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1.
In an attempt to overcome the problems associated with LiNiO2, the solid solution series of lithium nickel‐metal oxides, Li[Ni1–xMx]O2 (with M = Co, Mn, Al, Ti, Mg, etc.), have been investigated as favorable cathode materials for high‐energy and high‐power lithium‐ion batteries. However, along with the improvement in the electrochemical properties in Ni‐based cathode materials, the thermal stability has been a great concern, and thus violent reaction of the cathode with the electrolyte needs to be avoided. Here, we report a heterostructured Li[Ni0.54Co0.12Mn0.34]O2 cathode material which possesses both high energy and safety. The core of the particle is Li[Ni0.54Co0.12Mn0.34]O2 with a layered phase (R3‐m) and the shell, with a thickness of < 0.5 μm, is a highly stable Li1+x[CoNixMn2–x]2O4 spinel phase (Fd‐3m). The material demonstrates reversible capacity of 200 mAhg‐1 and retains 95% capacity retention under the most severe test condition of 60 °C. In addition, the amount of oxygen evolution from the lattice in the cathode with two heterostructures is reduced by 70%, compared to the reference sample. All these results suggest that the bulk Li[Ni0.54Co0.12Mn0.34]O2 consisting of two heterostructures satisfy the requirements for hybrid electric vehicles, power tools, and mobile electronics.  相似文献   

2.
The high‐energy‐density, Li‐rich layered materials, i.e., xLiMO2(1‐x)Li2MnO3, are promising candidate cathode materials for electric energy storage in plug‐in hybrid electric vehicles (PHEVs) and electric vehicles (EVs). The relatively low rate capability is one of the major problems that need to be resolved for these materials. To gain insight into the key factors that limit the rate capability, in situ X‐ray absorption spectroscopy (XAS) and X‐ray diffraction (XRD) studies of the cathode material, Li1.2Ni0.15Co0.1Mn0.55O2 [0.5Li(Ni0.375Co0.25 Mn0.375)O2·0.5Li2MnO3], are carried out. The partial capacity contributed by different structural components and transition metal elements is elucidated and correlated with local structure changes. The characteristic reaction kinetics for each element are identified using a novel time‐resolved XAS technique. Direct experimental evidence is obtained showing that Mn sites have much poorer reaction kinetics both before and after the initial activation of Li2MnO3, compared to Ni and Co. These results indicate that Li2MnO3 may be the key component that limits the rate capability of Li‐rich layered materials and provide guidance for designing Li‐rich layered materials with the desired balance of energy density and rate capability for different applications.  相似文献   

3.
A new approach to intentionally induce phase transition of Li‐excess layered cathode materials for high‐performance lithium ion batteries is reported. In high contrast to the limited layered‐to‐spinel phase transformation that occurred during in situ electrochemical cycles, a Li‐excess layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 is completely converted to a Li4Mn5O12‐type spinel product via ex situ ion‐exchanges and a post‐annealing process. Such a layered‐to‐spinel phase conversion is examined using in situ X‐ray diffraction and in situ high‐resolution transmission electron microscopy. It is found that generation of sufficient lithium ion vacancies within the Li‐excess layered oxide plays a critical role for realizing a complete phase transition. The newly formed spinel material exhibits initial discharge capacities of 313.6, 267.2, 204.0, and 126.3 mAh g?1 when cycled at 0.1, 0.5, 1, and 5 C (1 C = 250 mA g?1), respectively, and can retain a specific capacity of 197.5 mAh g?1 at 1 C after 100 electrochemical cycles, demonstrating remarkably improved rate capability and cycling stability in comparison with the original Li‐excess layered cathode materials. This work sheds light on fundamental understanding of phase transitions within Li‐excess layered oxides. It also provides a novel route for tailoring electrochemical performance of Li‐excess layered cathode materials for high‐capacity lithium ion batteries.  相似文献   

