Armoring LiNi1/3Co1/3Mn1/3O2 Cathode with Reliable Fluorinated Organic–Inorganic Hybrid Interphase Layer toward Durable High Rate Battery

Chen, Yu; Zhao, Weimin; Zhang, Quanhai; Yang, Guangzhi; Zheng, Jianming; Tang, Wei; Xu, Qing; Lai, Chunyan; Yang, Jing; Peng, Chengxin

doi:10.1002/adfm.202000396

Cited by 85 publications

(68 citation statements)

References 50 publications

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“…This region is usually attributed to surface film resistance in the literature, corresponding to the growth of a cathode-electrolyte interphase (CEI). [20,21] However, this simplified interpretation neglects to account for other resistive mechanisms inherent to the NMC-89 material and electrode configuration that can also contribute to the high-frequency impedance response, such as contact resistance between cathode particles and the Al current collector, and interparticle contact resistance (together denoted as R contact ). [22][23][24] Figure S3 (Supporting Information) reveals the relationship between the size of the first semicircle and the electrode porosity of NMA-89 in coin half cells compared against the size of the first semicircle in the uncalendered NCA-89 electrode.…”

Section: Electrochemical Characterizationmentioning

confidence: 99%

“…Even when using organic electrolyte with fluorinated additives, such as Li 2 PO 2 F 2 and fluorinated ethylene carbonate (FEC), no indication of fluoro-organic species is found on the surface of LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC111) after 400 cycles between 2.8 and 4.3 V in half cells. [21] Therefore, these peaks are likely generated from the charging effect of insulating species on the surface, an experimental artifact that broadens and shifts existing peaks (Figure S8, Supporting Information).…”

Section: Cathode-electrolyte Interphase (Cei)mentioning

confidence: 99%

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In‐Depth Analysis of the Degradation Mechanisms of High‐Nickel, Low/No‐Cobalt Layered Oxide Cathodes for Lithium‐Ion Batteries

Lee

Dolocan

et al. 2021

Advanced Energy Materials

106

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total global passenger car and light duty vehicle sales in 2020, EV sales in 2030 are forecasted to contribute over 30% of the total sales. [1] The demand for automotive lithium-ion batteries is going to surpass 1.5 TWh per year in 2030, nearly a tenfold increase from the current demand of EV battery capacity globally. [2] With 89% of the overall battery demand projected to come from EVs alone in 2030, the future direction of lithium-ion battery research and development will undoubtedly be shaped by the performance demand of EVs.Rapid commercial adoption of EVs is primarily hindered by a relatively expensive vehicle price and low driving range per a single charge. The bottleneck lies within the high cost and inadequate energy density of EV battery packs. Current lithium-ion battery packs for EVs cost on average US$137 kWh -1 and delivers 160-170 Wh kg -1 of energy density at the pack-level. [3,4] For EVs to achieve a cost and range parity with internal combustion vehicles, next-generation battery packs should cost less than US$100 kWh -1 and deliver at least 235 Wh kg -1 according to the Office of Energy Efficiency and Renewable Energy. [5] Achieving these performance metrics largely depends on the energy density and cost of nickel-based layered oxide cathode materials. The prevailing trend within EV battery manufacturers is to increase the nickel content of LiNi 1−x−y Mn x Co y O 2 (NMC) for higher energy density, progressing incrementally from LiNi 0.33 Mn 0.33 Co 0.33 O 2 (NMC111) → LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC532) → LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC622) → LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811). However, high-Ni layered oxide cathode materials generally suffer from lattice and surface instabilities that diminish the longevity of the battery. [6,7] Dopants like Al have been proven effective in mitigating these detrimental effects, giving rise to LiNi 1−x−y Co x Al y O 2 (NCA) as another subset of layered oxide cathode materials that is employed in the Tesla Model 3. [8] Incorporating Co in cathode materials for EVs, on the other hand, is problematic from a cost and sustainability perspective. Cobalt is the most expensive element in the cathode composition and has experienced volatile price movements from US$30 kg -1 to over US$90 kg -1 . A rational compositional design of high-nickel, cobalt-free layered oxide materials for high-energy and low-cost lithium-ion batteries would be expected to further propel the widespread adoption of electric vehicles (EVs), yet a composition with satisfactory electrochemical properties has yet to emerge. The previous work has demonstrated a promising LiNi 0.883 Mn 0.056 Al 0.061 O 2 (NMA-89) composition that outperformed high-nickel, cobalt-containing analogs in cycling stability and maintained a comparable rate performance and thermal stability. Herein, the capacity fading mechanism of NMA-89 in a pouch full cell with a 4.2 V cutoff is compared to that of its cobalt-containing analogs. The results reveal that particle cracking in LiNi 0.89 Mn 0.055 Co 0.055 O 2 (NMC-89) and LiNi...

