Abstract
SiO2-coated LiNi0.7Mn0.15Co0.15O2 materials were successfully prepared by electrostatic attraction forces method via adjusting the Zeta potential between SiO2 and LiNi0.7Co0.15Mn0.15O2 in the suspension with the followed heating process. The structure, morphology, and electrochemical performances were characterized by XRD, SEM, TEM, XPS, CV, and EIS. As a result, compared with that with 71.4% capacity retention of bare materials, 1.0 wt% SiO2-coated LiNi0.7Co0.15Mn0.15O2 (NCM-S10) could deliver 184.50 mAh g−1 with 86.4% capacity retention after 100 cycles at 1 C over 3–4.5 V. In high temperature (55 °C), NCM-S10 also has 76.2% capacity retention after 100 cycles (3–4.5 V, 1 C), showing better cycling stability than that of the pristine (61.5%). The SiO2 coating layer efficiently inhibits side reaction between electrode and electrolyte and maintains the surface structure of LiNi0.7Co0.15Mn0.15O2. The increase in impedance is suppressed during the cycle, thereby enhances electrochemical properties of LiNi0.7Co0.15Mn0.15O2 in high voltage.
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Introduction
Due to the high energy density and long cycle life, lithium-ion batteries (LIBs) have been considered as the most suitable replacer for lead-acid batteries and nickel-metal hydride batteries widely used in 3C products, energy storage systems, and electric vehicles [1,2,3,4]. Although great progress has been achieved, the limited energy density of LIBs is still regarded as the main restriction for widespread application in the past decades [5,6,7,8]. Therefore, it is necessary to search for high discharge capacity and high operating voltage cathode materials to satisfy the urgent demand.
In recent years, LiNi1-x-yCoxMnyO2 (marked as NCM) has captured worldwide attention owing to the characteristics of low cobalt content and high discharge capacity. By increasing the nickel content or charging cut-off voltage, NCM delivers higher discharge capacity [9,10,11,12]. LiNi0.5Co0.2Mn0.3O2 and LiNi0.6Co0.2Mn0.2O2 have been successfully adopted in commercial LIBs. Unfortunately, Ni-rich materials such as LiNi0.7Co0.15Mn0.15O2 and LiNi0.8Co0.1Mn0.1O2 have so far been retarded by the low capacity retention with dramatic voltage plateau dropping and high thermal instability [13,14,15,16]. As for Ni-rich cathode material, on the one hand, the Li/Ni mixing and high content of surface lithium residual (Li2CO3/LiOH) easily occurred during synthesis [10, 17,18,19]; on the other hand, the highly reactive Ni4+ presenting in the delithiated cathode materials is easy to produce side reaction between electrode and electrolyte, which leads to surface structure suffering from an irreversible transformation. Both of these behaviors deteriorate the electrochemical performances of Ni-rich materials [3, 20,21,22].
Surface coating is one of the most effective methods to enhance the electrochemical properties of cathode materials [23,24,25,26,27]. As previously reported, metal and nonmetal oxides such as ZrO2 [16, 28], Al2O3 [29, 30], TiO2 [31], Y2O3 [3], La2O3 [32], and SiO2 [33, 34] layer coated cathodes have been investigated. The coating layer plays an important role in the artificial physical barrier between cathode electrode materials and electrolyte, which can improve the stability of the structure and the electrochemical properties of the materials. Among these coating materials, SiO2 is considered an ideal coating material with an environmentally friendly advantage and abundant resources. SiO2 coating layer prevents the side reaction between electrode and electrolyte and plays a role of hydrogen fluoride (HF) scavenger in LiPF6 salt electrolyte [34, 35]. Moreover, the particular thermal properties of SiO2 may vitalize cathode materials a good thermal stability. Cathode materials coated with SiO2 via different routes have been reported in the previous literature. H. Omanda et al. [36] used a thin layer of SiO2 deposited to coat on the surface of LiNi0.8Co0.2O2 particles via chemical vapor deposition (CVD), and the coated sample showed an excellent electrochemical performance and thermal stability. Yonghyun Cho et al. [37] and Pengfei Zhou et al. [38] reported a one-step dry coating of amorphous SiO2 on spherical Ni-rich NCA cathode materials. This dry coating method is extremely popular for the companies due to its simple coating process. Daxian Zuo et al. [39], Meng Zhao et al. [40], and Yongxiang Chen et al. [35] used the wet coating method to coat NCM with a SiO2 layer, thus improving the electrochemical performance of NCM materials. However, there are few studies that coated LiNi0.7Mn0.15Co0.15O2 (mark as NCM715) with SiO2 via the electrostatic attraction forces method.