4.
The quest for high energy density and high power density electrode materials for lithium‐ion batteries has been intensified to meet strongly growing demand for powering electric vehicles. Conventional layered oxides such as Co‐rich LiCoO2 and Ni‐rich Li(NixMnyCoz)O2 that rely on only transition metal redox reaction have been faced with growing constraints due to soaring price on cobalt. Therefore, Mn‐rich electrode materials excluding cobalt would be desirable with respect to available resources and low cost. Here, the strategy of achieving both high energy density and high power density in Mn‐rich electrode materials by controlling the solubility of atoms between phases in a composite is reported. The resulting Mn‐rich material that is composed of defective spinel phase and partially cation‐disordered layered phase can achieve the highest energy density, ≈1100 W h kg?1 with superior power capability up to 10C rate (3 A g?1) among other reported Mn‐rich materials. This approach provides new opportunities to design Mn‐rich electrode materials that can achieve high energy density and high power density for Li‐ion batteries.  相似文献   

5.
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.  相似文献   

6.
The synthesis of a new layered cathode material, Na0.5[Ni0.23Fe0.13Mn0.63]O2, and its characterization in terms of crystalline structure and electrochemical performance in a sodium cell is reported. X‐ray diffraction studies and high resolution scanning electron microscopy images reveal a well‐defined P2‐type layered structure, while the electrochemical tests demonstrate excellent characteristics in terms of high capacity and cycle life. This performance, the low cost, and the environmental compatibility of its component poses Na0.5[Ni0.23Fe0.13Mn0.63]O2 to be among the most promising materials for the next generation of sodium‐ion batteries.  相似文献   

7.
Cobalt‐free layered lithium‐rich nickel manganese oxides, Li[LixNiyMn1?x?y]O2 (LLNMO), are promising positive electrode materials for lithium rechargeable batteries because of their high energy density and low materials cost. However, substantial voltage decay is inevitable upon electrochemical cycling, which makes this class of materials less practical. It has been proposed that undesirable voltage decay is linked to irreversible structural rearrangement involving irreversible oxygen loss and cation migration. Herein, the authors demonstrate that the voltage decay of the electrode is correlated to Mn4+/Mn3+ redox activation and subsequent cation disordering, which can be remarkably suppressed via simple compositional tuning to induce the formation of Ni3+ in the pristine material. By implementing our new strategy, the Mn4+/Mn3+ reduction is subdued by an alternative redox reaction involving the use of pristine Ni3+ as a redox buffer, which has been designed to be widened from Ni3+/Ni4+ to Ni2+/Ni4+, without compensation for the capacity in principle. Negligible change in the voltage profile of modified LLNMO is observed upon extended cycling, and manganese migration into the lithium layer is significantly suppressed. Based on these findings, we propose a general strategy to suppress the voltage decay of Mn‐containing lithium‐rich oxides to achieve long‐lasting high energy density from this class of materials.  相似文献   

8.
Li and Mn‐rich layered cathodes, despite their high specific capacity, suffer from capacity fading and discharge voltage decay upon cycling. Both specific capacity and discharge voltage of Li and Mn‐rich cathodes are stabilized upon cycling by optimized Al doping. Doping Li and Mn‐rich cathode materials Li1.2Ni0.16Mn0.56Co0.08O2 by Al on the account of manganese (as reflected by their stoichiometry) results in a decrease in their specific capacity but increases pronouncedly their stability upon cycling. Li1.2Ni0.16Mn0.51Al0.05Co0.08O2 exhibits 96% capacity retention as compared to 68% capacity retention for Li1.2Ni0.16Mn0.56Co0.08O2 after 100 cycles. This doping also reduces the decrease in the average discharge voltage upon cycling, which is the longstanding fatal drawback of these Li and Mn‐rich cathode materials. The electrochemical impedance study indicates that doping by Al has a surface stabilization effect on these cathode materials. The structural analysis of cycled electrodes by Raman spectroscopy suggests that Al doping also has a bulk stabilizing effect on the layered LiMO2 phase resulting in the better electrochemical performance of Al doped cathode materials as compared to the undoped counterpart. Results from a prolonged systematic work on these cathode materials are presented and the best results that have ever been obtained are reported.  相似文献   

