A New Spinel‐Layered Li‐Rich Microsphere as a High‐Rate Cathode Material for Li‐Ion Batteries

Li‐rich layered materials are considered to be the promising low‐cost cathodes for lithium‐ion batteries but they suffer from poor rate capability despite of efforts toward surface coating or foreign dopings. Here, spinel‐layered Li‐rich Li‐Mn‐Co‐O microspheres are reported as a new high‐rate cathode material for Li‐ion batteries. The synthetic procedure is relatively simple, involving the formation of uniform carbonate precursor under solvothermal conditions and its subsequent transformation to an assembled microsphere that integrates a spinel‐like component with a layered component by a heat treatment. When calcined at 700 °C, the amount of transition metal Mn and Co in the Li‐Mn‐Co‐O microspheres maintained is similar to at 800 °C, while the structures of constituent particles partially transform from 2D to 3D channels. As a consequence, when tested as a cathode for lithium‐ion batteries, the spinel‐layered Li‐rich Li‐Mn‐Co‐O microspheres obtained at 700 °C show a maximum discharge capacity of 185.1 mA h g^?1 at a very high current density of 1200 mA g^?1 between 2.0 and 4.6 V. Such a capacity is among the highest reported to date at high charge‐discharge rates. Therefore, the present spinel‐layered Li‐rich Li‐Mn‐Co‐O microspheres represent an attractive alternative to high‐rate electrode materials for lithium‐ion batteries.     

Unraveling the Dual Functionality of High‐Donor‐Number Anion in Lean‐Electrolyte Lithium‐Sulfur Batteries

Minimizing electrolyte use is essential to achieve high practical energy density of lithium–sulfur (Li–S) batteries. However, the sulfur cathode is more readily passivated under a lean electrolyte condition, resulting in low sulfur utilization. In addition, continuous electrolyte decomposition on the Li metal anode aggravates the problem, provoking rapid capacity decay. In this work, the dual functionalities of NO₃^? as a high‐donor‐number (DN) salt anion is presented, which improves the sulfur utilization and cycling stability of lean‐electrolyte Li–S batteries. The NO₃^? anion elevates the solubility of the sulfur species based on its high electron donating ability, achieving a high sulfur utilization of above 1200 mA h g^?1. Furthermore, the anion suppresses electrolyte decomposition on the Li metal by regulating the lithium ion (Li⁺) solvation sheath, enhancing the cycle performance of the lean electrolyte cell. By understanding the anionic effects, this work demonstrates the potential of the high‐DN electrolyte, which is beneficial for both the cathode and anode of Li–S batteries.     

Advanced Electrolytes for Fast‐Charging High‐Voltage Lithium‐Ion Batteries in Wide‐Temperature Range

LiNi_xMn_yCo_1?x?yO₂ (NMC) cathode materials with Ni ≥ 0.8 have attracted great interest for high energy‐density lithium‐ion batteries (LIBs) but their practical applications under high charge voltages (e.g., 4.4 V and above) still face significant challenges due to severe capacity fading by the unstable cathode/electrolyte interface. Here, an advanced electrolyte is developed that has a high oxidation potential over 4.9 V and enables NMC811‐based LIBs to achieve excellent cycling stability in 2.5–4.4 V at room temperature and 60 °C, good rate capabilities under fast charging and discharging up to 3C rate (1C = 2.8 mA cm^?2), and superior low‐temperature discharge performance down to ?30 °C with a capacity retention of 85.6% at C/5 rate. It is also demonstrated that the electrode/electrolyte interfaces, not the electrolyte conductivity and viscosity, govern the LIB performance. This work sheds light on a very promising strategy to develop new electrolytes for fast‐charging high‐energy LIBs in a wide‐temperature range.     