Taking the above factors into consideration, SiO2 coated NCM715 materials were successfully prepared by the electrostatic attraction forces method for the first time via adjusting the zeta potential between SiO2 and NCM715 in the suspension with the followed heating process. In the optimal pH, the larger zeta potential difference is 64 mV, and the SiO2 with positive charge was coated on the surface of NCM715 with negative charge. The positive effects of the SiO2 coating layer on NCM715 are systematically discussed. The SiO2-coated NCM715 cathode exhibits excellent electrochemical performances at high voltage (3.0–4.5 V) and high temperature (55 °C).
Experimental
Synthesis of LiNi0.7Mn0.15Co0.15O2
LiOH·H2O (analytical grade, Tianqi Lithium Co., Ltd., China) and commercial Ni0.7Co0.15Mn0.15(OH)2 (Hunan Brunp Recycling Corp., China) precursor were mixed thoroughly with a molar ratio (nLi/n(Ni+Co+Mn)) of 1.04:1 and calcining at 820 °C in O2 atmosphere for 10 h. Then, the pristine NCM715 materials were synthesized.
Synthesis of SiO2-coated LiNi0.7Mn0.15Co0.15O2
SiO2-coated NCM715 was prepared in the following steps and is shown in Fig. 1. Firstly, a certain amount of NCM715 particles were added into the mixture of ethanol and ultrapure water (volume ratio of 2:1), stirring for 10 min at 25 °C to achieve good dispersion. The nano-SiO2 sol (25 wt%, Xi’an Tongxin Semiconductor Materials Co., Ltd.) was added slowly to the above suspension at pH 8 with dilute HNO3 and NH3·H2O. Lastly, the suspension was rapidly completed the solid-liquid separation, and the pre-fabricated powders were calcinated (500 °C, 5 h) in O2 atmosphere to form the final product. The difference of zeta potential between NCM715 and SiO2 was measured in different pH, as shown in Fig. S1. In this work, SiO2-coated samples with various SiO2 amounts (0.5 wt%, 1.0 wt%, and 1.5 wt%) were synthesized and marked as NCM-S05, NCM-S10, and NCM-S15, respectively. In order to better compare with the SiO2-coated cathode materials, the NCM715 has also suffered the same heated process without SiO2 coating and the obtained cathode material was named as NCM-S00. Based on the ICP-OES test, the content of SiO2 for NCM-S05, NCM-S10, and NCM-S15 are 0.46 wt%, 0.94 wt%, and 1.38 wt%, respectively.
Scheme illustrating the coating process from pristine NCM715 cathodes to SiO2-coated NCM715cathodes
Physical characterization
X-ray diffraction (XRD, using Panaco X’Pert PRO) with a Cu Kα radiation source was carried out to characterize the structures of powders. The scan range was 10–80° at a scanning rate of 8°/min. Scanning electron microscopy (SEM, using Hitachi S3400N, Japan) and transmission electron microscopy (TEM, using Tecnai G12, 200 kV) were performed to measure particle morphology and the status of the coating layers. X-ray photoelectron spectroscopy (XPS, using VG Multilab 2000) was performed to investigate the element status on sample surface. Cycled CR2016 type button cells were disassembled in the argon glove box (MNIUIVESAR1220-100, MIKROUNA) and the powder scraped from the obtained electrodes washed by dimethyl carbonate (DMC) for further XRD analysis. Differential scanning calorimetry (DSC, using Netzsch STA449C) from 30 to 300 °C at a heating rate of 10 °C/min was performed to examine the thermal stability of the samples at a delithiated state of 4.5 V.
Electrochemical testing
The proper amount of N-methyl-2-pyrrolidone (NMP) was mixed with the prepared cathode materials, polyvinylidene fluoride (PVDF) and acetylene black (with a ratio of 80:10:10). The slurry was covered on the aluminum foil. After dried under vacuum at 120 °C for 12 h, the positive electrode with a diameter of 14 mm was pouched as the cathode electrode. Using lithium metal as the anode, Celgard 2400 as the separator, and electrolyte (1 M LiPF6 in EMC:EC:DMC = 1:1:1 vol ratio) as the electrolyte, CR2016 type coin button cells were assembled in the Ar-filled glove box (MNIUIVESAR1220-100, MIKROUNA, China).