9.
Li[Ni0.9Co0.1]O2 (NC90), Li[Ni0.9Co0.05Mn0.05]O2 (NCM90), and Li[Ni0.9Mn0.1]O2 (NM90) cathodes are synthesized for the development of a Co‐free high‐energy‐density cathode. NM90 maintains better cycling stability than the two Co‐containing cathodes, particularly under harsh cycling conditions (a discharge capacity of 236 mAh g?1 with a capacity retention of 88% when cycled at 4.4 V under 30 °C and 93% retention when cycled at 4.3 V under 60 °C after 100 cycles). The reason for the enhanced stability is mainly the ability of NM90 to absorb the strain associated with the abrupt anisotropic lattice contraction/extraction and to suppress the formation of microcracks, in addition to enhanced chemical stability from the increased presence of stable Mn4+. Although the absence of Co deteriorates the rate capability, this can be overcome as the rate capability of the NM90 approaches that of the NCM90 when cycled at 60 °C. The long‐term cycling stability of NM90 is confirmed in a full cell, demonstrating that it is one of the most promising Co‐free cathodes for high‐energy‐density applications. This study not only provides insight into redefining the role of Mn in a Ni‐rich cathode, it also represents a clear breakthrough in achieving a commercially viable Co‐free Ni‐rich layered cathode.  相似文献   

10.
An increase in the amount of nickel in LiMO2 (M = Ni, Co, Mn) layered system is actively pursued in lithium‐ion batteries to achieve higher capacity. Nevertheless, fundamental effects of Ni element in the three‐component layered system are not systematically studied. Therefore, to unravel the role of Ni as a major contributor to the structural and electrochemical properties of Ni‐rich materials, Co‐fixed LiNi0.5+xCo0.2Mn0.3–xO2 (x = 0, 0.1, and 0.2) layered materials are investigated. The results, on the basis of synchrotron‐based characterization techniques, present a decreasing trend of Ni2+ content in Li layer with increasing total Ni contents. Moreover, it is discovered that the chex.‐lattice parameter of layered system is not in close connection with the interslab thickness related to actual Li ion pathway. The interslab thickness increases with increasing Ni concentration even though the chex.‐lattice parameter decreases. Furthermore, the lithium ion pathway is preserved in spite of the fact that the c‐axis is collapsed at highly deintercalated states. Also, a higher Ni content material shows better structural properties such as larger interslab thickness, lower cation disorder, and smoother phase transition, resulting in better electrochemical properties including higher Li diffusivity and lower overpotential when comparing materials with lower Ni content.  相似文献   

11.
Ni‐rich Li[NixCoyMn1?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 LiNi0.8Co0.1Mn0.1O2 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.  相似文献   

12.
Li2MnO3 is a critical component in the family of “Li‐excess” materials, which are attracting attention as advanced cathode materials for Li‐ion batteries. Here, first‐principle calculations are presented to investigate the electrochemical activity and structural stability of stoichiometric LixMnO3 (0 ≤ x ≤ 2) as a function of Li content. The Li2MnO3 structure is electrochemically activated above 4.5 V on delithiation and charge neutrality in the bulk of the material is mainly maintained by the oxidization of a portion of the oxygen ions from O2? to O1?. While oxygen vacancy formation is found to be thermodynamically favorable for x < 1, the activation barriers for O2? and O1? migration remain high throughout the Li com­position range, impeding oxygen release from the bulk of the compound. Defect layered structures become thermodynamically favorable at lower Li content (x < 1), indicating a tendency towards the spinel‐like structure transformation. A critical phase transformation path for forming nuclei of spinel‐like domains within the matrix of the original layered structure is proposed. Formation of defect layered structures during the first charge is shown to manifest in a depression of the voltage profile on the first discharge, providing one possible explanation for the observed voltage fade of the Li‐excess materials.  相似文献   

