g^?1 at 20 C after 5000 cycles). The design provides a novel approach to open up possibilities for designing high‐power NIBs.     

Improved Electrochemical Performance of Na‐Ion Batteries in Ether‐Based Electrolytes: A Case Study of ZnS Nanospheres

Sodium‐ion batteries are considered as a promising technology for large‐scale energy storage applications, owing to their low cost. However, there are many challenges for developing sodium‐ion batteries with high capacity, long cycle life, and high‐rate capability. Herein, the development of high‐performance sodium‐ion batteries using ZnS nanospheres as anode material and an ether‐based electrolyte, which exhibit improved electrochemical performance over the pure alkyl carbonate electrolytes, is reported. ZnS nanospheres deliver a high specific capacity of 1000 mA h g^?1 and high initial Columbic efficiency of 90%. Electrochemical testing and first‐principle calculations demonstrate that the ether‐based solvent can facilitate charge transport, reduce the energy barrier for sodium‐ion diffusion, and thus enhance electrochemical performances. Ex situ measurements (X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) mapping) reveal that ZnS nanospheres maintain structural integrity during the charge and discharge processes over 100 cycles. As anode material for sodium‐ion batteries, ZnS nanospheres deliver high reversible sodium storage capacity, high Coulombic efficiencies, and extended cycle life.     

A Stable Layered Oxide Cathode Material for High‐Performance Sodium‐Ion Battery

As one of the most promising cathode candidates for room‐temperature sodium‐ion batteries (SIBs), P2‐type layered oxides face the challenge of simultaneously realizing high‐rate performance while achieving long cycle life. Here, a stable Na_2/3Ni_1/6Mn_2/3Cu_1/9Mg_1/18O₂ cathode material is proposed that consists of multiple‐layer oriented stacking nanoflakes, in which the nickel sites are partially substituted by copper and magnesium, a characteristic of the material that is confirmed by multiscale scanning transmission electron microscopy and electron energy loss spectroscopy techniques. Owing to the optimal morphology structure modulation and chemical element substitution strategy, the electrode displays remarkable rate performance (73% capacity retention at 30C compared to 0.5C) and outstanding cycling stability in Na half‐cell system couple with unprecedented full battery performance. The underlying thermal stability, phase stability, and Na⁺ storage mechanisms are clearly elucidated through the systematical characterizations of electrochemical behaviors, in situ X‐ray diffraction at different temperatures, and operando X‐ray diffraction upon Na⁺ deintercalation/intercalation. Surprisingly, a quasi‐solid‐solution reaction is switched to an absolute solid‐solution reaction and a capacitive Na⁺ storage mechanism is demonstrated via quantitative electrochemical kinetics calculation during charge/discharge process. Such a simple and effective strategy might reveal a new avenue into the rational design of excellent rate capability and long cycle stability cathode materials for practical SIBs.     

An Ultralong Lifespan and Low‐Temperature Workable Sodium‐Ion Full Battery for Stationary Energy Storage

Presently, commercialization of sodium‐ion batteries (SIBs) is still hindered by the relatively poor energy‐storage performance. In addition, low‐temperature (low‐T) Na storage is another principal concern for the wide application of SIBs. Unfortunately, the Na‐transfer kinetics is extremely sluggish at low‐T, as a result, there are few reports on low‐T SIBs. Here, an advanced low‐T sodium‐ion full battery (SIFB) assembled by an anode of 3D Se/graphene composite and a high‐voltage cathode (Na₃V₂(PO₄)₂O₂F) is developed, exhibiting ultralong lifespan (over even 15 000 cycles, the capacity retention is still up to 86.3% at 1 A g^?1), outstanding low‐T energy storage performance (e.g., all values of capacity retention are >75% after 1000 cycles at temperatures from 25 to ?25 °C at 0.4 A g^?1), and high‐energy/power properties. Such ultralong lifespan signifies that the developed sodium‐ion full battery can be used for longer than 60 years, if batteries charge/discharge once a day and 80% capacity retention is the standard of battery life. As a result, the present study not only promotes the practicability and commercialization of SIBs but also points out the new developing directions of next‐generation energy storage for wider range applications.     