The initial charge-discharge cycle was set at 0.1 C (1 C = 180 mAh g−1) and the following cycling performance at 1 C of the CR2016 type coin button cells was tested by Neware Test System (CT-4008-5V6A-S1, Shenzhen Neware Energy Tech Co., Ltd., China) at a voltage limit of 3.0–4.5 V at 25 °C and 55 °C. Cyclic voltammetry (CV, 3–4.5 V, 0.1 mV s−1) measurements and electrochemical impedance spectroscopy (EIS) analysis were carried out on a CHI750E electrochemical workstation (CHI750E, Shanghai, China). After the first and 50th cycles, we performed EIS of coin cells by charging the samples to 4.5 V over a frequency range from 0.01 Hz to 100 kHz and an AC voltage of 5-mV amplitude.
Results and discussion
Figure 2 shows the XRD patterns of the NCM-S00, NCM-S05, NCM-S10, and NCM-S15, in which all samples have a typical α-NaFeO2 structure in a hexagonal form with \( R\overline{3}m \) space group (JCPDS #09-0063), without any evidence of SiO2 peaks due to the small contents and/or low crystallinity. As shown in Fig. 2a, splitting of the peaks (006)/(012) and (018)/(110) can be found clearly, which reveals a well-ordered layered structure [41]. No obvious shift of (003) peaks (Fig. 2b) indicates that there are no significant crystal lattice changes after SiO2 coating. The XRD results indicate that the phase and crystalline structure of pristine is maintained after SiO2 coating. To identify the phase of the SiO2 coating layer, the Nano-SiO2 sol was treated with the same heating process in the Experimental section without NCM715 additions and the obtained XRD is shown in Fig. S2. The observed diffraction implies that the obtained powders are at the amorphous phase (JCPDS #46-1045). According to this result, we speculate that the coating layers could be mainly amorphous SiO2.
a XRD patterns of the NCM-S00, NCM-S05, NCM-S10, and NCM-S15 samples, and b the expanded view of (003) peaks
Typical SEM and TEM images of the NCM-S00 and NCM-S10 are presented in Fig. 3. It is clearly observed from Fig. 3 that all samples display spherical-like particles composed of 0.5–1-μm primary particles. The surfaces of the NCM-S00 (Fig. 3a) are clean and smooth, while NCM-S10 particles presented a similar morphology with some tiny nanoparticles covered (Fig. 3b). As shown in Fig. 3c, d, after SiO2 coating, an ultra-thin coating layer can be clearly found on the particle surface. For NCM-S10, a uniform modified thick layer attaches onto the surface of the primary particles. Further carefully observing in the HRTEM of the coating layer, it is hard to identify lattice fringes of the SiO2, implying the coating layer is mostly amorphous or low crystallinity, which is consistent with the XRD results.
SEM images for a NCM-S00 and b NCM-S10 spherical materials. TEM and high-resolution TEM (HRTEM) images for the corresponding c NCM-S00 and d NCM-S10 cathodes
Energy-dispersive X-ray spectroscopy (EDS) was applied to check the SiO2 coated NCM-S10. Figure 4a shows the element distribution of Si, Ni, Co, and Mn and it can be seen that Si is completely overlapped with Ni, Co, and Mn. It can be considered that SiO2 was homogeneously distributed on the NCM-S10 surface. Moreover, the line EDS of Ni, Co, Mn, and Si elements for cross section of NCM-S10 in Fig. 4b further demonstrates that Si elements mainly disperse on the LiNi0.7Co0.15Mn0.15O2 particle surface. This SiO2 coating layer is designed to be a role of artificial physical barrier between electrode and electrolyte, and it is possibly good for preventing the terrible side reactions. Thereby, it can improve the electrochemical stability of the cathodes.