13.
Subzero‐temperature Li‐ion batteries (LIBs) are highly important for specific energy storage applications. Although the nickel‐rich layered lithium transition metal oxides(LiNixCoyMnzO2) (LNCM) (x > 0.5, x + y +z = 1) are promising cathode materials for LIBs, their very slow Li‐ion diffusion is a main hurdle on the way to achieve high‐performance subzero‐temperature LIBs. Here, a class of low‐temperature organic/inorganic hybrid cathode materials for LIBs, prepared by grafting a conducting polymer coating on the surface of 3 µm sized LiNi0.6Co0.2Mn0.2O2 (LNCM‐3) material particles via a greener diazonium soft‐chemistry method is reported. Specifically, LNCM‐3 particles are uniformly coated with a thin polyphenylene film via the spontaneous reaction between LNCM‐3 and C6H5N2+BF4?. Compared with the uncoated one, the polyphenylene‐coated LNCM‐3 (polyphenylene/LNCM‐3) has shown much improved low‐temperature discharge capacity (≈148 mAh g?1 at 0.1 C, ?20 °C), outstanding rate capability (≈105 mAh g?1 at 1 C, ?20 °C), and superior low‐temperature long‐term cycling stability (capacity retention is up to 90% at 0.5 C over 1150 cycles). The low‐temperature performance of polyphenylene/LNCM‐3 is the best among the reported state‐of‐the art cathode materials for LIBs. The present strategy opens up a new avenue to construct advanced cathode materials for wider range applications.  相似文献   

14.
Safety has been a major technological concern hindering the deployment of lithium‐ion batteries for automobile applications. We investigated the decomposition mechanism of delithiated cathode materials at thermal abuse conditions using Li1.1[Ni1/3Mn1/3Co1/3]0.9O2 as a model cathode material. An in‐situ high‐energy X‐ray diffraction technique was established as an alternative to conventional thermal analysis techniques like differential scanning calorimetry and accelerating rate calorimetry. The X‐ray diffraction data revealed that the thermal decomposition pathway of delithiated Li1‐x[Ni1/3Mn1/3Co1/3]0.9O2 strongly depended on the exposed chemical environment, like solvents and lithium salts. A phase transformation of dry delithiated Li1‐x[Ni1/3Mn1/3Co1/3]0.9O2 was observed at about 278 °C, and its onset temperature was reduced to about 197°C with the presence of the electrolyte. It is suggested that the reduction in thermal stability is possibly related to proton intercalation into the delithiated material.  相似文献   

15.
16.
Using fast time‐resolved in situ X‐ray diffraction, charge‐rate dependent phase transition processes of layer structured cathode material LiNi1/3Mn1/3Co1/3O2 for lithium‐ion batteries are studied. During first charge, intermediate phases emerge at high rates of 10C, 30C, and 60C, but not at low rates of 0.1C and 1C. These intermediate phases can be continuously observed during relaxation after the charging current is switched off. After half‐way charging at high rate, sample studied by scanning transmission electron microscopy shows Li‐rich and Li‐poor phases' coexistence with tetrahedral occupation of Li in Li‐poor phase. The high rate induced overpotential is thought to be the driving force for the formation of this intermediate Li‐poor phase. The in situ quick X‐ray absorption results show that the oxidation of Ni accelerates with increasing charging rate and the Ni4+ state can be reached at the end of charge with 30C rate. These results give new insights in the understanding of the layered cathodes during high‐rate charging.  相似文献   

17.
A multicompositional particulate Li[Ni0.9Co0.05Mn0.05]O2 cathode in which Li[Ni0.94Co0.038Mn0.022]O2 at the particle center is encapsulated by a 1.5 µm thick concentration gradient (CG) shell with the outermost surface composition Li[Ni0.841Co0.077Mn0.082]O2 is synthesized using a differential coprecipitation process. The microscale compositional partitioning at the particle level combined with the radial texturing of the refined primary particles in the CG shell layer protracts the detrimental H2 → H3 phase transition, causing sharp changes in the unit cell dimensions. This protraction, confirmed by in situ X‐ray diffraction and transmission electron microscopy, allows effective dissipation of the internal strain generated upon the H2 → H3 phase transition, markedly improving cycling performance and thermochemical stability as compared to those of the conventional single‐composition Li[Ni0.9Co0.05Mn0.05]O2 cathodes. The compositionally partitioned cathode delivers a discharge capacity of 229 mAh g?1 and exhibits capacity retention of 88% after 1000 cycles in a pouch‐type full cell (compared to 68% for the conventional cathode). Thus, the proposed cathode material provides an opportunity for the rational design and development of a wide range of multifunctional cathodes, especially for Ni‐rich Li[NixCoyMn1‐x‐y]O2 cathodes, by compositionally partitioning the cathode particles and thus optimizing the microstructural response to the internal strain produced in the deeply charged state.  相似文献   