Lithium‐Pretreated Hard Carbon as High‐Performance Sodium‐Ion Battery Anodes

Hard carbon (HC) is the state‐of‐the‐art anode material for sodium‐ion batteries (SIBs). However, its performance has been plagued by the limited initial Coulombic efficiency (ICE) and mediocre rate performance. Here, experimental and theoretical studies are combined to demonstrate the application of lithium‐pretreated HC (LPHC) as high‐performance anode materials for SIBs by manipulating the solid electrolyte interphase in tetraglyme (TEGDME)‐based electrolyte. The LPHC in TEGDME can 1) deliver > 92% ICE and ≈220 mAh g^?1 specific capacity, twice of the capacity (≈100 mAh g^?1) in carbonate electrolyte; 2) achieve > 85% capacity retention over 1000 cycles at 1000 mA g^?1 current density (4 C rate, 1 C = 250 mA g^?1) with a specific capacity of ≈150 mAh g^?1, ≈15 times of the capacity (10 mAh g^?1) in carbonate. The full cell of Na₃V₂(PO₄)₃‐LPHC in TEGDME demonstrated close to theoretical specific capacity of ≈98 mAh g^?1 based on Na₃V₂(PO₄)₃ cathode, ≈2.5 times of the value (≈40 mAh g^?1) with nontreated HC. This work provides new perception on the anode development for SIBs.     

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.     

Viscoelastic and Nonflammable Interface Design–Enabled Dendrite‐Free and Safe Solid Lithium Metal Batteries

Herein, a composite polymer electrolyte with a viscoelastic and nonflammable interface is designed to handle the contact issue and preclude Li dendrite formation. The composite polymer electrolyte (cellulose acetate/polyethylene glycol/Li_1.4Al_0.4Ti_1.6P₃O₁₂) exhibits a wide electrochemical window of 5 V (vs Li⁺/Li), a high Li⁺ transference number of 0.61, and an excellent ionic conductivity of above 10^?4 S cm^?1 at 60 °C. In particular, the intimate contact, low interfacial impedance, and fast ion‐transport process between the electrodes and solid electrolytes can be simultaneously achieved by the viscoelastic and nonflammable layer. Benefiting from this novel design, solid lithium metal batteries with either LiFePO₄ or LiCoO₂ as cathode exhibit superior cyclability and rate capability, such as a discharge capacity of 157 mA h g^?1 after 100 cycles at C/2 and 97 mA h g^?1 at 5C for LiFePO₄ cathode. Moreover, the smooth and uniform Li surface after long‐term cycling confirms the successful suppression of dendrite formation. The viscoelastic and nonflammable interface modification of solid electrolytes provides a promising and general strategy to handle the interfacial issues and improves the operative safety of solid lithium metal batteries.     

High‐Performance All‐Solid‐State Lithium–Sulfur Batteries Enabled by Amorphous Sulfur‐Coated Reduced Graphene Oxide Cathodes

Safety and the polysulfide shuttle reaction are two major challenges for liquid electrolyte lithium–sulfur (Li–S) batteries. Although use of solid‐state electrolytes can overcome these two challenges, it also brings new challenges by increasing the interface resistance and stress/strain. In this work, the interface resistance and stress/strain of sulfur cathodes are significantly reduced by conformal coating ≈2 nm sulfur (S) onto reduced graphene oxide (rGO). An Li–S full cell consisting of an rGO@S‐Li₁₀GeP₂S₁₂‐acetylene black (AB) composite cathode is evaluated. At 60 °C, the all‐solid‐state Li–S cell demonstrates a similar electrochemical performance as in liquid organic electrolyte, with high rate capacities of 1525.6, 1384.5, 1336.3, 903.2, 502.6, and 204.7 mA h g^?1 at 0.05, 0.1, 0.5, 1.0, 2.0, and 5.0 C, respectively. It can maintain a high and reversible capacity of 830 mA h g^?1 at 1.0 C for 750 cycles. The uniform distribution of the rGO@S nanocomposite in the Li₁₀GeP₂S₁₂‐AB matrix generates uniform volume changes during lithiation/delithiation, significantly reducing the stress/strain, thus extending the cycle life. Minimization of the stress/strain of solid cells is the key for a long cycle life of all‐solid‐state Li–S batteries.     

