Countering Voltage Decay and Capacity Fading of Lithium‐Rich Cathode Material at 60 °C by Hybrid Surface Protection Layers

Li, Wen; Oh, Pilgun; Li, Haiping; Myeong, Seungjun; Cho, Woongrae; Cho, Jaephil

doi:10.1002/aenm.201500274

Cited by 179 publications

(142 citation statements)

References 56 publications

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“…That is why, surface coatings with Al 2 O 3 , AlF 3 , AlPO 4 , MgO, with a novel surface configuration of Mg 3 (PO 4 ) 2 or effective modification by Li 2 MnO 3 which suppress layered-to-spinel transitions can stabilize capacity and voltage decay upon prolonged cycling of Li-, Mn-rich cathodes. [60][61][62][63][64][65] Similar results were obtained by doping of these cathodes with foreign cations (Na, Mg, Al, Zr, etc.) as described below.…”

Section: Efforts To Reduce Capacity Fading and Discharge Voltage Decasupporting

confidence: 71%

Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li‐ and Mn‐Rich Cathode Materials for Li‐Ion Batteries

Nayak

Erickson

Schipper

et al. 2017

Advanced Energy Materials

489

304

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CO 2 emissions. Hence, transportation dependent on electrical propulsion (electric vehicles) instead of internal combustion engines can greatly reduce the pollution caused by our transportation infrastructure. While rechargeable Li-ion batteries are the major power source for portable electronic devices such as smartphones and laptop computers, further improvements in their energy density is required in order to promote electrochemical propulsion devices that can compete with internal combustion engines. [1] The energy density of Li-ion batteries depends on the specific capacities and redox potentials of their electrode materials. Layered lithiated transition metal oxides such as LiCoO 2 , LiNi 1/2 Mn 1/2 O 2 , and LiNi 1/3 Mn 1/3 Co 1/3 O 2 ("NMC 111") were extensively studied as cathodes, which can exhibit specific capacities ≤160 mA h g −1 with an upper potential limit of 4.3 V versus Li. [2] The high cost, low thermal stability, and fast capacity fading at high current rates or during deep cycling of currently used LiCoO 2 necessitated the development of other layered cathodes, such as LiNi 1/2 Mn 1/2 O 2 , NMC 111, etc. The electrochemical performance of these layered metal oxides was recently reviewed by Yushin and coworkers. [3] Higher capacities can be extracted from layered metal oxide cathodes by cycling to upper potentials of about 4.5 V, however, driving these layered cathode materials to such high potentials enhances the structural instability and impedance growth. [4,5] Another important direction is the development of Ni-rich NCM cathode materials. As the content of Ni is higher, the specific capacity that can be extracted is higher as

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Section: Efforts To Reduce Capacity Fading and Discharge Voltage Decasupporting

confidence: 71%

Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li‐ and Mn‐Rich Cathode Materials for Li‐Ion Batteries

Nayak

Erickson

Schipper

et al. 2017

Advanced Energy Materials

489

304

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“…Similar to other Li-rich layered oxides, both of them (Fig. 4a) exhibit a long plateau region at ∼ 4.5 V versus Li + /Li 0 , which usually is ascribed to the electrochemical activation of the Li 2 MnO 3 component during the initial charge process383940, although an electrolyte/electrode side reaction is expected in this region. Interestingly, the value of the initial discharge capacity for the GSIR LR-NCM can reach as high as 301 mAh g −1 compared with that of 276 mAh g −1 for the pristine LR-NCM.…”

Section: Resultsmentioning

confidence: 62%

Gas–solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries

et al. 2016

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Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas–solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g−1 with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g−1 still remains without any obvious decay in voltage. This study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries.

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“…It has been proposed that the Mg in the host structure can be existed in the lithium site, which prevents the phase transition. [127,128] In addition, the degree of the cation disorder (Ni/Li mixing) decreased in the Mg doped NCM622 with ≈1.6% (Mg-1), ≈1.8% (Mg-3), and ≈3.2% (Mn-5) compared with the pristine NCM622 (≈5.2%). This reduced degree of [90] Copyright 2015, The Electrochemical Society.…”

Section: Dopingmentioning

confidence: 99%

Prospect and Reality of Ni‐Rich Cathode for Commercialization

Kim

Lee

Cha

et al. 2017

Advanced Energy Materials

Self Cite

616

582

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practical candidate for the wide application of the LIBs with respect to the reversible capacity, rate capability, and capital cost. [4][5][6][7] In terms of nickel contents, the nickel-rich cathodes with nickel content above 80% have advantages in gravimetric capacity, allowing high gravimetric energy density, compared with the nickel content less than 80%. Currently, the nickel-rich cathodes with the amount of nickel less than 60% are fully commercialized. However, the nickel-rich cathodes with nickel content of ≥80% still have many difficulties in the commercialization with respect to powder properties and electrode fabrication process.The unstable powder properties originate from residual lithium compounds such as LiOH and Li 2 CO 3 that formed by the spontaneous reduction of sensitive trivalent nickel ions during the synthesis process and storage in air. [8][9][10][11] The Li 2 CO 3 significantly promotes the gas evolution and increase the moisture of the cathode powder, which strongly related to the safety issue. [12][13][14] Furthermore, the LiOH on the cathode increases the powder pH value, causing the gelation of the slurry during the electrode fabrication process. The nickel-rich cathode with nickel content of ≤60% have acceptable amount of residual lithium compounds for the practical use. By contrast, the cathode with amount of nickel of ≥80% should be treated by additional process to reduce the residual lithium compounds ( Table 1). Furthermore, other powder properties, such as powder pH and moisture, should be carefully controlled when nickel contents were exceeded of ≥80%. Thus, for the practical application of these cathode materials, most battery companies have adapted the washing process, in which the cathode power was stirred in purified water for 20-40 min. [15,16] The washing process could greatly reduce the residual lithium compounds and powder pH value. [15] However, the washing process not only increases process time and capital cost but also make the nickel-rich cathode more chemically sensitive than nonwashed cathodes. [16] More seriously, the water washing deteriorates the thermal stability of the nickel-rich cathodes, indicating that the washing process should be substituted by other methods for the battery safety.Another important factor for the commercialization of the nickel-rich cathodes is the electrode density directly related to the energy density. In general, the nickel-rich cathodesThe layered nickel-rich cathode materials are considered as promising cathode materials for lithium-ion batteries (LIBs) due to their high reversible capacity and low cost. However, several significant challenges, such as the unstable powder properties and limited electrode density, hindered the practical application of the nickel-rich cathode materials with the nickel content over 80%. Herein, important stability issues and in-depth understanding of the nickel-rich cathode materials on the basis of the industrial electrode fabrication condition for the commercialization of the nickel-rich cathode m...

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Countering Voltage Decay and Capacity Fading of Lithium‐Rich Cathode Material at 60 °C by Hybrid Surface Protection Layers

Cited by 179 publications

References 56 publications

Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li‐ and Mn‐Rich Cathode Materials for Li‐Ion Batteries

Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li‐ and Mn‐Rich Cathode Materials for Li‐Ion Batteries

Gas–solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries

Prospect and Reality of Ni‐Rich Cathode for Commercialization

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