18.
Li‐rich layered metal oxides have attracted much attention for their high energy density but still endure severe capacity fading and voltage decay during cycling, especially at elevated temperature. Here, facile surface treatment of Li1.17Ni0.17Co0.17Mn0.5O2 (0.4Li2MnO3·0.6LiNi1/3Co1/3Mn1/3O2) spherical cathode material is designed to address these drawbacks by hybrid surface protection layers composed of Mg2+ pillar and Li‐Mg‐PO4 layer. As a result, the surface coated Li‐rich cathode material exhibits much enhanced cycling stability at 60 °C, maintaining 72.6% capacity retention (180 mAh g?1) between 3.0 and 4.7 V after 250 cycles. More importantly, 88.7% average discharge voltage retention can be obtained after the rigorous cycle test. The strategy developed here with novel hydrid surface protection effect can provide a vital approach to inhibit the undesired side reactions and structural deterioration of Li‐rich cathode materials and may also be useful for other layered oxides to increase their cycling stability at elevated temperature.  相似文献   

19.
Layered lithium–nickel–cobalt–manganese oxide (NCM) materials have emerged as promising alternative cathode materials owing to their high energy density and electrochemical stability. Although high reversible capacity has been achieved for Ni‐rich NCM materials when charged beyond 4.2 V versus Li+/Li, full lithium utilization is hindered by the pronounced structural degradation and electrolyte decomposition. Herein, the unexpected realization of sustained working voltage as well as improved electrochemical performance upon electrochemical cycling at a high operating voltage of 4.9 V in the Ni‐rich NCM LiNi0.895Co0.085Mn0.02O2 is presented. The improved electrochemical performance at a high working voltage at 4.9 V is attributed to the removal of the resistive Ni2+O rock‐salt surface layer, which stabilizes the voltage profile and improves retention of the energy density during electrochemical cycling. The manifestation of the layered Ni2+O rock‐salt phase along with the structural evolution related to the metal dissolution are probed using in situ X‐ray diffraction, neutron diffraction, transmission electron microscopy, and X‐ray absorption spectroscopy. The findings help unravel the structural complexities associated with high working voltages and offer insight for the design of advanced battery materials, enabling the realization of fully reversible lithium extraction in Ni‐rich NCM materials.  相似文献   

20.
Boron‐doped Li[Ni0.90Co0.05Mn0.05]O2 cathodes are synthesized by adding B2O3 during the lithiation of the hydroxide precursor. Density functional theory confirms that boron doping at a level as low as 1 mol% alters the surface energies to produce a highly textured microstructure that can partially relieve the intrinsic internal strain generated during the deep charging of Li[Ni0.90Co0.05Mn0.05]O2. The 1 mol% B‐Li[Ni0.90Co0.05Mn0.05]O2 cathode thus delivers a discharge capacity of 237 mAh g?1 at 4.3 V, with an outstanding capacity retention of 91% after 100 cycles at 55 °C, which is 15% higher than that of the undoped Li[Ni0.90Co0.05Mn0.05]O2 cathode. This proposed synthesis strategy demonstrates that an optimal microstructure exists for extending the cycle life of Ni‐rich Li[Ni1‐xyCoxMny]O2 cathodes that have an inadequate cycling stability in electric vehicle applications and indicates that an optimal microstructure can be achieved through surface energy modification.  相似文献   

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