Thermal Induced Strain Relaxation of 1D Iron Oxide for Solid Electrolyte Interphase Control and Lithium Storage Improvement

High energy lithium ion battery based on multi‐electron redox reaction is often accompanied by inherent large volume expansions, sluggish kinetics, and unstable solid electrolyte interphase layer, leading to capacity failure. Here, thermal induced strain relaxation is proposed to realize the solid electrolyte interphase control. It is demonstrated that through thermal treatment, lattice strain is well released and defect density is well reduced, facilitating the charge transfer, improving the interparticle contacts and the contacts at the interface of electrode to withstand the huge volume expansion/contraction during cycling. In this way, the as‐prepared α‐Fe₂O₃ electrode at 800 °C with no protective shell shows an outstanding reversible capacity of 1200 mA h g^?1 at 100 mA g^?1 and an excellent high‐rate cyclability with a capacity fading of 0.056% per cycle for 1200 cycles at 5 A g^?1. It is expected that such findings facilitate the applications of high capacity anode and cathode material systems that undergo large volume expansion.     

Insight of a Phase Compatible Surface Coating for Long‐Durable Li‐Rich Layered Oxide Cathode

Li‐rich layered oxides (LLOs) can deliver almost double the capacity of conventional electrode materials such as LiCoO₂ and LiMn₂O₄; however, voltage fade and capacity degradation are major obstacles to the practical implementation of LLOs in high‐energy lithium‐ion batteries. Herein, hexagonal La_0.8Sr_0.2MnO_3?y (LSM) is used as a protective and phase‐compatible surface layer to stabilize the Li‐rich layered Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ (LM) cathode material. The LSM is Mn? O? M bonded at the LSM/LM interface and functions by preventing the migration of metal ions in the LM associated with capacity degradation as well as enhancing the electrical transfer and ionic conductivity at the interface. The LSM‐coated LM delivers an enhanced reversible capacity of 202 mAh g^?1 at 1 C (260 mA g^?1) with excellent cycling stability and rate capability (94% capacity retention after 200 cycles and 144 mAh g^?1 at 5 C). This work demonstrates that interfacial bonding between coating and bulk material is a successful strategy for the modification of LLO electrodes for the next‐generation of high‐energy Li‐ion batteries.     

Superassembly of Porous Fetet(NiFe)octO Frameworks with Stable Octahedron and Multistage Structure for Superior Lithium–Oxygen Batteries

Promising lithium–oxygen batteries (LOBs) with extra‐high capacities have attracted increasing attention for use in future electric devices. However, the challenges facing this complicated battery system still limit their practical applications. These challenges mainly consist of inefficient product evolution and low‐activity catalysts. In present work, a cation occupying, modified 3D‐architecture NiFeO cubic spinel is constructed via superassembly strategy to achieve a high rate, stable electrocatalyst for LOBs. The octahedron predominant spinel provides a stable polycrystal structure and optimized electronic structure, which dominates the discharge/charge products evolution with multiformation kinetics of crystal Li₂O₂ and Li_2?xO₂ at low and high rate conditions and energetically favors the mass transport between the electrode/electrolyte interface. Simultaneously, the porous NiFeO framework provides adequate spaces for Li₂O₂ accommodation and complex channels for sufficient electrolyte, oxygen, and ion transportation, which dramatically alter the cathode catalysis for an unprecedented performance. As a consequence, a large specific capacity of 23413 mAh g^?1 and an excellent cyclability of 193 cycles at a high current of 1000 mA g^?1, and 300 cycles at a current of 500 mA g^?1, are achieved. The present work provides intrinsic insights into designing high‐performance metal oxide electrocatalysts for Li–O₂ batteries with fine‐tuned electronic and frame structure.     

An Improved Li–SeS2 Battery with High Energy Density and Long Cycle Life

Selenium–sulfur solid solutions are a class of potential cathode materials for high energy batteries, since they have higher theoretical capacities than selenium and improved conductivity over sulfur. Here, a high‐performance cathode material by confining 70 wt% of SeS₂ in a highly ordered mesoporous carbon (CMK‐3) framework with a polydopamine (PDA) protection sheath for novel Li–Se/S batteries is reported. With a relatively high SeS₂ mass loading of 2.6–3 mg cm^?2, the CMK‐3/SeS₂@PDA cathode exhibits a high capacity of >1200 mA h g^?1 at 0.2 A g^?1, excellent C‐rate capability of 535 mA h g^?1 at 5 A g^?1, and prolonged life over 500 cycles. Benefitting from the unique advantages of SeS₂ and the rationally designed host framework, this new cathode material demonstrates a feasible strategy to overcome the bottlenecks of current Li–S systems for high energy density rechargeable batteries.     