Nanoparticles Encapsulated in Porous Carbon Matrix Coated on Carbon Fibers: An Ultrastable Cathode for Li‐Ion Batteries

Nanostructured V₂O₅ is emerging as a new cathode material for lithium ion batteries for its distinctly high theoretic capacity over the current commercial cathodes. The main challenges associated with nanostructured V₂O₅ cathodes are structural degradation, instability of the solid‐electrolyte interface layer, and poor electron conductance, which lead to low capacity and rapid decay of cyclic stability. Here, a novel composite structure of V₂O₅ nanoparticles encapsulated in 3D networked porous carbon matrix coated on carbon fibers (V₂O₅/3DC‐CFs) is reported that effectively addresses the mentioned problems. Remarkably, the V₂O₅/3DC‐CF electrode exhibits excellent overall lithium‐storage performance, including high Coulombic efficiency, excellent specific capacity, outstanding cycling stability and rate property. A reversible capacity of ≈183 mA h g^?1 is obtained at a high current density of 10 C, and the battery retains 185 mA h g^?1 after 5000 cycles, which shows the best cycling stability reported to date among all reported cathodes of lithium ion batteries as per the knowledge. The outstanding overall properties of the V₂O₅/3DC‐CF composite make it a promising cathode material of lithium ion batteries for the power‐intensive energy storage applications.     

Ultrafast Aqueous Potassium‐Ion Batteries Cathode for Stable Intermittent Grid‐Scale Energy Storage

The inherent short‐term transience of solar and wind sources cause significant challenges for the electricity grid. Energy storage systems that can simultaneously provide high power, long cycle life, and high energy efficiency are required to accommodate the fast‐changing output fluctuations. Here, an ultrafast aqueous K‐ion battery based on the potassium‐rich mesoporous nickel ferrocyanide (II) (K₂NiFe(CN)₆·1.2H₂O) is developed. This battery achieves an unprecedented rate capability up to 500 C (8214 W kg^?1), which only takes 4.1 s for one charge or discharge. The open‐framework structure of K₂NiFe(CN)₆·1.2H₂O with small volume variation supports the capacity retention of 98.6% after 5000 cycles, and a superior round‐trip energy efficiency of 95.6% at a 5 C rate. Beyond monovalent ion storage, K₂NiFe(CN)₆·1.2H₂O can also function as a versatile high‐rate cathode for divalent‐ion batteries (Mg²⁺), trivalent‐ion batteries (Al³⁺), and hybrid full‐cells applications. These properties represent a significant step forward in the exploitation of ultrafast metal ions storage, and accelerate the development of intermittent grid‐scale energy storage technologies.     

NaCa0.6V6O16·3H2O as an Ultra‐Stable Cathode for Zn‐Ion Batteries: The Roles of Pre‐Inserted Dual‐Cations and Structural Water in V3O8 Layer

Rechargeable aqueous batteries with Zn²⁺ as a working‐ion are promising candidates for grid‐scale energy storage because of their intrinsic safety, low‐cost, and high energy‐intensity. However, suitable cathode materials with excellent Zn²⁺‐storage cyclability must be found in order for Zinc‐ion batteries (ZIBs) to find practical applications. Herein, NaCa_0.6V₆O₁₆·3H₂O (NaCaVO) barnesite nanobelts are reported as an ultra‐stable ZIB cathode material. The original capacity reaches 347 mAh g^?1 at 0.1 A g^?1, and the capacity retention rate is 94% after 2000 cycles at 2 A g^?1 and 83% after 10 000 cycles at 5 A g^?1, respectively. Through a combined theoretical and experimental approach, it is discovered that the unique V₃O₈ layered structure in NaCaVO is energetically favorable for Zn²⁺ diffusion and the structural water situated between V₃O₈ layers promotes a fast charge‐transfer and bulk migration of Zn²⁺ by enlarging gallery spacing and providing more Zn‐ion storage sites. It is also found that Na⁺ and Ca²⁺ alternately suited in V₃O₈ layers are the essential stabilizers for the layered structure, which play a crucial role in retaining long‐term cycling stability.     

