Stabilizing Nickel Ions by Local Magnetic Order Modulation for Durable Ultrahigh-Nickel Cathode

Stabilizing Nickel Ions by Local Magnetic Order Modulation for Durable Ultrahigh-Nickel Cathode | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Stabilizing Nickel Ions by Local Magnetic Order Modulation for Durable Ultrahigh-Nickel Cathode yanqiong tan, Shuaijing Ji, yulu zhang, Shun Tang, Yuancheng Cao, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8578612/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract We report successfully synthesized ultra-high-performance LiNi 0.95 Mn 0.05 O 2 (NM) and its TiO 2 -doped modified material Li[Ni 0.95 Mn 0.05 ] 1− x Ti x O 2 (0 ≤ x ≤ 0.1) (LNMTO) via a high-temperature solid-state method. The introduction of TiO 2 as a dopant aims to stabilize the crystal structure, modulate the local magnetic order of nickel ions, reduce Ni/Li exchange and magnetic frustration, enhancing electrochemical stability. X-ray diffraction (XRD) results confirm successful TiO 2 doping into the lattice, effectively increasing the interlayer spacing. Magnetic measurements reveal weakened average exchange interactions. The introduction of non-magnetic Ti 4+ ions significantly alters the low-temperature magnetic ordering state, indicating that Ti 4+ modulates the super-exchange interactions between TM layer, forming a more stable antiferromagnetic coupling network. Electrochemical testing confirms that at Ti 4+ doping concentration of 2.5%, the Li[Ni 0.95 Mn 0.05 ] 1− x Ti x O 2 (0 ≤ x ≤ 0.1) cathode material exhibits optimal capacity retention and cycling stability. After 40 cycles, the capacity retention increases from 70.5% to 95%, while the specific discharge capacity increased from 140 mAh g − 1 to 155 mAh g − 1 after stable cycling. This study reveals that TiO 2 doping induced local magnetic ordering in LiNi 0.95 Mn 0.05 O 2 is an effective strategy for stabilizing the crystal structure and enhancing the electrochemical stability of high-nickel cathode materials. Lithium-ion battery High-nickel cathode material Ti doping Local magnetic order Cation mixing Cycling stability Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Introduction Recent studies indicate that the degradation of electrochemical behaviour in high-nickel materials (such as LiNiO₂ and its derivatives) is closely associated with the magnetic interactions between nickel ions within the transition metal layer and their ordered states 1 , 2 , 3 , 4 . From the perspective of crystal field theory, Ni 3+ (t 2 g 6 eg 1 ) is a typical Jahn-Teller ion whose presence induces lattice distortion 5 , 6 . From the perspective of magnetic exchange interactions, within the trigonal lattice of LiNiO 2 -based materials, Ni ions form a complex magnetic order - intralayer ferromagnetism and interlayer antiferromagnetism through O 2− -mediated super-exchange. This geometric configuration readily leads to magnetic frustration, where the antiferromagnetic interactions between neighboring spins cannot be simultaneously satisfied, trapping them in an energetically degenerate ground state 7 , 8 . This magnetic instability, synergizing with the Jahn-Teller effect and cation mixing, collectively lowers the lattice formation energy barrier. Consequently, the material becomes more prone to phase transitions and structural degradation under electrochemical cycling stresses. Therefore, Unlike traditional structural modification strategies, regulating local magnetic order and resolving magnetic frustration offer a novel approach to stabilizing high-nickel cathode materials 9 . Ion doping serves as an effective means to achieve this goal. Among various dopants, Ti 4+ exhibits unique advantages due to its stable 3 d 0 electronic configuration, strong Ti-O bonding, and ability to regulate charge distribution 10 , 11 , 12 , 13 , 14 , 15 , 16 . We hypothesize that introducing non-magnetic Ti 4+ into the transition metal layer disrupts the symmetric triangular lattice formed by Ni ions. By diluting magnetic ions and reconfiguring super-exchange pathways, it effectively relieves magnetic frustration, reduces the system's magnetic free energy, and fundamentally enhances material structural stability 17 . Based on this, this study employs a high-temperature solid-state method to synthesize a series of Ti 4+ -doped Li[Ni 0.95 Mn 0.05 ] 1− x Ti x O 2 (0 ≤ x ≤ 0.1) polycrystalline samples. We aim to systematically investigate the stability modification mechanism of Ti 4+ doping in LiNi 0.95 Mn 0.05 O 2 through comprehensive crystal structure (XRD), magnetic (SQUID), and electrochemical characterization. The core of this work lies in elucidating how Ti 4+ doping synergistically reduces cation mixing and enhances lattice stability by regulating local magnetic order and suppressing magnetic resistance frustration. This ultimately achieves significant improvements in electrochemical performance, providing new theoretical foundations and practical pathways for designing next-generation high-nickel cathode materials. Experimental Method Material Synthesis Polycrystalline samples of Ti 4+ -doped LiNi 0.95 Mn 0.05 O 2 (NM-0) were prepared using the standard high-temperature solid-state method. The material was modified with Ti 4+ at doping concentrations of 0, 2.5, 5, and 10%. The precursor Ni 0.95 Mn 0.05 (OH) 2 (Dongguan Songhu Shengjian Technology Co., Ltd., China) and LiOH·H 2 O (AR, Shanghai Aladdin Bio-Chemical Technology Co., Ltd., China) were weighed at a molar ratio of 1:1.05 18 , 19 , 20 . All raw materials were precisely weighed according to the stoichiometric ratio, mixed with anhydrous ethanol in an agate mortar, and ball-milled for 12 hours to ensure thorough homogenization. The uniformly mixed slurry was dried at 80°C, and the dried precursor powder was pre-sintered at 500°C for 5 hours under air atmosphere. Subsequently, the pre-sintered product was reground and calcined at 950°C for 15 hours under an oxygen atmosphere, followed by cooling to room temperature in the furnace to obtain the final product. This process was repeated 2–3 times to yield a black powder sample. The doping sample was prepared identically to the above steps, with TiO 2 used as the doping material. Material Characterization The crystal structure of the samples was analyzed using X-ray diffraction (XRD, Bruker D8 Advance) with Cu Kα radiation ( λ = 1.5406 Å). Rietveld refinement software (e.g., GSAS) was used to refine the XRD patterns to obtain lattice parameters and cation mixing degrees. The magnetic susceptibilities and magnetization were measured by using a Quantum Design superconducting quantum interference device (SQUID) magnetometer. The magnetic susceptibility data were collected during the zero-field cooled (ZFC) heating process followed by field-cooled (FC) cooling process in the temperature range of 2–300 K under an applied magnetic field of 1000 Oe. Electrochemical Testing The active material, acetylene black, and polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 8:1:1 in N-methyl-2-pyrrolidone (NMP) to form a uniform slurry. The slurry was coated on aluminum foil current collectors and vacuum-dried at 120°C for 12 hours to prepare the cathode electrodes. CR2032-type coin cells were assembled in an argon-filled glove box using lithium metal as both the counter and reference electrodes, Celgard 2400 as the separator, and 1 M LiPF 6 in EC/DEC (1:1, v/v) as the electrolyte. Constant current charge-discharge tests were conducted using a LAND battery testing system within a voltage range of 2.7–4.3 V. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests were also performed using the LAND battery testing system. Results and Discussion Structural analysis Figure 1 displays the XRD patterns of NM9505 at different Ti doping concentrations, along with an enlarged view of the 003 peak. As shown in Fig. 1(a), the XRD diffraction peaks of NM-0, NM-2.5, NM-5, and NM-10 match those of NM9505, all belonging to the R -3m space group with a hexagonal crystal structure. hexagonal LiNiO 2 structure, with no additional impurity peaks observed 21 . This confirms that Ti 4+ has successfully intercalated into the lattice of the layered matrix material NM9505 without altering its original crystal structure. The figure shows distinct splitting in the (006)/(102) and (108)/(110) pairs of diffraction peaks for all samples, indicating an ordered layered structure 22 , 23 . The enlarged region of the (003) peak is shown in Fig. 1(b). Since the (003) peak resides in the transition metal layer plane, it reflects changes in the c-axis. Its peak position shifts slightly toward the low-angle region, indicating that the c-axis lattice parameter gradually increases with rising Ti 4+ doping concentration 24 , consistent with Gsas refinement results. This occurs because Ti 4+ ( r = 0.605 Å) possesses a larger ionic radius (Mn 4+ : r = 0.53 Å, Ni 3+ : r = 0.56 Å, Ni 2+ : r = 0.69 Å). Consequently, when Ti 4+ successfully enters the transition metal layer, the lithium interlayer spacing expands, thereby enhancing lithium-ion diffusion 25 . The refined XRD results reveal that NM-0 belongs to the space group R -3m with lattice constants a = 2.8837(1) Å, b = 2.8837(1) Å, c = 14.2207(1) Å, α = 90(1)°, β = 90 (1)°, γ = 120 (1)°, and V = 118.2595(1) Å 3 , consistent with literature reports 26 . The refinement optimization indices were R p = 3.95%, R wp = 5.1%, and λ 2 = 1.181, indicating high phase purity of the sample. the lattice parameter c gradually increases, consistent with the previously described. All samples are summarized in Table 1. All samples consists of the lithium layer and the transition metal layer, where each transition metal atom is surrounded by six oxygen atoms forming an oxygen octahedral structure, and a small amount of lithium-nickel anti-site defects occur. Magnetic Analysis Figure 2(a) shows the temperature-dependent magnetic susceptibility curves measured at a magnetic field of 1000 Oe for all samples. Zero-Field Cooling(ZFC) and Field Cooling(FC) curves exhibit obvious thermal hysteresis. ZFC and FC split prior to the magnetic transition temperature, exhibiting full peak shapes, with FC showing a slight upward trend in the low-temperature region. This is a typical manifestation of cluster glass. All samples exhibit a distinct magnetic transition at low temperatures. The magnetic transition temperature is approximately 18 K and shifts toward lower temperatures with increasing doping concentration. This indicates that the exchange interactions responsible for antiferromagnetic ordering within the material are weakened, likely due to nonmagnetic Ti 4+ ions breaking the Ni-O-Ni antiferromagnetic super-exchange pathways. This confirms that the nonmagnetic Ti 4+ ions have successfully incorporated into the lattice and played a role. All curves follow the Curie-Weiss law in the high-temperature region (T > 100 K). Table 2 shows the Curie-Weiss fitting parameters for all samples. The fitted Curie-Weiss temperatures exhibit an overall decreasing trend and are all positive, indicating ferromagnetic exchange interactions dominate in the NM series of high-nickel materials 27 . With increasing Ti 4+ doping concentration, the effective magnetic moment ( µ eff ) of the material decreases significantly. This phenomenon can be explained by magnetic dilution dominance: when Ti 4+ (3 d ⁰, no localized magnetic moment) replaces magnetic ions in the transition metal layer, the introduction of Ti 4+ zero magnetic moment causes the dilution effect of the overall magnetic ion concentration to dominate, leading to a decrease in the total effective magnetic moment. This result provides strong magnetic evidence confirming the successful incorporation of Ti 4+ into the lattice. However, the magnetic moment increases in the 10% doping concentration sample, likely due to severe structural distortion caused by excessive doping. After Ti 4+ occupies the transition metal site, to maintain charge balance, the sum of positive charges in the transition metal layer and lithium layer must remain constant. When the positive charge in the transition metal layer increases, the positive charge in the lithium layer must decrease. thus forcing Ni 2+ from the lithium layer to return to Li + sites in the transition metal layer. The introduction of Ti 4+ significantly reduces lithium-nickel anti-site defects, diminishing magnetic clusters 9,27 . Secondly, even if magnetic clusters exist, the introduction of Ti 4+ will disrupt the geometric frustration caused by a small fraction of lithium-nickel anti-site defects and also overcome the frustration at Ti-doped sites resulting from ferromagnetic exchange interactions within the transition metal layer. Figure 2(b) shows the M-H curves of all doped samples at 2 K. All samples exhibit a certain degree of hysteresis, which first increases and then decreases with increasing doping concentration, reaching a peak at approximately 2.5% doping concentration. Table 1 NM-0、NM-2.5、NM-5、NM-10 lattice constants, c/a ratio, volume (V0), Rwp(%), Rp(%), c 2 . Materials a (Å) c (Å) c/a V 0 (Å 3 ) R wp (%) R p (%) χ 2 NM-0 2.8837 14.2207 4.9314 118.2554 5.1 3.95 1.181 NM-2.5 2.8824 14.2282 4.9362 118.2112 4.5 3.54 1.048 NM-5 2.8834 14.2415 4.9391 118.4038 4.4 3.48 1.041 NM-10 2.8930 14.2971 4.9420 119.6588 4.1 4.08 0.978 Table 2 NM-0、NM-2.5、NM-5、NM-10 the Curie-Weiss fitting parameters. Materials θ cw (K) µ eff( µ b) NM-0 78.52 2.24 NM-2.5 59.06 2.23 NM-5 62.94 1.74 NM-10 46.54 2.02 Electrochemical Performance Figure 3(a) shows the first-cycle charge-discharge curves of NM9505 series samples at a 1C rate. The first-cycle discharge capacity of the Ti-doped samples is slightly lower, possibly due to the introduction of electrochemically inert Ti 4+ . Their first-cycle coulombic efficiencies are nearly identical, indicating irreversible phase transitions and side reactions within the material slightly. Figure 3(b) displays the long-term cycling performance of both materials at a 1C rate. NM9505 exhibits an initial discharge capacity of 170 mAh g − 1 with a capacity retention of 70.5% after 40 cycles, followed by rapid capacity decay with increasing cycles. In contrast, the Ti-doped samples demonstrate outstanding cycling stability: NM-2.5 shows an initial discharge capacity of 155 mAh g − 1 and maintains a remarkable capacity retention of 95% after 40 cycles. This may be attributed to the non-magnetic Ti 4+ ions disrupting the magnetic frustration. Ti 4+ doping stabilizes the crystal structure, suppresses phase transitions and microcrack formation during cycling, and reduces cation mixing, thereby ensuring unobstructed lithium-ion diffusion pathways. The CV curves in Fig. 4(a-d) reveal that the redox peak potential difference in the doped samples is smaller than that in the undoped samples, indicating that the Ti-doped samples exhibit lower polarization and better reaction reversibility. After the cycle, EIS spectra (Fig. 5) reveal that the Nyquist plots for all samples comprise a semicircle in the high-frequency region (representing charge transfer impedance Rc) and a slope in the low-frequency region (representing Warburg impedance). The charge transfer impedance of the doped samples is significantly lower than that of the undoped samples, consistent with the conclusion that Ti 4+ doping expands the lithium interlayer spacing and improves Li + diffusion kinetics. Ti doping effectively suppressed side reactions at the electrode/electrolyte interface, formed a more stable CEI film, and enhanced charge transfer rates, consistent with the excellent cycling stability observed. Summaries and Conclusions This study successfully synthesized Li[Ni 0.95 Mn 0.05 ] 1− x Ti x O 2 (0 ≤ x ≤ 0.1) cathode materials with varying Ti 4+ doping concentrations via a high-temperature solid-state method. Their structure, magnetic properties, and electrochemical performance were systematically investigated. Key findings are as follows: Structure: Appropriate Ti 4+ doping (≈ 2.5%) effectively reduces cation mixing and enhances the order of the layered structure. Magnetism: Magnetization measurements reveal that Ti 4+ doping replaces transition metal layers and, through charge compensation mechanisms, induces the conversion of anti-site Ni 2+ sites to anti-site L i+ sites. The dilution effect of non-magnetic ions leads to a reduction in the material's overall effective magnetic moment. Through the synergistic “chemical doping - charge compensation - magnetic ordering regulation” mechanism, Ti 4+ doping achieves multi-level optimization from the atomic scale to the microscopic magnetic structure. Ti 4+ substitution not only reduces structural anti-site defects via direct “pillar effect” and indirect “charge compensation effect,” but also modulates the local magnetic environment by eliminating magnetic clusters and breaking geometric frustration. This optimized magnetic structure endows the material with enhanced intrinsic stability, enabling superior resistance to Jahn-Teller distortion and accumulated mechanical stress during repeated lithium ion intercalation/deintercalation cycles. This ultimately manifests as exceptional electrochemical cycling stability. Electrochemistry: The 2.5% Ti 4+ -doped sample exhibits the most outstanding comprehensive electrochemical performance, including high capacity and excellent cycling stability (95% capacity retention after 40 cycles). This study demonstrates that actively designing and controlling the magnetic properties of transition metal oxide cathode materials represents a highly promising approach to overcoming their performance limitations. Declarations Author information Yanqiong Tana, Shuaijing Jia, Yulu Zhanga, Shun Tangb, Yuancheng Caob, Zhongwen Ouyanga, Zhenxing Wanga contributed equally to this work. Funding This work was supported by the National Key Research and Development Program of China (2023YFB3809300). Author Contribution Y T responsible for drafting the full text, conducting data testing, performing data analysis, and producing charts and graphs.S J, Y Z responsible for conducting partial data testing and data analysis.S T, Y Cao, Z O, Z W provide analysis of partial experimental data for the thesis alongside comprehensive guidance throughout the process, and supply testing apparatus. Acknowledgements This work was supported by the National Key Research and Development Program of China (2023YFB3809300). Data Availability No datasets were generated or analysed during the current study. References [] EUM D, KIM B, KIM S J, et al. Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes [J]. Nature materials, 2020, 19(4): 419 − 27. [] CHERNOVA N A, NOLIS G M, OMENYA F O, et al. What can we learn about battery materials from their magnetic properties? [J]. Journal of Materials Chemistry, 2011, 21(27). [] MUKHERJEE P, PADDISON J A M, XU C, et al. Sample Dependence of Magnetism in the Next-Generation Cathode Material LiNi0.8Mn0.1Co0.1O2 [J]. Inorganic Chemistry, 2020, 60(1): 263 − 71. [] WIKBERG J M, MåNSSON M, DAHBI M, et al. Magnetic Order and Frustrated Dynamics in Li (Ni0.8Co0.1Mn0.1)O2: A Study by µ + SR and SQUID Magnetometry [J]. Physics Procedia, 2012, 30: 202-5. [] LIN W, YE Y, CHEN T, et al. Defect-mediated Jahn-Teller effect in layered LiNiO2 [J]. Science China Materials, 2022, 65(6): 1696 − 700. [] GENREITH-SCHRIEVER A R, ALEXIU A, PHILLIPS G S, et al. Jahn-Teller Distortions and Phase Transitions in LiNiO(2): Insights from Ab Initio Molecular Dynamics and Variable-Temperature X-ray Diffraction [J]. Chemistry of materials : a publication of the American Chemical Society, 2024, 36(5): 2289 − 303. [] DAMLE K. Low temperature ordering in easy-axis S = 1 kagome and triangular lattice antiferromagnets [J]. Physica A: Statistical Mechanics and its Applications, 2007, 384(1): 28–33. [] YAN H, HA Y, YE T, et al. High performance of Co-free LiNi Mn1-O2 cathodes realized by nonmagnetic ion substitution for Li-ion batteries [J]. Chemical Engineering Journal, 2023, 465. [] SHEN Y, YIN D, WANG L, et al. A universal multifunctional dual cation doping strategy towards stabilized ultra-high nickel cobalt-free lithium layered oxide cathode [J]. Journal of Energy Chemistry, 2024, 95: 296–305. [] SI Z, SHI B, HUANG J, et al. Titanium and fluorine synergetic modification improves the electrochemical performance of Li(Ni0.8Co0.1Mn0.1)O2 [J]. Journal of Materials Chemistry A, 2021, 9. [] ZHANG Z, HONG B, YI M, et al. In situ co-doping strategy for achieving long-term cycle stability of single-crystal Ni-rich cathodes at high voltage [J]. Chemical Engineering Journal, 2022, 445: 136825. [] KIM S, PIAO J, HEO K, et al. Co-modification strategy of Li + and Ti4 + cations in Ni-rich NCM cathode for high-performance lithium-ion batteries [J]. Journal of Energy Storage, 2025, 140: 118901. [] ZOU K, JIANG M, NING T, et al. Thermodynamics-directed bulk/grain-boundary engineering for superior electrochemical durability of Ni-rich cathode [J]. Journal of Energy Chemistry, 2024, 97: 321 − 31. [] DU R, BI Y, YANG W, et al. Improved cyclic stability of LiNi0.8Co0.1Mn0.1O2 via Ti substitution with a cut-off potential of 4.5V [J]. Ceramics International, 2015, 41(5, Part B): 7133-9. []CHENG Y, SUN Y, CHU C, et al. Stabilizing effects of atomic Ti doping on high-voltage high-nickel layered oxide cathode for lithium-ion rechargeable batteries [J]. Nano Research, 2022, 15(5): 4091-9. [] ZHANG D, LIU Y, WU L, et al. Effect of Ti ion doping on electrochemical performance of Ni-rich LiNi0.8Co0.1Mn0.1O2 cathode material [J]. Electrochimica Acta, 2019, 328. [] SUN Y, HUANG W, ZHAO G, et al. LiNi0.9Co0.09Mo0.01O2 Cathode with Li3PO4 Coating and Ti Doping for Next-Generation Lithium-Ion Batteries [J]. ACS Energy Letters, 2023, 8(3): 1629-38. [] ZHU C, XU M, HUANG K, et al. Al- and Nb-Comodified Ni-Rich NCM Cathode for High-Performance Lithium-Ion Batteries [J]. Industrial & Engineering Chemistry Research, 2024, 63(6): 2740-9. [] MENG K, WANG Z, GUO H, et al. Improving the cycling performance of LiNi0.8Co0.1Mn0.1O2 by surface coating with Li2TiO3 [J]. Electrochimica Acta, 2016, 211: 822 − 31. [] LI Y, SU Q, HAN Q, et al. Synthesis and characterization of Mo-doped LiNi0.5Co0.2Mn0.3O2 cathode materials prepared by a hydrothermal process [J]. Ceramics International, 2017, 43(4): 3483-8. [] CHEN J, YANG Y, TANG Y, et al. Constructing a Thin Disordered Self‐Protective Layer on the LiNiO2 Primary Particles Against Oxygen Release [J]. Advanced Functional Materials, 2022, 33(6). [] HU S, LIANG X, YUAN H, et al. Enhancing Long‐Term Cycling Stability of Co‐Free Ultrahigh‐Ni Layered Cathode Materials via Synergistic Structure/Interface Engineering [J]. Advanced Functional Materials, 2025. [] HE P, ZHANG M, WANG S, et al. Enhanced high-rate and cyclic performance of Co-free and Ni-rich LiNi0.95Mn0.05O2 cathodes by coating electronic/Li + conductive PANI-PEG layer [J]. Journal of Solid State Electrochemistry, 2024, 28(11): 4259-71. [] SU T, LI Y, ZHANG Z, et al. Synergistic Nb Doping and Carbon Coating for Stabilized Ultrahigh-Ni-Layered Cathodes in Durable Lithium-Ion Batteries [J]. Energy & Fuels, 2025, 39(26): 12745-55. [] HEBERT A J, MCCALLA E J M A. The role of metal substitutions in the development of Li batteries, part I: cathodes [J]. 2021. [] NI L, GUO R, FANG S, et al. Crack-free single-crystalline Co-free Ni-rich LiNi0.95Mn0.05O2 layered cathode [J]. eScience, 2022, 2(1): 116 − 24. [] CHAPPEL E, NúñEZ-REGUEIRO M D, DE BRION S, et al. Interlayer magnetic frustration in quasistoichiometric [J]. Physical Review B, 2002, 66(13): 132412. Additional Declarations No competing interests reported. Supplementary Files Data.zip Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8578612","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":578507592,"identity":"61c46a22-6876-4563-9d7f-c7a3871b23fe","order_by":0,"name":"yanqiong tan","email":"","orcid":"","institution":"华中科技大学","correspondingAuthor":false,"prefix":"","firstName":"yanqiong","middleName":"","lastName":"tan","suffix":""},{"id":578507596,"identity":"c62a97c9-ebe0-489b-a23d-73e6ae6f6dc8","order_by":1,"name":"Shuaijing 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18:03:11","extension":"html","order_by":16,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":52844,"visible":true,"origin":"","legend":"","description":"","filename":"earlyproof.html","url":"https://assets-eu.researchsquare.com/files/rs-8578612/v1/30f603520467763bc8718992.html"},{"id":101006679,"identity":"06e80d84-e562-494e-9be1-49af77095e5f","added_by":"auto","created_at":"2026-01-23 18:03:10","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":147341,"visible":true,"origin":"","legend":"\u003cp\u003eXRD Patterns of NM9505 with Different Ti Doping Concentrations.