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Section: Electrochemical Characterizationmentioning

confidence: 99%

Section: Cathode-electrolyte Interphase (Cei)mentioning

confidence: 99%

In‐Depth Analysis of the Degradation Mechanisms of High‐Nickel, Low/No‐Cobalt Layered Oxide Cathodes for Lithium‐Ion Batteries

Lee

Dolocan

et al. 2021

Advanced Energy Materials

106

View full text Add to dashboard Cite

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“…Considering that fluorine-containing species, Li 2 CO 3 and poly(CO 3 ) are beneficial to maintain the structural integrity of active materials. [12,21,22] the CEI generated at 55 °C should hold better stability. This is supported by the XPS analysis on the Pre25-NMC and Pre55-NMC electrodes after long-term cycling (Figure S9, Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Enabling the High‐Voltage Operation of Layered Ternary Oxide Cathodes via Thermally Tailored Interphase

Zhu

Cao

et al. 2022

Small Methods

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demanded to push up the operating voltage of NMC-based cathodes to release their full benefits for high-energy LIBs. [4] One of the main issues limiting the high-voltage operation of NMC-based cathodes is the undesirable detrimental side reactions between cathode and electrolytes, which usually lead to severe electrolyte decomposition and surface structure distortion. [5] Additionally, the decomposition of electrolytes would generate hydrofluoric acid, which is likely to dissolve transition metal ions in the cathode. [6] Currently two approaches have been widely used to minimize these parasitic reactions. [7] One is coating of the cathode particles with an artificial protective layer, [8] the other is introducing electrolyte additives to build a robust cathode/ electrolyte interphase (CEI). [9] However, the electrochemical inactivity of the coating materials generally sacrifices the specific capacity, [10] while the usage of new electrolyte components will increase the production costs. It is thus desirable to develop facile and effective methods to create an efficient protective layer on NMC-based cathodes.Temperature is a determinant factor for the electrolyte decomposition. [11] For instance, the oxidation potentials of the commercial electrolyte of 1 m LiPF 6 in ethylene carbonate/ dimethyl carbonate/diethyl carbonate (EC/DMC/DEC, 1:1:1 by volume, Sigma-Aldrich) continuously decreases as the temperature increases (Figure 1a), showing the significant influence of temperature on the oxidation of electrolytes. Since the CEI layer is derived from the electrolyte decomposition, [7,12] temperature should play a key role in determining the CEI properties. However, the underlying scientific principle of temperature on the CEI growth behavior as well as how temperature can be used to regulate the CEI properties remains unexplored.Herein, we proposed an novel high-temperature pre-cycling approach to modulate the CEI and demonstrated the operation for improving the cycle stability of a representative NMC-based cathode LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC111) in 3.0−4.5 V. Specifically, elevating the temperature from 25 °C to 55 °C during the first five cycles could promote the electrolyte decomposition, yielding a robust and uniform CEI layer enriched with fluorine-containing species, Li 2 CO 3 and poly(CO 3 ). Such a CEI layer can suppress the interfacial parasitic reactions during extended cycling at 25 °C, endowing the NMC111 electrode with a reversible capacity of 162 mAh/g at 1C (1C = 150 mA g −1 )Layered ternary oxides LiNi x Mn y Co z O 2 are promising cathode candidates for high-energy lithium-ion batteries (LIBs), but they usually suffer from the severe interfacial parasitic reactions at voltages above 4.3 V versus Li + /Li, which greatly limit their practical capacities. Herein, using LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC111) as the model system, a novel high-temperature pre-cycling strategy is proposed to realize its stable cycling in 3.0−4.5 V by constructing a robust cathode/electrolyte interphase (CEI). Specific...