A Novel High Capacity Positive Electrode Material with Tunnel‐Type Structure for Aqueous Sodium‐Ion Batteries

Aqueous sodium‐ion batteries have shown desired properties of high safety characteristics and low‐cost for large‐scale energy storage applications such as smart grid, because of the abundant sodium resources as well as the inherently safer aqueous electrolytes. Among various Na insertion electrode materials, tunnel‐type Na_0.44MnO₂ has been widely investigated as a positive electrode for aqueous sodium‐ion batteries. However, the low achievable capacity hinders its practical applications. Here, a novel sodium rich tunnel‐type positive material with a nominal composition of Na_0.66[Mn_0.66Ti_0.34]O₂ is reported. The tunnel‐type structure of Na_0.44MnO₂ obtained for this compound is confirmed by X‐ray diffraction and atomic‐scale spherical aberration‐corrected scanning transmission electron microscopy/electron energy‐loss spectrum. When cycled as positive electrode in full cells using NaTi₂(PO₄)₃/C as negative electrode in 1 m Na₂SO₄ aqueous electrolyte, this material shows the highest capacity of 76 mAh g^?1 among the Na insertion oxides with an average operating voltage of 1.2 V at a current rate of 2 C. These results demonstrate that Na_0.66[Mn_0.66Ti_0.34]O₂ is a promising positive electrode material for rechargeable aqueous sodium‐ion batteries.     

A Novel Surface Treatment Method and New Insight into Discharge Voltage Deterioration for High‐Performance 0.4Li2MnO3–0.6LiNi1/3Co1/3Mn1/3O2 Cathode Materials

The Li‐rich cathode materials have been considered as one of the most promising cathodes for high energy Li‐ion batteries. However, realization of these materials for use in Li‐ion batteries is currently limited by their intrinsic problems. To overcome this barrier, a new surface treatment concept is proposed in which a hybrid surface layer composed of a reduced graphene oxide (rGO) coating and a chemically activated layer is created. A few layers of GO are first coated on the surface of the Li‐rich cathode material, followed by a hydrazine treatment to produce the reducing agent of GO and the chemical activator of the Li₂MnO₃ phase. Compared to previous studies, this surface treatment provides substantially improved electrochemical performance in terms of initial Coulombic effiency and retention of discharge voltage. As a result, the surface‐treated 0.4Li­₂MnO_3–0.6LiNi_1/3Co_1/3Mn_1/3O₂ exhibits a high capacity efficiency of 99.5% during the first cycle a the discharge capacity of 250 mAh g^?1 (2.0–4.6 V under 0.1C), 94.6% discharge voltage retention during 100 cycles (1C) and the superior capacity retention of 60% at 12C at 24 °C.     

A Low‐Cost Durable Na‐FeCl2 Battery with Ultrahigh Rate Capability

Na‐based batteries have long been regarded as an inexpensive, sustainable candidate for large‐scale stationary energy storage applications. Unfortunately, the market penetration of conventional Na‐NiCl₂ batteries is approaching its limit for several reasons, including limited rate capability and high Ni cost. Herein, a Na‐FeCl₂ battery operating at 190 °C is reported that allows a capacity output of 116 mAh g^?1 at an extremely high current density of 33.3 mA cm^?2 (≈0.6C). The superior rate performance is rooted in the intrinsically fast kinetics of the Fe/Fe²⁺ redox reaction. Furthermore, it is demonstrated that a small amount of Ni additive (10 mol%) effectively mitigates capacity fading of the Fe/NaCl cathode caused by Fe particle pulverization during long‐term cycling. The modified Fe/Ni cathode exhibits excellent cycling stability, maintaining a discharge energy density of over 295 Wh kg^?1 for 200 cycles at 10 mA cm^?2 (≈C/5).     