\u003c/p\u003e\n\u003cp\u003e(a) XRD pattern (b) Magnified view of the 003 peak.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-8578612/v1/b828ea7b910eb16d506180f3.png"},{"id":101006681,"identity":"6556c2d5-06bb-4472-8729-87870d4e9947","added_by":"auto","created_at":"2026-01-23 18:03:10","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":204939,"visible":true,"origin":"","legend":"\u003cp\u003eMagnetization curves of NM9505 doped with Ti concentration gradients.\u003c/p\u003e\n\u003cp\u003e(a) Zero-Field Cooling(ZFC) and Field Cooling(FC) curves of NM series samples (b) Magnetic hysteresis (MH) curves of NM series samples.\u003c/p\u003e","description":"","filename":"floatimage2.png","url":"https://assets-eu.researchsquare.com/files/rs-8578612/v1/cf4a3d98e74ff4695eadf6f3.png"},{"id":101006689,"identity":"f7ac9821-d15f-4d5f-ba48-9891b08cf326","added_by":"auto","created_at":"2026-01-23 18:03:11","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":217818,"visible":true,"origin":"","legend":"\u003cp\u003eElectrochemical cycling curves of NM9505 doped with Ti concentration gradients. (a) First charge-discharge curves of NM series samples. (b) Cycling capacity curves and coulombic efficiency curves of NM series samples.\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-8578612/v1/3ac58c50e1b2bd9d3e1f8c0d.png"},{"id":101006685,"identity":"8e396339-fb01-4a88-9896-d83365228324","added_by":"auto","created_at":"2026-01-23 18:03:11","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":251964,"visible":true,"origin":"","legend":"\u003cp\u003e2sd CV curves (a–d) of NM series samples.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-8578612/v1/f6abb31114c61f5ae21dbf89.png"},{"id":101006684,"identity":"dd836d44-6e9c-4f5c-9415-ddc28209d552","added_by":"auto","created_at":"2026-01-23 18:03:10","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":74076,"visible":true,"origin":"","legend":"\u003cp\u003eEIS spectra of NM series samples after cycling.\u003c/p\u003e","description":"","filename":"floatimage5.png","url":"https://assets-eu.researchsquare.com/files/rs-8578612/v1/a09724fce39c684f09bd92e3.png"},{"id":101752622,"identity":"1121d3f4-fddd-4def-b995-0bc9a53c0897","added_by":"auto","created_at":"2026-02-03 10:28:34","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1327393,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8578612/v1/94eec155-d37b-4cf4-9a15-9a47d0ad29fb.pdf"},{"id":101006680,"identity":"a75ae93d-b906-43e1-9e17-217138225f21","added_by":"auto","created_at":"2026-01-23 18:03:10","extension":"zip","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":1321688,"visible":true,"origin":"","legend":"","description":"","filename":"Data.zip","url":"https://assets-eu.researchsquare.com/files/rs-8578612/v1/a4d71b42583f53ceff5de09b.zip"}],"financialInterests":"No competing interests reported.","formattedTitle":"Stabilizing Nickel Ions by Local Magnetic Order Modulation for Durable Ultrahigh-Nickel Cathode","fulltext":[{"header":"Introduction","content":"\u003cp\u003eRecent studies indicate that the degradation of electrochemical behaviour in high-nickel materials (such as LiNiO₂ and its derivatives) is closely associated with the magnetic interactions between nickel ions within the transition metal layer and their ordered states\u003csup\u003e1\u003c/sup\u003e\u003csup\u003e,\u003c/sup\u003e\u003csup\u003e2\u003c/sup\u003e\u003csup\u003e,\u003c/sup\u003e\u003csup\u003e3\u003c/sup\u003e\u003csup\u003e,\u003c/sup\u003e\u003csup\u003e4\u003c/sup\u003e. From the perspective of crystal field theory, Ni\u003csup\u003e3+\u003c/sup\u003e(t\u003csub\u003e2\u003c/sub\u003eg\u003csup\u003e6\u003c/sup\u003eeg\u003csup\u003e1\u003c/sup\u003e) is a typical Jahn-Teller ion whose presence induces lattice distortion\u003csup\u003e5\u003c/sup\u003e\u003csup\u003e,\u003c/sup\u003e\u003csup\u003e6\u003c/sup\u003e. From the perspective of magnetic exchange interactions, within the trigonal lattice of LiNiO\u003csub\u003e2\u003c/sub\u003e-based materials, Ni ions form a complex magnetic order - intralayer ferromagnetism and interlayer antiferromagnetism through O\u003csup\u003e2\u0026minus;\u003c/sup\u003e-mediated super-exchange. This geometric configuration readily leads to magnetic frustration, where the antiferromagnetic interactions between neighboring spins cannot be simultaneously satisfied, trapping them in an energetically degenerate ground state\u003csup\u003e7\u003c/sup\u003e\u003csup\u003e,\u003c/sup\u003e\u003csup\u003e8\u003c/sup\u003e. This magnetic instability, synergizing with the Jahn-Teller effect and cation mixing, collectively lowers the lattice formation energy barrier. Consequently, the material becomes more prone to phase transitions and structural degradation under electrochemical cycling stresses. Therefore, Unlike traditional structural modification strategies, regulating local magnetic order and resolving magnetic frustration offer a novel approach to stabilizing high-nickel cathode materials\u003csup\u003e9\u003c/sup\u003e. Ion doping serves as an effective means to achieve this goal. Among various dopants, Ti\u003csup\u003e4+\u003c/sup\u003e exhibits unique advantages due to its stable 3\u003cem\u003ed\u003c/em\u003e\u003csup\u003e0\u003c/sup\u003e electronic configuration, strong Ti-O bonding, and ability to regulate charge distribution\u003csup\u003e10\u003c/sup\u003e\u003csup\u003e,\u003c/sup\u003e\u003csup\u003e11\u003c/sup\u003e\u003csup\u003e,\u003c/sup\u003e\u003csup\u003e12\u003c/sup\u003e\u003csup\u003e,\u003c/sup\u003e\u003csup\u003e13\u003c/sup\u003e\u003csup\u003e,\u003c/sup\u003e\u003csup\u003e14\u003c/sup\u003e\u003csup\u003e,\u003c/sup\u003e\u003csup\u003e15\u003c/sup\u003e\u003csup\u003e,\u003c/sup\u003e\u003csup\u003e16\u003c/sup\u003e. We hypothesize that introducing non-magnetic Ti\u003csup\u003e4+\u003c/sup\u003e into the transition metal layer disrupts the symmetric triangular lattice formed by Ni ions. By diluting magnetic ions and reconfiguring super-exchange pathways, it effectively relieves magnetic frustration, reduces the system's magnetic free energy, and fundamentally enhances material structural stability\u003csup\u003e17\u003c/sup\u003e. Based on this, this study employs a high-temperature solid-state method to synthesize a series of Ti\u003csup\u003e4+\u003c/sup\u003e-doped Li[Ni\u003csub\u003e0.95\u003c/sub\u003eMn\u003csub\u003e0.05\u003c/sub\u003e]\u003csub\u003e1\u0026minus;\u003cem\u003ex\u003c/em\u003e\u003c/sub\u003eTi\u003csub\u003e\u003cem\u003ex\u003c/em\u003e\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e(0\u0026thinsp;\u0026le;\u0026thinsp;x\u0026thinsp;\u0026le;\u0026thinsp;0.1) polycrystalline samples. We aim to systematically investigate the stability modification mechanism of Ti\u003csup\u003e4+\u003c/sup\u003e doping in LiNi\u003csub\u003e0.95\u003c/sub\u003eMn\u003csub\u003e0.05\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e through comprehensive crystal structure (XRD), magnetic (SQUID), and electrochemical characterization. The core of this work lies in elucidating how Ti\u003csup\u003e4+\u003c/sup\u003e doping synergistically reduces cation mixing and enhances lattice stability by regulating local magnetic order and suppressing magnetic resistance frustration. This ultimately achieves significant improvements in electrochemical performance, providing new theoretical foundations and practical pathways for designing next-generation high-nickel cathode materials.