Structural and Electrochemical Study of Al2O3 and TiO2 Coated Li1.2Ni0.13Mn0.54Co0.13O2 Cathode Material Using ALD

Zhang, Xiaofeng; Belharouak, Ilias; Li, Li; Yu, Lei; Elam, Jeffrey W.; Nie, Anmin; Chen, Xinqi; Yassar, Reza S.; Axelbaum, Richard L.

doi:10.1002/aenm.201300269

Cited by 426 publications

(267 citation statements)

References 58 publications

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“…[1][2][3][4][5] Motivated by this, high-specifi ccapacity layered Li-rich materials and high-rate-capability spinel cathodes have attracted much attention. [6][7][8][9][10] Layered Li-rich materials can deliver a capacity larger than 200 mA h g −1 when charged above 4.5 V, [ 11 ] which however suffer from an inferior know the signifi cant infl uences of synthesis temperatures on compositions and the contents of the layered and spinel phases in composite.…”

Section: Introductionmentioning

confidence: 99%

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

Luo

et al. 2014

Advanced Energy Materials

170

103

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rate capability. [ 12,13 ] In contrast, spinel cathodes exhibit a high-rate capability due to the effi cient 3D diffusion of lithium ions, nevertheless the discharge capacity is low, only about 130 mA h g −1 . [ 14,15 ] Then, a highly interesting, but also challenging question appears: can the rate capability be much improved by introducing spinel component into the layered oxides? Previous investigations have shown that the cubic close-packed oxygen arrays in both the layered and spinel oxides are structurally compatible. [ 16 ] Therefore, it is possible to integrate the Li-rich layered and spinel oxides into a composite, which might show both a high capacity and an excellent rate capability.Much effort has been devoted to the preparation of composites that intergrate both layered Li-rich oxides and spinel oxides (i.e., spinel-layered materials), which have led to several high-energy and power electrodes, [17][18][19][20] such as the outstanding cathode materials of spinel/ layered heterostructure, [ 17 ] [ 18 ] Unfortunately, most synthetic methods still suffer from several shortcomings. For instance, it is diffi cult to obtain a homogeneous mixture of layered and spinel oxides. The preparation procedures are always tedious, which may introduce uncertain factors in reproducing the electrochemical performance. On the other hand, metal-ion impurities, such as K + , were inevitably introduced into the fi nal products. In particular, the synthetic methods ever reported cannot allow the control over the morphology to give microspheres of spinellayered materials, due to the multiple transition metal ions and phases involved. As a consequence, spherical spinel-layered cathode materials are highly necessary, which expect to impose a signifi cant impact on electrochemical performance (especially for rate capability) of Li-ions batteries.Here, we report on the preparation of a spinel-layered Lirich Li-Mn-Co-O microsphere using a solvothermal-precursor method. This method is an extension of ther oxalate-precursor method, [ 21 ] which has been successfully applied to prepare Lirich layered composite cathodes. This new method has the advantages of the oxalate-precursor method where lithium ions and transition metal ions are precipitated simultaneously in the absence of alkali metal ions to form uniform precursors, and provides the possibility for regulation of spherical morphology and dimension. Based on previous results, [ 16,22 ] we 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...

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Section: Introductionmentioning

confidence: 99%

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

Luo

et al. 2014

Advanced Energy Materials

170

103

View full text Add to dashboard Cite

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“…84,85 Also transition metal ion dissolution may be 86 An additional benefit may come in the form of lower first cycle irreversible capacity, since the coating restricts oxygen evolution and the subsequent irreversible transition metal migration to the Li + layer, ultimately leading to spinel formation. 84 MnO 2 coatings may take advantage of these phenomena, since formation of this material occurs at the surface of Li-rich materials during their electrochemical activation step anyways. [87][88][89] Most coatings generally take the form of monovalent oxides, such as Al 2 92 An interesting coating with promising results came from utilizing a thin film of the olivine cathode material, LiFePO 4 .…”

Section: Stabilization Of Voltage and Capacity Fadementioning

confidence: 99%

Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes

Erickson

Schipper

Penki

et al. 2017

J. Electrochem. Soc.

152

102

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Electrodes prepared from lithium-rich (Li-rich) xLi 2 MnO 3 ·(1-x)LiNi a Co b Mn c O 2 materials (a + b + c = 1) show extremely high discharge capacities, arising from excess Li + present in their Li 2 MnO 3 component, and the ability to reversibly store charge with O 2− anions. These electrodes suffer serious voltage and capacity fading however, due to the migration of transition metals to the Li-layer at advanced states of charging, partial structural layered-to-spinel transformation and other reasons. In this focus paper, the current understanding of the above materials is summarized, briefly concluding with attempts by our groups to mitigate the voltage and capacity fade of these electrodes.