Construction of Hierarchical K1.39Mn3O6 Spheres via AlF3 Coating for High‐Performance Potassium‐Ion Batteries

Potassium‐ion batteries are attracting great interest for emerging large‐scale energy storage owing to their advantages such as low cost and high operational voltage. However, they are still suffering from poor cycling stability and sluggish thermodynamic kinetics, which inhibits their practical applications. Herein, the synthesis of hierarchical K_1.39Mn₃O₆ microspheres as cathode materials for potassium‐ion batteries is reported. Additionally, an effective AlF₃ surface coating strategy is applied to further improve the electrochemical performance of K_1.39Mn₃O₆ microspheres. The as‐synthesized AlF₃ coated K_1.39Mn₃O₆ microspheres show a high reversible capacity (about 110 mA h g^?1 at 10 mA g^?1), excellent rate capability, and cycling stability. Galvanostatic intermittent titration technique results demonstrate that the increased diffusion kinetics of potassium‐ion insertion and extraction during discharge and charge processes benefit from both the hierarchical sphere structure and surface modification. Furthermore, ex situ X‐ray diffraction measurements reveal that the irreversible structure evolution can be significantly mitigated via surface modification. This work sheds light on rational design of high‐performance cathode materials for potassium‐ion batteries.     

Layer‐by‐Layer Na3V2(PO4)3 Embedded in Reduced Graphene Oxide as Superior Rate and Ultralong‐Life Sodium‐Ion Battery Cathode

Na₃V₂(PO₄)₃ (NVP) is regarded as a promising cathode for advanced sodium‐ion batteries (SIBs) due to its high theoretical capacity and stable sodium (Na) super ion conductor (NASICON) structure. However, strongly impeded by its low electronic conductivity, the general NVP delivers undesirable rate capacity and fails to meet the demands for quick charge. Herein, a novel and facile synthesis of layer‐by‐layer NVP@reduced graphene oxide (rGO) nanocomposite is presented through modifying the surface charge of NVP gel precursor. The well‐designed layered NVP@rGO with confined NVP nanocrystal in between rGO layers offers high electronic and ionic conductivity as well as stable structure. The NVP@rGO nanocomposite with merely ≈3.0 wt% rGO and 0.5 wt% amorphous carbon, yet exhibits extraordinary electrochemical performance: a high capacity (118 mA h g^?1 at 0.5 C attaining the theoretical value), a superior rate capability (73 mA h g^?1 at 100 C and even up to 41 mA h g^?1 at 200 C), ultralong cyclability (70.0% capacity retention after 15 000 cycles at 50 C), and stable cycling performance and excellent rate capability at both low and high operating temperatures. The proposed method and designed layer‐by‐layer active nanocrystal@rGO strategy provide a new avenue to create nanostructures for advanced energy storage applications.     

A Practicable Li/Na‐Ion Hybrid Full Battery Assembled by a High‐Voltage Cathode and Commercial Graphite Anode: Superior Energy Storage Performance and Working Mechanism

With the rapidly growing demand for low‐cost and safe energy storage, the advanced battery concepts have triggered strong interests beyond the state‐of‐the‐art Li‐ion batteries (LIBs). Herein, a novel hybrid Li/Na‐ion full battery (HLNIB) composed of the high‐energy and lithium‐free Na₃V₂(PO₄)₂O₂F (NVPOF) cathode and commercial graphite anode mesophase carbon micro beads is for the first time designed. The assembled HLNIBs exhibit two high working voltage at about 4.05 and 3.69 V with a specific capacity of 112.7 mA h g^?1. Its energy density can reach up to 328 W h kg^?1 calculated from the total mass of both cathode and anode materials. Moreover, the HLNIBs show outstanding high‐rate capability, long‐term cycle life, and excellent low‐temperature performance. In addition, the reaction kinetics and Li/Na‐insertion/extraction mechanism into/out NVPOF is preliminarily investigated by the galvanostatic intermittent titration technique and ex situ X‐ray diffraction. This work provides a new and profound direction to develop advanced hybrid batteries.     

K‐Birnessite Electrode Obtained by Ion Exchange for Potassium‐Ion Batteries: Insight into the Concerted Ionic Diffusion and K Storage Mechanism

Novel and low‐cost rechargeable batteries are of considerable interest for application in large‐scale energy storage systems. In this context, K‐Birnessite is synthesized using a facile solid‐state reaction as a promising cathode for potassium‐ion batteries. During synthesis, an ion exchange protocol is applied to increase K content in the K‐Birnessite electrode, which results in a reversible capacity as high as 125 mAh g^?1 at 0.2 C. Upon K⁺ exchange the reversible phase transitions are verified by in situ X‐ray diffraction (XRD) characterization. The underlying mechanism is further revealed to be the concerted K⁺ ion diffusion with quite low activation energies by first‐principle simulations. These new findings provide new insights into electrode process kinetics, and lay a solid foundation for material design and optimization of potassium‐ion batteries for large‐scale energy storage.     