\u003c/p\u003e"},{"header":"Experimental Method","content":"\u003cp\u003eMaterial Synthesis\u003c/p\u003e \u003cp\u003ePolycrystalline samples of Ti\u003csup\u003e4+\u003c/sup\u003e-doped LiNi\u003csub\u003e0.95\u003c/sub\u003eMn\u003csub\u003e0.05\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e(NM-0) were prepared using the standard high-temperature solid-state method. The material was modified with Ti\u003csup\u003e4+\u003c/sup\u003e at doping concentrations of 0, 2.5, 5, and 10%. The precursor Ni\u003csub\u003e0.95\u003c/sub\u003eMn\u003csub\u003e0.05\u003c/sub\u003e(OH)\u003csub\u003e2\u003c/sub\u003e (Dongguan Songhu Shengjian Technology Co., Ltd., China) and LiOH\u0026middot;H\u003csub\u003e2\u003c/sub\u003eO (AR, Shanghai Aladdin Bio-Chemical Technology Co., Ltd., China) were weighed at a molar ratio of 1:1.05\u003csup\u003e18\u003c/sup\u003e\u003csup\u003e,\u003c/sup\u003e\u003csup\u003e19\u003c/sup\u003e\u003csup\u003e,\u003c/sup\u003e\u003csup\u003e20\u003c/sup\u003e. All raw materials were precisely weighed according to the stoichiometric ratio, mixed with anhydrous ethanol in an agate mortar, and ball-milled for 12 hours to ensure thorough homogenization. The uniformly mixed slurry was dried at 80\u0026deg;C, and the dried precursor powder was pre-sintered at 500\u0026deg;C for 5 hours under air atmosphere. Subsequently, the pre-sintered product was reground and calcined at 950\u0026deg;C for 15 hours under an oxygen atmosphere, followed by cooling to room temperature in the furnace to obtain the final product. This process was repeated 2\u0026ndash;3 times to yield a black powder sample. The doping sample was prepared identically to the above steps, with TiO\u003csub\u003e2\u003c/sub\u003e used as the doping material.\u003c/p\u003e \u003cp\u003eMaterial Characterization\u003c/p\u003e \u003cp\u003eThe crystal structure of the samples was analyzed using X-ray diffraction (XRD, Bruker D8 Advance) with Cu Kα radiation (\u003cem\u003eλ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;1.5406 \u0026Aring;). Rietveld refinement software (e.g., GSAS) was used to refine the XRD patterns to obtain lattice parameters and cation mixing degrees. The magnetic susceptibilities and magnetization were measured by using a Quantum Design superconducting quantum interference device (SQUID) magnetometer. The magnetic susceptibility data were collected during the zero-field cooled (ZFC) heating process followed by field-cooled (FC) cooling process in the temperature range of 2\u0026ndash;300 K under an applied magnetic field of 1000 Oe.\u003c/p\u003e \u003cp\u003eElectrochemical Testing\u003c/p\u003e \u003cp\u003eThe active material, acetylene black, and polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 8:1:1 in N-methyl-2-pyrrolidone (NMP) to form a uniform slurry. The slurry was coated on aluminum foil current collectors and vacuum-dried at 120\u0026deg;C for 12 hours to prepare the cathode electrodes. CR2032-type coin cells were assembled in an argon-filled glove box using lithium metal as both the counter and reference electrodes, Celgard 2400 as the separator, and 1 M LiPF\u003csub\u003e6\u003c/sub\u003e in EC/DEC (1:1, v/v) as the electrolyte. Constant current charge-discharge tests were conducted using a LAND battery testing system within a voltage range of 2.7\u0026ndash;4.3 V. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests were also performed using the LAND battery testing system.\u003c/p\u003e"},{"header":"Results and Discussion","content":"\u003cp\u003eStructural analysis\u003c/p\u003e \u003cp\u003eFigure 1 displays the XRD patterns of NM9505 at different Ti doping concentrations, along with an enlarged view of the 003 peak. As shown in Fig.\u0026nbsp;1(a), the XRD diffraction peaks of NM-0, NM-2.5, NM-5, and NM-10 match those of NM9505, all belonging to the \u003cem\u003eR\u003c/em\u003e-3m space group with a hexagonal crystal structure. hexagonal LiNiO\u003csub\u003e2\u003c/sub\u003e structure, with no additional impurity peaks observed\u003csup\u003e21\u003c/sup\u003e. This confirms that Ti\u003csup\u003e4+\u003c/sup\u003e has successfully intercalated into the lattice of the layered matrix material NM9505 without altering its original crystal structure. The figure shows distinct splitting in the (006)/(102) and (108)/(110) pairs of diffraction peaks for all samples, indicating an ordered layered structure\u003csup\u003e22\u003c/sup\u003e\u003csup\u003e,\u003c/sup\u003e\u003csup\u003e23\u003c/sup\u003e. The enlarged region of the (003) peak is shown in Fig.\u0026nbsp;1(b). Since the (003) peak resides in the transition metal layer plane, it reflects changes in the c-axis. Its peak position shifts slightly toward the low-angle region, indicating that the c-axis lattice parameter gradually increases with rising Ti\u003csup\u003e4+\u003c/sup\u003e doping concentration\u003csup\u003e24\u003c/sup\u003e, consistent with Gsas refinement results. This occurs because Ti\u003csup\u003e4+\u003c/sup\u003e (\u003cem\u003er\u003c/em\u003e\u0026thinsp;=\u0026thinsp;0.605 \u0026Aring;) possesses a larger ionic radius (Mn\u003csup\u003e4+\u003c/sup\u003e: \u003cem\u003er\u003c/em\u003e\u0026thinsp;=\u0026thinsp;0.53 \u0026Aring;, Ni\u003csup\u003e3+\u003c/sup\u003e: \u003cem\u003er\u003c/em\u003e\u0026thinsp;=\u0026thinsp;0.56 \u0026Aring;, Ni\u003csup\u003e2+\u003c/sup\u003e: \u003cem\u003er\u003c/em\u003e\u0026thinsp;=\u0026thinsp;0.69 \u0026Aring;). Consequently, when Ti\u003csup\u003e4+\u003c/sup\u003e successfully enters the transition metal layer, the lithium interlayer spacing expands, thereby enhancing lithium-ion diffusion\u003csup\u003e25\u003c/sup\u003e. The refined XRD results reveal that NM-0 belongs to the space group \u003cem\u003eR\u003c/em\u003e-3m with lattice constants \u003cem\u003ea\u003c/em\u003e\u0026thinsp;=\u0026thinsp;2.8837(1) \u0026Aring;, \u003cem\u003eb\u003c/em\u003e\u0026thinsp;=\u0026thinsp;2.8837(1) \u0026Aring;, \u003cem\u003ec\u003c/em\u003e\u0026thinsp;=\u0026thinsp;14.2207(1) \u0026Aring;, \u003cem\u003eα\u003c/em\u003e\u0026thinsp;=\u0026thinsp;90(1)\u0026deg;, \u003cem\u003eβ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;90 (1)\u0026deg;, \u003cem\u003eγ\u003c/em\u003e\u0026thinsp;=\u0026thinsp;120 (1)\u0026deg;, and \u003cem\u003eV\u003c/em\u003e\u0026thinsp;=\u0026thinsp;118.2595(1) \u0026Aring;\u003csup\u003e3\u003c/sup\u003e, consistent with literature reports\u003csup\u003e26\u003c/sup\u003e. The refinement optimization indices were \u003cem\u003eR\u003c/em\u003e\u003csub\u003ep\u003c/sub\u003e = 3.95%, \u003cem\u003eR\u003c/em\u003e\u003csub\u003ewp\u003c/sub\u003e = 5.1%, and \u003cem\u003eλ\u003c/em\u003e\u003csup\u003e2\u003c/sup\u003e\u0026thinsp;=\u0026thinsp;1.181, indicating high phase purity of the sample. the lattice parameter c gradually increases, consistent with the previously described. All samples are summarized in Table\u0026nbsp;1. All samples consists of the lithium layer and the transition metal layer, where each transition metal atom is surrounded by six oxygen atoms forming an oxygen octahedral structure, and a small amount of lithium-nickel anti-site defects occur.\u003c/p\u003e \u003cp\u003eMagnetic Analysis\u003c/p\u003e \u003cp\u003eFigure 2(a) shows the temperature-dependent magnetic susceptibility curves measured at a magnetic field of 1000 Oe for all samples. Zero-Field Cooling(ZFC) and Field Cooling(FC) curves exhibit obvious thermal hysteresis. ZFC and FC split prior to the magnetic transition temperature, exhibiting full peak shapes, with FC showing a slight upward trend in the low-temperature region. This is a typical manifestation of cluster glass. All samples exhibit a distinct magnetic transition at low temperatures. The magnetic transition temperature is approximately 18 K and shifts toward lower temperatures with increasing doping concentration. This indicates that the exchange interactions responsible for antiferromagnetic ordering within the material are weakened, likely due to nonmagnetic Ti\u003csup\u003e4+\u003c/sup\u003e ions breaking the Ni-O-Ni antiferromagnetic super-exchange pathways. This confirms that the nonmagnetic Ti\u003csup\u003e4+\u003c/sup\u003e ions have successfully incorporated into the lattice and played a role. All curves follow the Curie-Weiss law in the high-temperature region (T\u0026thinsp;\u0026gt;\u0026thinsp;100 K). Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e2\u003c/span\u003e shows the Curie-Weiss fitting parameters for all samples. The fitted Curie-Weiss temperatures exhibit an overall decreasing trend and are all positive, indicating ferromagnetic exchange interactions dominate in the NM series of high-nickel materials\u003csup\u003e27\u003c/sup\u003e. With increasing Ti\u003csup\u003e4+\u003c/sup\u003e doping concentration, the effective magnetic moment (\u003cem\u003e\u0026micro;\u003c/em\u003e\u003csub\u003eeff\u003c/sub\u003e) of the material decreases significantly. This phenomenon can be explained by magnetic dilution dominance: when Ti\u003csup\u003e4+\u003c/sup\u003e (3\u003cem\u003ed\u003c/em\u003e⁰, no localized magnetic moment) replaces magnetic ions in the transition metal layer, the introduction of Ti\u003csup\u003e4+\u003c/sup\u003e zero magnetic moment causes the dilution effect of the overall magnetic ion concentration to dominate, leading to a decrease in the total effective magnetic moment. This result provides strong magnetic evidence confirming the successful incorporation of Ti\u003csup\u003e4+\u003c/sup\u003e into the lattice. However, the magnetic moment increases in the 10% doping concentration sample, likely due to severe structural distortion caused by excessive doping. After Ti\u003csup\u003e4+\u003c/sup\u003e occupies the transition metal site, to maintain charge balance, the sum of positive charges in the transition metal layer and lithium layer must remain constant. When the positive charge in the transition metal layer increases, the positive charge in the lithium layer must decrease. thus forcing Ni\u003csup\u003e2+\u003c/sup\u003e from the lithium layer to return to Li\u003csup\u003e+\u003c/sup\u003e sites in the transition metal layer. The introduction of Ti\u003csup\u003e4+\u003c/sup\u003e significantly reduces lithium-nickel anti-site defects, diminishing magnetic clusters\u003csup\u003e9,27\u003c/sup\u003e. Secondly, even if magnetic clusters exist, the introduction of Ti\u003csup\u003e4+\u003c/sup\u003e will disrupt the geometric frustration caused by a small fraction of lithium-nickel anti-site defects and also overcome the frustration at Ti-doped sites resulting from ferromagnetic exchange interactions within the transition metal layer. Figure\u0026nbsp;2(b) shows the \u003cem\u003eM-H\u003c/em\u003e curves of all doped samples at 2 K. All samples exhibit a certain degree of hysteresis, which first increases and then decreases with increasing doping concentration, reaching a peak at approximately 2.5% doping concentration.\u003c/p\u003e \u003cp\u003e\u003cstrong\u003eTable\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003e1\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eNM-0、NM-2.5、NM-5、NM-10 lattice constants, c/a ratio, volume (V0), Rwp(%), Rp(%),\u0026nbsp;c\u003csup\u003e2\u003c/sup\u003e.\u003c/p\u003e\n\u003ctable border=\"1\" cellspacing=\"0\" cellpadding=\"0\"\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003eMaterials\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003ea\u003c/em\u003e (\u0026Aring;)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003ec\u003c/em\u003e (\u0026Aring;)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003ec/a\u003c/em\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003eV\u003c/em\u003e\u003csub\u003e0\u003c/sub\u003e (\u0026Aring;\u003csup\u003e3\u003c/sup\u003e)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003eR\u003c/em\u003e\u003csub\u003ewp\u003c/sub\u003e (%)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u003cem\u003eR\u003c/em\u003e\u003csub\u003ep\u003c/sub\u003e (%)\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e\u0026chi;\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003eNM-0\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e2.8837\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e14.2207\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e4.9314\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd\u003e\n \u003cp\u003e118.2554\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e5.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e3.95\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e1.181\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003eNM-2.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd\u003e\n \u003cp\u003e2.8824\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e14.2282\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd\u003e\n \u003cp\u003e4.9362\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd\u003e\n \u003cp\u003e118.2112\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e4.5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e3.54\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e1.048\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003eNM-5\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd\u003e\n \u003cp\u003e2.8834\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e14.2415\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd\u003e\n \u003cp\u003e4.9391\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd\u003e\n \u003cp\u003e118.4038\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e4.4\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e3.48\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e1.041\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003eNM-10\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd\u003e\n \u003cp\u003e2.8930\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e14.2971\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd\u003e\n \u003cp\u003e4.9420\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd\u003e\n \u003cp\u003e119.6588\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e4.1\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e4.08\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd valign=\"top\"\u003e\n \u003cp\u003e0.978\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n\u003c/table\u003e\u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eNM-0、NM-2.5、NM-5、NM-10 the Curie-Weiss fitting parameters.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"3\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMaterials\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eθ\u003csub\u003ecw\u003c/sub\u003e(K)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u003cem\u003e\u0026micro;\u003c/em\u003e\u003csub\u003eeff(\u003c/sub\u003e\u003cem\u003e\u0026micro;\u003c/em\u003e\u003csub\u003eb)\u003c/sub\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNM-0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e78.52\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.24\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNM-2.5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e59.06\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.23\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNM-5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e62.94\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e1.74\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNM-10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e46.54\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e2.02\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eElectrochemical Performance\u003c/p\u003e \u003cp\u003eFigure 3(a) shows the first-cycle charge-discharge curves of NM9505 series samples at a 1C rate. The first-cycle discharge capacity of the Ti-doped samples is slightly lower, possibly due to the introduction of electrochemically inert Ti\u003csup\u003e4+\u003c/sup\u003e. Their first-cycle coulombic efficiencies are nearly identical, indicating irreversible phase transitions and side reactions within the material slightly. Figure\u0026nbsp;3(b) displays the long-term cycling performance of both materials at a 1C rate. NM9505 exhibits an initial discharge capacity of 170 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e with a capacity retention of 70.5% after 40 cycles, followed by rapid capacity decay with increasing cycles. In contrast, the Ti-doped samples demonstrate outstanding cycling stability: NM-2.5 shows an initial discharge capacity of 155 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and maintains a remarkable capacity retention of 95% after 40 cycles. This may be attributed to the non-magnetic Ti\u003csup\u003e4+\u003c/sup\u003e ions disrupting the magnetic frustration. Ti\u003csup\u003e4+\u003c/sup\u003e doping stabilizes the crystal structure, suppresses phase transitions and microcrack formation during cycling, and reduces cation mixing, thereby ensuring unobstructed lithium-ion diffusion pathways. The CV curves in Fig.