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“…and polyanion doping based on nonmetal elements, such as BO 4 5− , [28] SiO 4 4− , [29] PO 4 3-, [30] etc., have been employed to improve the cyclic durability by weakening the TM-O covalency in the oxygen closepacked structure. In addition, surface coatings using metal oxides, [31][32][33][34] fluorides and phosphates, [35][36][37] LiNiPO 4 and Li 3 VO 4 , [38][39][40] have been applied to protect the surface structure from side reactions with the electrolyte under high voltage and to restrain the layered-to-spinel transformation which occurs preferentially on the crystal surface and leads to capacity fading of LLO materials. However, the ionic dopants and coating materials are mostly electrochemically inactive, so the improved cycling stability is achieved at the expense of reduced specific capacity/energy density of the cathode.…”

mentioning

confidence: 99%

Surface Structural Transition Induced by Gradient Polyanion‐Doping in Li‐Rich Layered Oxides: Implications for Enhanced Electrochemical Performance

Zhao

Liu

Wang

et al. 2016

Adv Funct Materials

157

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To meet the demanding requirements in plug-in hybrid electric vehicles (PHEVs) or electric vehicles (EVs), higher energy density materials, such as the Li-rich, layered manganese-based oxides (LLOs) with the general formula xLi 2 MnO 3 ·(1-x)LiTMO 2 (TM = Mn, Ni, Co, etc.), are promising candidates as they possess higher reversible capacity (>250 mAh g −1 ), improved safety and much reduced cost. [4][5][6][7][8][9] Recent microscopic evidence reveals the intergrowth of rhombohedral LiTMO 2 (R-3m) and the monoclinic Li 2 MnO 3 -like layered structure (C/2m) at the atomic scale in the oxide grains. [10] The Li 2 MnO 3 component serves as an electrochemically active phase for Li storage when cycled above 4.5 V versus Li/Li + . [8,[11][12][13][14] Nevertheless, these LLO materials undergo steady voltage/capacity decay when cycled above 4.5 V, resulting in a substantial decrease of the cathode energy density. [15][16][17][18] The origin of voltage/capacity decay upon cycling stems from cation migration between TM layers and Li layers and subsequent phase transformation. [19,20] The cationic doping with other metallic cations (such as Mg, [21] Al, [22] Ti, [23] Sn, [24] Ru, [25] Y, [26] Zn, [27] etc.) and polyanion doping based on nonmetal elements, such as BO 4 5− , [28] SiO 4 4− , [29] PO 4 3-, [30] etc., have been employed to improve the cyclic durability by weakening the TM-O covalency in the oxygen closepacked structure. In addition, surface coatings using metal oxides, [31][32][33][34] fluorides and phosphates, [35][36][37] LiNiPO 4 and Li 3 VO 4 , [38][39][40] have been applied to protect the surface structure from side reactions with the electrolyte under high voltage and to restrain the layered-to-spinel transformation which occurs preferentially on the crystal surface and leads to capacity fading of LLO materials. However, the ionic dopants and coating materials are mostly electrochemically inactive, so the improved cycling stability is achieved at the expense of reduced specific capacity/energy density of the cathode. Moreover, a conformal and continuous coating on the surface of oxide particles is rather difficult to obtain practically. Hence, advancing the structural and cycling stability in both the bulk material and the surface structure through a simple way is highly desired for potential applications of LLO materials.Herein, we develop a novel LLO material with a nanoscaled spinel-like surface layer through gradient doping of polyanions Surface Structural Transition Induced by Gradient Polyanion-Doping in Li-Rich Layered Oxides: Implications for Enhanced Electrochemical PerformanceYing Zhao, Jiatu Liu, Shuangbao Wang, Ran Ji, Qingbing Xia, Zhengping Ding, Weifeng Wei,* Yong Liu, Peng Wang,* and Douglas G. Ivey Lithium-rich layered oxides (LLOs) exhibit great potential as high-capacity cathode materials for lithium-ion batteries, but usually suffer from capacity/ voltage fade during electrochemical cycling. Herein, a gradient polyaniondoping strategy is developed to initiate surface structural trans...

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Structural and Electrochemical Study of Al₂O₃ and TiO₂ Coated Li_1.2Ni_0.13Mn_0.54Co_0.13O₂ Cathode Material Using ALD

Cited by 426 publications

References 58 publications

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

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

Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes

Surface Structural Transition Induced by Gradient Polyanion‐Doping in Li‐Rich Layered Oxides: Implications for Enhanced Electrochemical Performance

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