Slurry‐Fabricable Li+‐Conductive Polymeric Binders for Practical All‐Solid‐State Lithium‐Ion Batteries Enabled by Solvate Ionic Liquids

For mass production of all‐solid‐state lithium‐ion batteries (ASLBs) employing highly Li⁺ conductive and mechanically sinterable sulfide solid electrolytes (SEs), the wet‐slurry process is imperative. Unfortunately, the poor chemical stability of sulfide SEs severely restrict available candidates for solvents and in turn polymeric binders. Moreover, the binders interrupt Li⁺‐ionic contacts at interfaces, resulting in the below par electrochemical performance. In this work, a new scalable slurry fabrication protocol for sheet‐type ASLB electrodes made of Li⁺‐conductive polymeric binders is reported. The use of intermediate‐polarity solvent (e.g., dibromomethane) for the slurry allows for accommodating Li₆PS₅Cl and solvate‐ionic‐liquid‐based polymeric binders (NBR‐Li(G3)TFSI, NBR: nitrile?butadiene rubber, G3: triethylene glycol dimethyl ether, LiTFSI: lithium bis(trifluoromethanesulfonyl)imide) together without suffering from undesirable side reactions or phase separation. The LiNi_0.6Co_0.2Mn_0.2O₂ and Li₄Ti₅O₁₂ electrodes employing NBR‐Li(G3)TFSI show high capacities of 174 and 160 mA h g^?1 at 30 °C, respectively, which are far superior to those using conventional NBR (144 and 76 mA h g^?1). Moreover, high areal capacity of 7.4 mA h cm^?2 is highlighted for the LiNi_0.7Co_0.15Mn_0.15O₂ electrodes with ultrahigh mass loading of 45 mg cm^?2. The facilitated Li⁺‐ionic contacts at interfaces paved by NBR‐Li(G3)TFSI are evidenced by the complementary analysis from electrochemical and ⁷Li nuclear magnetic resonance measurements.     

Countersolvent Electrolytes for Lithium‐Metal Batteries

Development of electrolytes that simultaneously have high ionic conductivity, wide electrochemical window, and lithium dendrite suppression ability is urgently required for high‐energy lithium‐metal batteries (LMBs). Herein, an electrolyte is designed by adding a countersolvent into LiFSI/DMC (lithium bis(fluorosulfonyl)amide/dimethyl carbonate) electrolytes, forming countersolvent electrolytes, in which the countersolvent is immiscible with the salt but miscible with the carbonate solvents. The solvation structure and unique properties of the countersolvent electrolyte are investigated by combining electroanalytical technology with a Molecular Dynamics simulation. Introducing the countersolvent alters the coordination shell of Li⁺ cations and enhances the interaction between Li⁺ cations and FSI^? anions, which leads to the formation of a LiF‐rich solid electrolyte interphase, arising from the preferential reduction of FSI^? anions. Notably, the countersolvent electrolyte suppresses Li dendrites and enables stable cycling performance of a Li||NCM622 battery at a high cut‐off voltage of 4.6 V at both 25 and 60 °C. This study provides an avenue to understand and design electrolytes for high‐energy LMBs in the future.     

Polysulfide‐Shuttle Control in Lithium‐Sulfur Batteries with a Chemically/Electrochemically Compatible NaSICON‐Type Solid Electrolyte

A NaSICON‐type Li⁺‐ion conductive membrane with a formula of Li_{1+ x} Y _x Zr_{2? x} (PO₄)₃ (LYZP) (x = 0–0.15) has been explored as a solid‐electrolyte/separator to suppress polysulfide‐crossover in lithium‐sulfur (Li‐S) batteries. The LYZP membrane with a reasonable Li⁺‐ion conductivity shows both favorable chemical compatibility with the lithium polysulfide species and exhibits good electrochemical stability under the operating conditions of the Li‐S batteries. Through an integration of the LYZP solid electrolyte with the liquid electrolyte, the hybrid Li‐S batteries show greatly enhanced cyclability in contrast to the conventional Li‐S batteries with the porous polymer (e.g., Celgard) separator. At a rate of C/5, the hybrid Li ||LYZP|| Li₂S₆ batteries developed in this study (with a Li‐metal anode, a liquid/LYZP hybrid electrolyte, and a dissolved lithium polysulfide cathode) delivers an initial discharge capacity of ≈1000 mA h g^?1 (based on the active sulfur material) and retains ≈90% of the initial capacity after 150 cycles with a low capacity fade‐rate of <0.07% per cycle.     