\u0026nbsp;4(a-d) reveal that the redox peak potential difference in the doped samples is smaller than that in the undoped samples, indicating that the Ti-doped samples exhibit lower polarization and better reaction reversibility. After the cycle, EIS spectra (Fig.\u0026nbsp;5) reveal that the Nyquist plots for all samples comprise a semicircle in the high-frequency region (representing charge transfer impedance Rc) and a slope in the low-frequency region (representing Warburg impedance). The charge transfer impedance of the doped samples is significantly lower than that of the undoped samples, consistent with the conclusion that Ti\u003csup\u003e4+\u003c/sup\u003e doping expands the lithium interlayer spacing and improves Li\u003csup\u003e+\u003c/sup\u003e diffusion kinetics. Ti doping effectively suppressed side reactions at the electrode/electrolyte interface, formed a more stable CEI film, and enhanced charge transfer rates, consistent with the excellent cycling stability observed.\u003c/p\u003e\n\u003ch3\u003eSummaries and Conclusions\u003c/h3\u003e\n\u003cp\u003eThis study successfully synthesized Li[Ni\u003csub\u003e0.95\u003c/sub\u003eMn\u003csub\u003e0.05\u003c/sub\u003e]\u003csub\u003e1\u0026minus;\u003cem\u003ex\u003c/em\u003e\u003c/sub\u003eTi\u003csub\u003e\u003cem\u003ex\u003c/em\u003e\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e(0\u0026thinsp;\u0026le;\u0026thinsp;x\u0026thinsp;\u0026le;\u0026thinsp;0.1) cathode materials with varying Ti\u003csup\u003e4+\u003c/sup\u003e doping concentrations via a high-temperature solid-state method. Their structure, magnetic properties, and electrochemical performance were systematically investigated. Key findings are as follows: Structure: Appropriate Ti\u003csup\u003e4+\u003c/sup\u003e doping (\u0026asymp;\u0026thinsp;2.5%) effectively reduces cation mixing and enhances the order of the layered structure. Magnetism: Magnetization measurements reveal that Ti\u003csup\u003e4+\u003c/sup\u003e doping replaces transition metal layers and, through charge compensation mechanisms, induces the conversion of anti-site Ni\u003csup\u003e2+\u003c/sup\u003e sites to anti-site L\u003csup\u003ei+\u003c/sup\u003e sites. The dilution effect of non-magnetic ions leads to a reduction in the material's overall effective magnetic moment. Through the synergistic \u0026ldquo;chemical doping - charge compensation - magnetic ordering regulation\u0026rdquo; mechanism, Ti\u003csup\u003e4+\u003c/sup\u003e doping achieves multi-level optimization from the atomic scale to the microscopic magnetic structure. Ti\u003csup\u003e4+\u003c/sup\u003e substitution not only reduces structural anti-site defects via direct \u0026ldquo;pillar effect\u0026rdquo; and indirect \u0026ldquo;charge compensation effect,\u0026rdquo; but also modulates the local magnetic environment by eliminating magnetic clusters and breaking geometric frustration. This optimized magnetic structure endows the material with enhanced intrinsic stability, enabling superior resistance to Jahn-Teller distortion and accumulated mechanical stress during repeated lithium ion intercalation/deintercalation cycles. This ultimately manifests as exceptional electrochemical cycling stability. Electrochemistry: The 2.5% Ti\u003csup\u003e4+\u003c/sup\u003e-doped sample exhibits the most outstanding comprehensive electrochemical performance, including high capacity and excellent cycling stability (95% capacity retention after 40 cycles). This study demonstrates that actively designing and controlling the magnetic properties of transition metal oxide cathode materials represents a highly promising approach to overcoming their performance limitations.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eAuthor information\u003c/h2\u003e \u003cp\u003eYanqiong Tana, Shuaijing Jia, Yulu Zhanga, Shun Tangb, Yuancheng Caob, Zhongwen Ouyanga, Zhenxing Wanga contributed equally to this work.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eFunding\u003c/h2\u003e \u003cp\u003eThis work was supported by the National Key Research and Development Program of China (2023YFB3809300).\u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eY T responsible for drafting the full text, conducting data testing, performing data analysis, and producing charts and graphs.S J, Y Z responsible for conducting partial data testing and data analysis.S T, Y Cao, Z O, Z W provide analysis of partial experimental data for the thesis alongside comprehensive guidance throughout the process, and supply testing apparatus.\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e \u003cp\u003eThis work was supported by the National Key Research and Development Program of China (2023YFB3809300).\u003c/p\u003e\u003ch2\u003eData Availability\u003c/h2\u003e\u003cp\u003eNo datasets were generated or analysed during the current study.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003e[] EUM D, KIM B, KIM S J, et al. Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes [J]. Nature materials, 2020, 19(4): 419\u0026thinsp;\u0026minus;\u0026thinsp;27.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] CHERNOVA N A, NOLIS G M, OMENYA F O, et al. What can we learn about battery materials from their magnetic properties? [J]. Journal of Materials Chemistry, 2011, 21(27).\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] MUKHERJEE P, PADDISON J A M, XU C, et al. Sample Dependence of Magnetism in the Next-Generation Cathode Material LiNi0.8Mn0.1Co0.1O2 [J]. Inorganic Chemistry, 2020, 60(1): 263\u0026thinsp;\u0026minus;\u0026thinsp;71.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] WIKBERG J M, M\u0026aring;NSSON M, DAHBI M, et al. Magnetic Order and Frustrated Dynamics in Li (Ni0.8Co0.1Mn0.1)O2: A Study by \u0026micro;\u0026thinsp;+\u0026thinsp;SR and SQUID Magnetometry [J]. Physics Procedia, 2012, 30: 202-5.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] LIN W, YE Y, CHEN T, et al. Defect-mediated Jahn-Teller effect in layered LiNiO2 [J]. Science China Materials, 2022, 65(6): 1696\u0026thinsp;\u0026minus;\u0026thinsp;700.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] GENREITH-SCHRIEVER A R, ALEXIU A, PHILLIPS G S, et al. Jahn-Teller Distortions and Phase Transitions in LiNiO(2): Insights from Ab Initio Molecular Dynamics and Variable-Temperature X-ray Diffraction [J]. Chemistry of materials : a publication of the American Chemical Society, 2024, 36(5): 2289\u0026thinsp;\u0026minus;\u0026thinsp;303.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] DAMLE K. Low temperature ordering in easy-axis S\u0026thinsp;=\u0026thinsp;1 kagome and triangular lattice antiferromagnets [J]. Physica A: Statistical Mechanics and its Applications, 2007, 384(1): 28\u0026ndash;33.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] YAN H, HA Y, YE T, et al. High performance of Co-free LiNi Mn1-O2 cathodes realized by nonmagnetic ion substitution for Li-ion batteries [J]. Chemical Engineering Journal, 2023, 465.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] SHEN Y, YIN D, WANG L, et al. A universal multifunctional dual cation doping strategy towards stabilized ultra-high nickel cobalt-free lithium layered oxide cathode [J]. Journal of Energy Chemistry, 2024, 95: 296\u0026ndash;305.