a EDS mapping of the NCM-S10 cathodes. b Line EDS of the particle cross section of Ni, Co, Mn, and Si elements
NCM-S00 and SiO2-coated NCM-S10 were analyzed by XPS to ascertain the surface chemical compositions (Fig. 5). Typical Ni, Mn, Co peaks appear in the XPS survey spectra for both samples. Most importantly, Si photoemission peaks could only be found in the NCM-S10 sample (Fig. 5a). The spectra of Ni 2p of both samples are shown in Fig. 5b. There were no obvious variations in the binding energies, suggesting that SiO2 coating does not affect the bulk cathode. This phenomenon is consistent with the results discussed in previous XRD analysis. The binding energy (BE) of Si 2p around 103.1 eV (Fig. 5c) observed in NCM-S10 can be assigned to the contribution of SiO chemical bond of SiO2 [32, 37, 42]. As is shown in the C 1s spectra (Fig. 5d), the peaks around 284.8 and 289.9 eV are ascribed to hydrocarbon contaminants and the carbonate compounds of the surface lithium residual which inevitably generated in Ni-rich materials [19, 43]. Figure 5e exhibits the O 1s spectra of two samples. The binding energy (BE) located at 531.6 eV corresponds to the absorbed oxygen from surface lithium residual, while the small peak located at 529.8 eV attributed to the oxygen in the metal framework [44]. Compared with that of NCM-S00, the O1s peak of NCM-S10 at 531.6 eV is slightly reduced, indicating that SiO2 coating may decrease amounts of the lithium residues, which may be favorable to improve the interfacial properties and lead to excellent electrochemical properties.
XPS spectra of a full spectra, b Ni, c Si, d C, and e O for NCM-S00 and NCM-S10 samples
The electrochemical properties of NCM-S00 and SiO2-coated samples (NCM-S05, NCM-S10, and NCM-S15) are investigated by using half-cells. Figure 6a exhibits the first charge-discharge curves between 3.0 and 4.5 V at 0.1 C at ambient temperature. The initial discharge capacities for NCM-S00, NCM-S05, NCM-S10, and NCM-S15 are 200.2, 196.4, 193.6, and 191.7 mAh g−1 and correspond to the coulombic efficiencies of 89.14%, 89.10%, 89.01%, and 88.72%, respectively. The discharge capacity of the NCM-S00 electrode is better than that of SiO2-coated NCM715 electrode because of the fact that SiO2 is electrochemically inactive in the voltage range. Figure 6b shows the 3.0–4.5-V cycling performance of the four samples at a constant current of 1 C and 25 °C, in which NCM-S00, NCM-S05, NCM-S10 and NCM-S15 deliver discharge capacities of 190.2, 187.1, 184.5 and 181.1 mAh.g−1 at 1 C corresponding to 71.4, 81.0, 86.4 and 88.7% capacity retentions after 100 cycles, respectively. This result is comparable with the data reported in related NCM literatures (Table S1)[3, 6, 10, 42, 45,46,47,48,49]. Obviously, the SiO2 coating improved the cycle stability of NCM715, which is consistent with the above analysis. A sample NCM-S10 shows the best balance of discharge capacity and cycle stability. Therefore, the following studies for SiO2-coated samples mainly focus on NCM-S10.
Electrochemical test of the NCM-S00 and NCM-S10 cathodes: a charge-discharge curve at 0.1 C, b 1-C cycling performance and coulombic efficiency at 25 °C, c, e discharge profile at different cycles, d, f the corresponding dQ/dV profiles
Figure 6c–f depict the discharge curves and the corresponding dQ/dV profiles of NCM-S00 and NCM-S10 for different cycles at a rate of 1 C between 3.0 and 4.5 V. The results show that NCM-S10 electrode exhibited excellent stability for discharge voltage platform during cycling in comparison with NCM-S00 electrode. Voltage fading resulted from the enhanced resistance that is discussed in the next analysis and the formation of a rock-like structural framework, thus leading to the continuous capacity loss. From dQ/dV curves, a smaller peak shift can be found in the NCM-S10 electrode, indicating the suppressed polarizations after SiO2 coating.
To evaluate the impacts of SiO2 coating on electrochemical performance at high temperature, half-cells with NCM-S00 and NCM-S10 for cathode electrode were tested at 55 °C between 3 and 4.5 V at a 1-C rate. As shown in Fig. 7, after 100 cycles, the NCM-S10 sample can maintain 76.2% capacity retention, which is higher than 61.5% of the NCM-S00 cathode. The excellent high-temperature electrochemical performance of NCM-S10 maybe originated that SiO2 has good thermal stability and relieve the severe side reaction at high temperature.