The Sodium Storage Mechanism in Tunnel‐Type Na0.44MnO2 Cathodes and the Way to Ensure Their Durable Operation

Tunnel‐type sodium manganese oxide is a promising cathode material for aqueous/nonaqueous sodium‐ion batteries, however its storage mechanism is not fully understood, in part due to the complicated sodium intercalation process. In addition, low cyclability due to manganese dissolution has limited its practical application in rechargeable batteries. Here, the intricate sodium intercalation mechanism of Na_0.44MnO₂ is revealed by combination of electrochemical characterization, structure determination from powder X‐ray diffraction data, 3D bond valence difference maps, and barrier‐energy calculations of the sodium diffusion. NaI is proposed as an important electrolyte solution additive. It is shown to form a thin, beneficial, and durable cathode surface film that prevents manganese dissolution. The addition of 0.01 m NaI to electrolyte solutions based on alkyl carbonate solvents and NaClO₄ greatly improves the cycling efficiency, raising the capacity retention from 86% to 96% after 600 cycles. This study determines the core aspects of the sodium intercalation mechanism in tunnel‐type sodium manganese oxide and shows how it can serve as a durable cathode material for rechargeable Na batteries.     

KVOPO4: A New High Capacity Multielectron Na‐Ion Battery Cathode

Sodium ion batteries have attracted much attention in recent years, due to the higher abundance and lower cost of sodium, as an alternative to lithium ion batteries. However, a major challenge is their lower energy density. In this work, we report a novel multi‐electron cathode material, KVOPO₄, for sodium ion batteries. Due to the unique polyhedral framework, the V³⁺ ? V⁴⁺ ? V⁵⁺ redox couple was for the first time fully activated by sodium ions in a vanadyl phosphate phase. The KVOPO₄ based cathode delivered reversible multiple sodium (i.e. maximum 1.66 Na⁺ per formula unit) storage capability, which leads to a high specific capacity of 235 Ah kg^?1. Combining an average voltage of 2.56 V vs. Na/Na⁺, a high practical energy density of over 600 Wh kg^?1 was achieved, the highest yet reported for any sodium cathode material. The cathode exhibits a very small volume change upon cycling (1.4% for 0.64 sodium and 8.0% for 1.66 sodium ions). Density functional theory (DFT) calculations indicate that the KVOPO₄ framework is a 3D ionic conductor with a reasonably, low Na⁺ migration energy barrier of ≈450 meV, in line with the good rate capability obtained.     

Ethylene Carbonate‐Free Electrolytes for High‐Nickel Layered Oxide Cathodes in Lithium‐Ion Batteries

Layered lithium nickel oxide (LiNiO₂) can provide very high energy density among intercalation cathode materials for lithium‐ion batteries, but suffers from poor cycle life and thermal‐abuse tolerance with large lithium utilization. In addition to stabilization of the active cathode material, a concurrent development of electrolyte systems of better compatibility is critical to overcome these limitations for practical applications. Here, with nonaqueous electrolytes based on exclusively aprotic acyclic carbonates free of ethylene carbonate (EC), superior electrochemical and thermal characteristics are obtained with an ultrahigh‐nickel cathode (LiNi_0.94Co_0.06O₂), capable of reaching a 235 mA h g^?1 specific capacity. Pouch‐type graphite|LiNi_0.94Co_0.06O₂ cells in EC‐free electrolytes withstand several hundred charge–discharge cycles with minor degradation at both ambient and elevated temperatures. In thermal‐abuse tests, the cathode at full charge, while reacting aggressively with EC‐based electrolytes below 200 °C, shows suppressed self‐heating without EC. Through 3D chemical and structural analyses, the intriguing impact of EC is visualized in aggravating unwanted surface parasitic reactions and irreversible bulk structural degradation of the cathode at high voltages. These results provide important insights in designing high‐energy electrodes for long‐lasting and reliable lithium‐ion batteries.