Effects of Li2SiO3 coating on the performance of LiNi0.5Co0.2Mn0.3O2 cathode material for lithium ion batteries

doi:10.1016/j.jallcom.2016.08.187

Journal of Alloys and Compounds

Volume 690, 5 January 2017, Pages 589-597

https://doi.org/10.1016/j.jallcom.2016.08.187 Get rights and content

Highlights

•
LiNi_0.5Co_0.2Mn_0.3O₂ has been functionally coated with Li₂SiO₃ via a two-step method.
•
Li₂SiO₃ possesses a high Li⁺-ion conduction and excellent structural stability.
•
The Li₂SiO₃-coated sample shows improved electrochemical properties.

Abstract

Layered LiNi_0.5Co_0.2Mn_0.3O₂ (NCM523) material has been functionally coated with a uniform and thin layer of Li₂SiO₃ via a two-step method. Owing to its high lithium ion conduction and excellent structural stability against electrolyte decomposition, Li₂SiO₃ could greatly improve the Li⁺ ion diffusion rate and ameliorate the electrochemical capability of the layered oxide materials. Electrochemical tests illustrate that Li₂SiO₃ used as a Li⁺-ion conductor greatly improves electrochemical performance of the NCM523 cathode at high current density under high cutoff voltage. Particularly, the Li₂SiO₃-modified sample delivers an initial capacity of 140.0 mAh g⁻¹ and remains 134.1 mAh g⁻¹ even at a high current density of 10 C after 100 cycles, while the capacity of the pristine decreased sharply to 81.5 mAh g⁻¹. The capacity retention of Li₂SiO₃-modified NCM523 is 96.1%, while only 55.3% for the bare sample. This result demonstrates an efficient method for the Li₂SiO₃-modified NCM523 cathode with enhanced electrochemical performance, which has a certain reference for other cathode materials of Li-ion batteries.

Graphical abstract

LiNi_0.5Co_0.2Mn_0.3O₂ has been functionally coated with Li₂SiO₃ via a two-step method. The Li₂SiO₃-coated sample shows improved electrochemical properties.

Section snippets

Introductions

Nickel-rich layered oxide materials LiNi_xMn_yCo_1−x−yO₂ (NCM) have attracted more and more attention as cathode materials for lithium-ion batteries (LIBs), due to their lower cost, higher specific capacity and better thermal stability than those of LiCoO₂ [1], [2]. Layered cathode materials LiNi_0.5Co_0.2Mn_0.3O₂, as one of the representatives, have been applied in many commercial cells [3]. However, there are still some drawbacks to restrict its sustainable and high-power applications, such as poor

Preparation of Li₂SiO₃-coated LiNi_0.5Co_0.2Mn_0.3O₂

First, the LiNi_0.5Co_0.2Mn_0.3O₂ cathode material was coated with SiO₂ through a hydrolysis process. For this purpose (Calculated by 1.0 wt% Li₂SiO₃ amount), 10 g of LiNi_0.5Co_0.2Mn_0.3O₂ was dispersed into 20 mL of ethanol and deionized water solution (9:1, in volume), followed by addition of ammonia solution and Si(OC₂H₅)₄ (Xilong Chemical, AR) (TEOS, 0.26 mL) diluted into 10 mL ethanol solution respectively. The resulting precipitate was collected and washed with ethanol to remove residual TEOS

Material characterization

The structural information for the pristine and modified materials has been detected by XRD which is portrayed in Fig. 1. Both diffraction patterns of these materials can be well determined as α-NaFeO₂ structure with space group $R \bar{3} m$ when the (003) peak of the host material shows no shift after Li₂SiO₃ coating, indicating a coating layer does not influence the original structure of layered material [30], [31]. The distinct splitting of paired diffraction peaks (018)/(110) and (006)/(102) could

Conclusions

As suggested above, a uniform Li₂SiO₃ layer has been successfully coated on the surface of NCM523 via a two-step method. Li₂SiO₃, as a Li-ion conductor, largely improves the velocity of delithiation/lithiation and reduces the charge transfer resistance of the electrode. As a result, the Li₂SiO₃ modified material showed an enhanced cycling performance and rate capability. This excellent performance could be mainly attributed to the protective layer and ion conductivity of Li₂SiO₃.