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“…There are many reports in the literature on the use of solution additives for stabilization of LMLO cathodes. Good examples include lithium difluoro(bisoxalato) phosphate (LiDFBP), [ 159 ] lithium difluorophosphate (LiPO 2 F 2 ), [ 160 ] tris(2,2,2‐trifluoroethyl) phosphite (TTFP), [ 161 ] lithium difluoro(oxalate) borate (LiDFOB), [ 162 ] lithium fluoromalonato(difluoro)borate (LiFMDFB), [ 163 ] and lithium bis(oxalate)borate (LiBOB), [ 164 ] all of which react on the surface of LMLO cathodes and stabilize them by formation of effective surface films. For instance, a series of reactions between a phosphorus radical intermediate from LiDFBP and active oxygen intermediates on LMLO form semicarbonate protective layers on these cathode surfaces, which effectively passivate them.…”

Section: Fabrication Methods For Surface Modificationmentioning

confidence: 99%

Surface Modification of Li‐Rich Mn‐Based Layered Oxide Cathodes: Challenges, Materials, Methods, and Characterization

Lei

et al. 2020

Advanced Energy Materials

125

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high energy and power density, long cycle life, low cost, and environmental benignity. [3] Due to the high capacity of the currently used graphite anode −372 mAh g-1 , [1b,4] commercial cathodes have become the bottleneck for improving the energy density. [5] In addition, cathode materials take up about 40% of the total material cost of typical LIB cells. It is therefore crucial to develop cathode materials with high energy density and low cost, while maintaining superior safety features. [6] Driven by the wide deployment of electric vehicles in recent years, the demand for safer cathode materials with higher capacity and lower cost has become imperative. [2b] The specific capacity depends on the inherent physical properties of the cathode materials. Commercial materials such as LiCoO 2 , Li(Ni x Mn y Co z)O 2 , Li(Ni x Co y Al z)O 2 , LiMn 2 O 4 and LiFePO 4 all possess discharge capacities below 200 mAh g-1. [7] Ni-rich NCM, NCA, and Li-rich oxides are all prospective cathodes for high-energy LIBs as they can exhibit high specific discharge capacities above 200 mAh g-1. [6c] As compared with Ni-rich NCM and NCA, Li-rich Mn-based layered oxide (LMLO) cathode materials are cheaper and have higher specific capacity. They can deliver an initial specific discharge capacity that approaches 300 mAh g-1 , nearly doubling the capacity of commercially used cathodes and close to the limit for lithiated transition metal oxides. [8] Figure 1 lists the main development milestones of LMLO. In 1997 a novel material, LiCoO 2-Li 2 MnO 3 , was found by Numata et al., [9] a discovery that initiated intensive work on high energy density cathode materials. This group studied these materials intensively and demonstrated their cycling stability in the range of 3.0-4.3 V versus Li. [10] In 1999, Kalyani et al. reported that Li 2 MnO 3 can undergo electrochemical activation at potentials >4.5 V versus Li. [11] Dahn et al. described the charge compensation mechanism of LMLO, [12] and these cathodes were shown to provide high capacity at high operational voltage (>4.5 V). [13] In 2004, Thackeray et al. explored xLi 2 M′O 3-(1-x)LiMn 0.5 Ni 0.5 O 2 cathode materials with M′ = Zn, Ti, or Mn, concluding that Li 2 M′O 3 and LiMn 0.5 Ni 0.5 O 2 in these composite materials were integrated by short-range interactions. [14] The following Rechargeable lithium-ion batteries have become the dominant power sources for portable electronic devices, and are regarded as the battery technology of choice for electric vehicles and as potential candidates for grid-scale storage. Commercial lithium-ion batteries, after three decades of cell engineering, are approaching their energy density limits. Toward continually improving the energy density and reducing cost, Li-rich Mn-based layered oxide (LMLO) cathodes are receiving more and more attention due to their high discharge capacity and low cost. However, commercialization has been hampered by severe capacity and voltage decay, sluggish rate capability, and poor safety performance during charge/discharge cyc...

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Armoring LiNi_1/3Co_1/3Mn_1/3O₂ Cathode with Reliable Fluorinated Organic–Inorganic Hybrid Interphase Layer toward Durable High Rate Battery

Cited by 85 publications

References 50 publications

In‐Depth Analysis of the Degradation Mechanisms of High‐Nickel, Low/No‐Cobalt Layered Oxide Cathodes for Lithium‐Ion Batteries

In‐Depth Analysis of the Degradation Mechanisms of High‐Nickel, Low/No‐Cobalt Layered Oxide Cathodes for Lithium‐Ion Batteries

Enabling the High‐Voltage Operation of Layered Ternary Oxide Cathodes via Thermally Tailored Interphase

Surface Modification of Li‐Rich Mn‐Based Layered Oxide Cathodes: Challenges, Materials, Methods, and Characterization

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