High‐Fluorinated Electrolytes for Li–S Batteries

Rechargeable Li–S batteries are regarded as one of the most promising next‐generation energy‐storage systems. However, the inevitable formation of Li dendrites and the shuttle effect of lithium polysulfides significantly weakens electrochemical performance, preventing its practical application. Herein, a new class of localized high‐concentration electrolyte (LHCE) enabled by adding inert fluoroalkyl ether of 1H,1H,5H‐octafluoropentyl‐1,1,2,2‐tetrafluoroethyl ether into highly‐concentrated electrolytes (HCE) lithium bis(fluorosulfonyl) imide/dimethoxyether (DME) system is reported to suppress Li dendrite formation and minimize the solubility of the high‐order polysulfides in electrolytes, thus reducing the amount of electrolyte in cells. Such a unique LHCE can achieve a high coulombic efficiency of Li plating/stripping up to 99.3% and completely suppressing the shuttling effect, thus maintaining a S cathode capacity of 775 mAh g^?1 for 150 cycles with a lean electrolyte of 4.56 g A^?1 h^?1. The LHCE reduces the solubility of lithium polysulfides, allowing the Li/S cell to achieve super performance in a lean electrolyte. This conception of using inert diluents in a highly concentrated electrolyte can accelerate commercialization of Li–S battery technology.     

Nature of FeSe2/N‐C Anode for High Performance Potassium Ion Hybrid Capacitor

Potassium ion hybrid capacitors have great potential for large‐scale energy devices, because of the high power density and low cost. However, their practical applications are hindered by their low energy density, as well as electrolyte decomposition and collector corrosion at high potential in potassium bis(fluoro‐sulfonyl)imide‐based electrolyte. Therefore, anode materials with high capacity, a suitable voltage platform, and stability become a key factor. Here, N‐doping carbon‐coated FeSe₂ clusters are demonstrated as the anode material for a hybrid capacitor, delivering a reversible capacity of 295 mAh g^?1 at 100 mA g^?1 over 100 cycles and a high rate capability of 158 mAh g^?1 at 2000 mA g^?1 over 2000 cycles. Meanwhile, through density functional theory calculations, in situ X‐ray diffraction, and ex situ transmission electron microscopy, the evolution of FeSe₂ to Fe₃Se₄ for the electrochemical reaction mechanism is successfully revealed. The battery‐supercapacitor hybrid using commercial activated carbon as the cathode and FeSe₂/N‐C as the anode is obtained. It delivers a high energy density of 230 Wh kg^?1 and a power density of 920 W kg^?1 (the energy density and power density are calculated based on the total mass of active materials in the anode and cathode).     

Carbon‐Sheathed MoS2 Nanothorns Epitaxially Grown on CNTs: Electrochemical Application for Highly Stable and Ultrafast Lithium Storage

Molybdenum disulfide (MoS₂), which possesses a layered structure and exhibits a high theoretical capacity, is currently under intensive research as an anode candidate for next generation of Li‐ion batteries. However, unmodified MoS₂ suffers from a poor cycling stability and an inferior rate capability upon charge/discharge processes. Herein, a unique nanocomposite comprising MoS₂ nanothorns epitaxially grown on the backbone of carbon nanotubes (CNTs) and coated by a layer of amorphous carbon is synthesized via a simple method. The epitaxial growth of MoS₂ on CNTs results in a strong chemical coupling between active nanothorns and carbon substrate via C? S bond, providing a high stability as well as a high‐efficiency electron‐conduction/ion‐transportation system on cycling. The outer carbon layer can well‐accommodate the structural strain in the electrode upon lithium‐ion insertion/extraction. When employed as an anode for lithium storage, the prepared material exhibits remarkable electrochemical properties with a high specific capacity of 982 mA h g^?1 at 0.1 A g^?1, as well as excellent long‐cycling stability (905 mA h g^?1 at 1 A g^?1 after 500 cycles) and superior rate capability, confirming its potential application in high‐performance Li‐ion batteries.     