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LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) has garnered significant research attention as a high-power battery cathode for electric vehicles. However, low-rate capability and poor cyclic performance limit the widespread applications of NCM cathodes. Although surface coating is an effective strategy to suppress these drawbacks, single-phase coating does not meet the application requirements. Herein, Li₂SiO₃ and PPy are used to prepare dual coating and improve both rate capability and cyclic performance. Results reveal that Li₂SiO₃/PPy-coated NCM811 exhibits a specific discharge capacity of 145.1 mAh/g and capacity retention of 96.4% after 100 charge/discharge cycles at 10 C. Various analytical and electrochemical characterization techniques demonstrate that Li₂SiO₃ in the inner layer is helpful to enhance Li⁺ diffusion coefficient and PPy in the outer layer is conducive to improve electronic transmission and decrease polarization. Besides, the dual-phase coating can alleviate adverse side reactions at the interface by acting as a strong barrier between the cathode and electrolyte.
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Surface and interfacial instability is a critical issue for nickel-based layered oxides LiNi_xCo_yMn_1−x−yO₂ (NCM) (x ≥ 0.5) operating at high cut-off voltages (≥4.5 V). In this work, precise nanofilm coating and doping (PNCD), which combines conformal surface coating by atomic layer deposition and Al surface doping by post-annealing, is used to modify the surface structure of NCM523 (P-NCM523). After PNCD, the rate capability of P-NCM523 at 10C is significantly improved to 160.3 mAh/g with a high cut-off voltage (4.55 V). Furthermore, an excellent reversible capacity of 167.5 mAh/g with a capacity retention of 87.4 % is achieved after 800 cycles at 0.5C within 3.0–4.5 V in the pouch cell constructed by P-NCM523 and a commercial graphite anode. Not only does P-NCM523 have a comparable energy density at 4.5 V to that of NCM811 at 4.2 V, but its thermal stability is also much better. Through surface and phase-transition analysis during the electrochemical process, we conclude that PNCD treatment promotes the formation of a LiAlO₂-rich surface layer and plays a crucial role in high-voltage cycling and safety. By increasing the cut-off voltages of other cathode materials, the PNCD process achieves high energy density while preserving stability.
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Citation Excerpt :
One of the coating layers is considered to be amorphous SiO2, which originates from TEOS after calcination [66], as shown in Fig. 4D. The lattice fringes of the other coating layer exhibit an interplanar distance of 0.23 nm, which can be assigned to the (002) planes of Li2SiO3 crystals [67], as shown in Fig. 4F. This result is well consistent with that reported by Yang et al. [68].
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Study of electrochemical performance and thermal property of LiNi<inf>0.5</inf>Co<inf>0.2</inf>Mn<inf>0.3</inf>O<inf>2</inf> cathode materials coated with a novel oligomer additive for high-safety lithium-ion batteries
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It is believed that higher nickel (Ni) content in LiNi1−x−yCoxMnyO2 (denoted as LNCM) can improve the specific capacity while the incorporation of cobalt (Co) and manganese (Mn) elements can enhance the electronic property, rate capability and stability of the layer-structured LNCM cathode materials [2,3]. Ni- and Mn-based layered compounds with the compositions of LNCM as promising cathode materials exhibit many advantages including higher energy density, better thermal stability, and relatively low cost [4–9]. However, LNCM cathode materials exhibit structural and thermal instabilities at fully charged states, thereby leading to poor rate capability and lower capacity retention (CR), especially under high cut-off voltage and high-temperature conditions.
LiNi_0.5Co_0.2Mn_0.3O₂ (LNCM) cathode surfaces coated with 1–2 wt% Bismaleimide/trithiocyanuric acid (BMI/TCA, BT) oligomer as an additive are successfully prepared for lithium-ion batteries (LIBs). Coin cells comprising the LNCM electrode with 1 wt% BT (1 wt% BT@LNCM) demonstrate similar capacity retention of ca. 91% to the bare LNCM cells at 0.1C for 30 cycles. Electrochemical impedance results confirm that the 1 wt% BT@LNCM cells exhibit identical Li⁺ diffusion coefficients of ca. 1.1 × 10⁻¹⁰ cm² s⁻¹ to the bare LNCM cells. TGA/DSC thermal studies show that the delithiated 1 wt% BT@LNCM sample decomposes at a higher temperature than the bare one without electrolyte (ca. 317 vs. 284˚C). In addition, the total heat generation (Q_t) of the 1 wt% BT@LNCM electrode with electrolyte is much lower than that of the bare electrode (ca. 599 vs. 824 J g⁻¹). There was strong evidence that the surface coating of BT oligomer on the LNCM could not only reduce the generated heat, but also extended the decomposition temperature. Furthermore, the Q_t of the 1 wt% BT@LNCM cells performed at 1C isothermally is reduced by ca. 17% via operando micro-calorimetry; the Q_t of the 1 wt% BT@LNCM cells at fully-charged state is also smaller (ca. 3–5%) when the temperature elevates to 300 °C. In summary, LNCM523 cathode materials coated with the 1 wt% BT oligomer show potential for high-energy LIBs application without suffering thermal runaway.

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Effects of Li2SiO3 coating on the performance of LiNi0.5Co0.2Mn0.3O2 cathode material for lithium ion batteries

Highlights

Abstract

Graphical abstract

Section snippets

Introductions

Preparation of Li2SiO3-coated LiNi0.5Co0.2Mn0.3O2

Material characterization

Conclusions

J. Power Sources

J. Power Sources

J. Power Sources

J. Power Sources

J. Alloys Compd.

J. Power Sources

J. Power Sources

J. Power Sources

J. Power Sources

J. Power Sources

J. Alloys Compd.

J. Power Sources

Electrochim. Acta

Electrochim. Acta

J. Power Sources

J. Power Sources

J. Power Sources

J. Power Sources

Electrochim. Acta

J. Alloys Compd.

J. Power Sources

High-energy cathode material for long-life and safe lithium batteries

Nat. Mater.

Effects of Li₂SiO₃ coating on the performance of LiNi_0.5Co_0.2Mn_0.3O₂ cathode material for lithium ion batteries

Preparation of Li₂SiO₃-coated LiNi_0.5Co_0.2Mn_0.3O₂