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] SI Z, SHI B, HUANG J, et al. Titanium and fluorine synergetic modification improves the electrochemical performance of Li(Ni0.8Co0.1Mn0.1)O2 [J]. Journal of Materials Chemistry A, 2021, 9.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] ZHANG Z, HONG B, YI M, et al. In situ co-doping strategy for achieving long-term cycle stability of single-crystal Ni-rich cathodes at high voltage [J]. Chemical Engineering Journal, 2022, 445: 136825.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] KIM S, PIAO J, HEO K, et al. Co-modification strategy of Li\u0026thinsp;+\u0026thinsp;and Ti4\u0026thinsp;+\u0026thinsp;cations in Ni-rich NCM cathode for high-performance lithium-ion batteries [J]. Journal of Energy Storage, 2025, 140: 118901.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] ZOU K, JIANG M, NING T, et al. Thermodynamics-directed bulk/grain-boundary engineering for superior electrochemical durability of Ni-rich cathode [J]. Journal of Energy Chemistry, 2024, 97: 321\u0026thinsp;\u0026minus;\u0026thinsp;31.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] DU R, BI Y, YANG W, et al. Improved cyclic stability of LiNi0.8Co0.1Mn0.1O2 via Ti substitution with a cut-off potential of 4.5V [J]. Ceramics International, 2015, 41(5, Part B): 7133-9.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[]CHENG Y, SUN Y, CHU C, et al. Stabilizing effects of atomic Ti doping on high-voltage high-nickel layered oxide cathode for lithium-ion rechargeable batteries [J]. Nano Research, 2022, 15(5): 4091-9.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] ZHANG D, LIU Y, WU L, et al. Effect of Ti ion doping on electrochemical performance of Ni-rich LiNi0.8Co0.1Mn0.1O2 cathode material [J]. Electrochimica Acta, 2019, 328.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] SUN Y, HUANG W, ZHAO G, et al. LiNi0.9Co0.09Mo0.01O2 Cathode with Li3PO4 Coating and Ti Doping for Next-Generation Lithium-Ion Batteries [J]. ACS Energy Letters, 2023, 8(3): 1629-38.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] ZHU C, XU M, HUANG K, et al. Al- and Nb-Comodified Ni-Rich NCM Cathode for High-Performance Lithium-Ion Batteries [J]. Industrial \u0026amp; Engineering Chemistry Research, 2024, 63(6): 2740-9.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] MENG K, WANG Z, GUO H, et al. Improving the cycling performance of LiNi0.8Co0.1Mn0.1O2 by surface coating with Li2TiO3 [J]. Electrochimica Acta, 2016, 211: 822\u0026thinsp;\u0026minus;\u0026thinsp;31.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] LI Y, SU Q, HAN Q, et al. Synthesis and characterization of Mo-doped LiNi0.5Co0.2Mn0.3O2 cathode materials prepared by a hydrothermal process [J]. Ceramics International, 2017, 43(4): 3483-8.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] CHEN J, YANG Y, TANG Y, et al. Constructing a Thin Disordered Self‐Protective Layer on the LiNiO2 Primary Particles Against Oxygen Release [J]. Advanced Functional Materials, 2022, 33(6).\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] HU S, LIANG X, YUAN H, et al. Enhancing Long‐Term Cycling Stability of Co‐Free Ultrahigh‐Ni Layered Cathode Materials via Synergistic Structure/Interface Engineering [J]. Advanced Functional Materials, 2025.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] HE P, ZHANG M, WANG S, et al. Enhanced high-rate and cyclic performance of Co-free and Ni-rich LiNi0.95Mn0.05O2 cathodes by coating electronic/Li\u0026thinsp;+\u0026thinsp;conductive PANI-PEG layer [J]. Journal of Solid State Electrochemistry, 2024, 28(11): 4259-71.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] SU T, LI Y, ZHANG Z, et al. Synergistic Nb Doping and Carbon Coating for Stabilized Ultrahigh-Ni-Layered Cathodes in Durable Lithium-Ion Batteries [J]. Energy \u0026amp; Fuels, 2025, 39(26): 12745-55.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] HEBERT A J, MCCALLA E J M A. The role of metal substitutions in the development of Li batteries, part I: cathodes [J]. 2021.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] NI L, GUO R, FANG S, et al. Crack-free single-crystalline Co-free Ni-rich LiNi0.95Mn0.05O2 layered cathode [J]. eScience, 2022, 2(1): 116\u0026thinsp;\u0026minus;\u0026thinsp;24.\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003e[] CHAPPEL E, N\u0026uacute;\u0026ntilde;EZ-REGUEIRO M D, DE BRION S, et al. Interlayer magnetic frustration in quasistoichiometric [J]. Physical Review B, 2002, 66(13): 132412.\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Lithium-ion battery, High-nickel cathode material, Ti doping, Local magnetic order, Cation mixing, Cycling stability","lastPublishedDoi":"10.21203/rs.3.rs-8578612/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8578612/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eWe report successfully synthesized ultra-high-performance LiNi\u003csub\u003e0.95\u003c/sub\u003eMn\u003csub\u003e0.05\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e (NM) and its TiO\u003csub\u003e2\u003c/sub\u003e-doped modified material Li[Ni\u003csub\u003e0.95\u003c/sub\u003eMn\u003csub\u003e0.05\u003c/sub\u003e]\u003csub\u003e1\u0026minus;\u003cem\u003ex\u003c/em\u003e\u003c/sub\u003eTi\u003csub\u003e\u003cem\u003ex\u003c/em\u003e\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e(0\u0026thinsp;\u0026le;\u0026thinsp;x\u0026thinsp;\u0026le;\u0026thinsp;0.1) (LNMTO) via a high-temperature solid-state method. The introduction of TiO\u003csub\u003e2\u003c/sub\u003e as a dopant aims to stabilize the crystal structure, modulate the local magnetic order of nickel ions, reduce Ni/Li exchange and magnetic frustration, enhancing electrochemical stability. X-ray diffraction (XRD) results confirm successful TiO\u003csub\u003e2\u003c/sub\u003e doping into the lattice, effectively increasing the interlayer spacing. Magnetic measurements reveal weakened average exchange interactions. The introduction of non-magnetic Ti\u003csup\u003e4+\u003c/sup\u003e ions significantly alters the low-temperature magnetic ordering state, indicating that Ti\u003csup\u003e4+\u003c/sup\u003e modulates the super-exchange interactions between TM layer, forming a more stable antiferromagnetic coupling network. Electrochemical testing confirms that at Ti\u003csup\u003e4+\u003c/sup\u003e doping concentration of 2.5%, the Li[Ni\u003csub\u003e0.95\u003c/sub\u003eMn\u003csub\u003e0.05\u003c/sub\u003e]\u003csub\u003e1\u0026minus;\u003cem\u003ex\u003c/em\u003e\u003c/sub\u003eTi\u003csub\u003e\u003cem\u003ex\u003c/em\u003e\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e(0\u0026thinsp;\u0026le;\u0026thinsp;x\u0026thinsp;\u0026le;\u0026thinsp;0.1) cathode material exhibits optimal capacity retention and cycling stability. After 40 cycles, the capacity retention increases from 70.5% to 95%, while the specific discharge capacity increased from 140 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e to 155 mAh g\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e after stable cycling. This study reveals that TiO\u003csub\u003e2\u003c/sub\u003e doping induced local magnetic ordering in LiNi\u003csub\u003e0.95\u003c/sub\u003eMn\u003csub\u003e0.05\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e is an effective strategy for stabilizing the crystal structure and enhancing the electrochemical stability of high-nickel cathode materials.\u003c/p\u003e","manuscriptTitle":"Stabilizing Nickel Ions by Local Magnetic Order Modulation for Durable Ultrahigh-Nickel Cathode","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-01-23 18:02:59","doi":"10.21203/rs.3.rs-8578612/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"cfbc3244-2f81-44ce-8112-5ab41aa99c60","owner":[],"postedDate":"January 23rd, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2026-01-31T15:10:01+00:00","versionOfRecord":[],"versionCreatedAt":"2026-01-23 18:02:59","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8578612","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8578612","identity":"rs-8578612","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}