Ultrathin Anatase TiO2 Nanosheets Embedded with TiO2‐B Nanodomains for Lithium‐Ion Storage: Capacity Enhancement by Phase Boundaries

A new form of TiO₂ microspheres comprised of anatase/TiO₂‐B ultrathin composite nanosheets has been synthesized successfully and used as Li‐ion storage electrode material. By comparison between samples obtained with different annealing temperatures, it is demonstrated that the anatase/TiO₂‐B coherent interfaces may contribute additional lithium storage venues due to a favorable charge separation at the boundary between the two phases. The as‐prepared hierarchical nanostructures show capacities of 180 and 110 mAh g^?1 after 1000 cycles at current densities of 3400 and 8500 mA g^?1. The ultrathin nanosheet structure which provides short lithium diffusion length and high electrode/electrolyte contact area also accounts for the high capacity and long‐cycle stability.     

Lithium Difluorophosphate‐Based Dual‐Salt Low Concentration Electrolytes for Lithium Metal Batteries

The safety hazards and low Coulombic efficiency originating from the growth of lithium dendrites and decomposition of the electrolyte restrict the practical application of Li metal batteries (LMBs). Inspired by the low cost of low concentration electrolytes (LCEs) in industrial applications, dual‐salt LCEs employing 0.1 m Li difluorophosphate (LiDFP) and 0.4 m LiBOB/LiFSI/LiTFSI are proposed to construct a robust and conductive interphase on a Li metal anode. Compared with the conventional electrolyte using 1 m LiPF₆, the ionic conductivity of LCEs is reduced but the conductivity decrement of the separator immersed in LCEs is moderate, especially for the LiDFP–LiFSI and LiDFP–LiTFSI electrolytes. The accurate Coulombic efficiency (CE) of the Li||Cu cells increases from 83.3% (electrolyte using 1 m LiPF₆) to 97.6%, 94.5%, and 93.6% for LiDFP–LiBOB, LiDFP–LiFSI, and LiDFP–LiTFSI electrolytes, respectively. The capacity retention of Li||LiFePO₄ cells using the LiDFP–LiBOB electrolyte reaches 95.4% along with a CE over 99.8% after 300 cycles at a current density of 2.0 mA cm^?2 and the capacity reaches 103.7 mAh g^?1 at a current density of up to 16.0 mA cm^?2. This work provides a dual‐salt LCE for practical LMBs and presents a new perspective for the design of electrolytes for LMBs.     

Radially Oriented Single‐Crystal Primary Nanosheets Enable Ultrahigh Rate and Cycling Properties of LiNi0.8Co0.1Mn0.1O2 Cathode Material for Lithium‐Ion Batteries

Ni‐rich Li[Ni_xCo_yMn_1?x?y]O₂ (x ≥ 0.8) layered oxides are the most promising cathode materials for lithium‐ion batteries due to their high reversible capacity of over 200 mAh g^?1. Unfortunately, the anisotropic properties associated with the α‐NaFeO₂ structured crystal grains result in poor rate capability and insufficient cycle life. To address these issues, a micrometer‐sized Ni‐rich LiNi_0.8Co_0.1Mn_0.1O₂ secondary cathode material consisting of radially aligned single‐crystal primary particles is proposed and synthesized. Concomitant with this unique crystallographic texture, all the exposed surfaces are active {010} facets, and 3D Li⁺ ion diffusion channels penetrate straightforwardly from surface to center, remarkably improving the Li⁺ diffusion coefficient. Moreover, coordinated charge–discharge volume change upon cycling is achieved by the consistent crystal orientation, significantly alleviating the volume‐change‐induced intergrain stress. Accordingly, this material delivers superior reversible capacity (203.4 mAh g^?1 at 3.0–4.3 V) and rate capability (152.7 mAh g^?1 at a current density of 1000 mA g^?1). Further, this structure demonstrates excellent cycling stability without any degradation after 300 cycles. The anisotropic morphology modulation provides a simple, efficient, and scalable way to boost the performance and applicability of Ni‐rich layered oxide cathode materials.