1-C cycling performance and coulombic efficiency at 55 °C of the NCM-S00 and NCM-S10 cathodes
The comparison on the cyclic voltammograms of the NCM-S00 and NCM-S10 after the first and the 50th cycle is drawn in Fig. 8a, b. A distinct pair of anodic/cathodic peaks around 3.7 V correspond to the oxidation/reductions of the Ni2+/Ni4+ redox couples and a small pair anodic/cathodic peaks around 4.3 V correspond to the structural transformations of hexagonal structures (H2–H3), respectively [9, 50]. The potential differences (ΔE) between the cathodic peak and the anodic peak of NCM-S00 after 1st and 50th cycles are 0.074 and 0.206 V, respectively, which are higher than the compared result of NCM-S10 (0.047 and 0.152 V). According to previous reports [23, 51], a smaller ΔE which represents the electrochemical reversibility indicates a smaller reaction polarization. In our work, after SiO2 coating, the ΔE becomes smaller, indicating that the SiO2 coating was helpful to reduce the electrochemical polarization and improve the electrochemical performance of the cathode.
CV profile of a NCM-S00 and b NCM-S10 at different cycles at a scanning rate of 0.1 mV s−1 in a voltage range of 3.0–4.5 V at 25 °C
To better understand the origin for the cycle performance improvement, electrochemical impedance spectroscopy (EIS) (Fig. 9) for the NCM-S00 and NCM-S10 was measured at a rate of 1 C after the 1st and 50th cycle at 100% state of charge to 4.5 V. In Fig. 9a, b, each of the plot was composed of a high-frequency point related to the solution resistance (Rs), a high-frequency semicircle related to the surface interface resistance (Rf), and a middle-frequency semicircle related to the charge transfer resistance (Rct) [52]. The fitting resistance values are obtained and listed in Table 1 based on the equivalent circuit (Fig. 9c). The value of Rf for NCM-S00 is obviously increased through cycling, whereas that is increased slightly in the NCM-S10 sample. As presented in Table 1, after 50 cycles, Rct values of both samples are increased significantly, but the increasing Rct value of NCM-S00 (20.23 Ω → 824.6 Ω) is remarkably bigger than that of the NCM-S10 (48.85 Ω → 172.0 Ω). The above results suggest that the SiO2 coating effectively suppressed the enhancement of the impedance by reducing the side reactions between electrolyte and cathode.
EIS comparisons revealed by Nyquist plots of the NCM-S00 and NCM-S10 cathodes, which are analyzed at a rate of 1 C after a the 1st cycle and b the 50th cycle in a state fully charged to 4.5 V (vs. Li/Li+). The corresponding equivalent circuit used for fitting is given in (c)
To further explain the effect of SiO2 coating on the structure and morphology of NCM715 cathode after cycles, the cycled electrodes of NCM-S00 and NCM-S10 are investigated by XRD and SEM after 100 cycles. As can be seen in Fig. 10a, the diffraction peaks intensities of NCM-S00 became weaker than those in the NCM-S10 obviously, which confirm that the structure of NCM-S10 undergone more tremendous changes. In addition, the SEM image (Fig. 10b) of the cycled NCM-S00 electrode displays some cracks, but SiO2-coated NCM-S10 maintains comparatively integrated morphology. The above results indicate that the SiO2 coating is effective to stabilize the structure of NCM715 cathode, which might effectively alleviate the side reaction and resulting in relatively higher capacity retention of NCM-S10 [53].
a XRD patterns of NCM-S00 and NCM-S10 samples after 100 cycles. SEM images of b the NCM-S10 and c NCM-S00 electrodes after 100 cycles
Differential scanning calorimetry (DSC) scans for the NCM-S00 and NCM-S10 were determined to further verify the effect of SiO2 coating on the thermal properties of NCM 715 cathode. All samples were tested in a highly delithiated state (4.5 V). As presented in Fig. 11, the NCM-S10 electrode exhibits an exothermic reaction with the peak located at 241.6 °C, which is higher than the value of 237.7 °C for the NCM-S00 electrode. It can be assumed that SiO2 coating enhances the thermal stability of the LiNi0.7Co0.15Mn0.15O2 material.
Differential scanning calorimetry (DSC) profiles of the NCM-S00 and NCM-S10 cathodes after initially charged to 4.5 V
Conclusions
In summary, SiO2 coating layer was deposited on the surface of LiNi0.7Co0.15Mn0.15O2 materials via electrostatic attraction forces method with the followed heating process. The structures, morphologies, and electrochemical performances of the obtained samples have been carefully investigated. The SiO2 coating on the surface of LiNi0.7Co0.15Mn0.15O2 significantly protected the interface structure of the electrode by reducing the side reaction between electrolyte and cathode, leading to a lower increasing in impedance. It also shows an excellent electrochemical performance at an elevated cut-off voltage 4.5 V. Moreover, the SiO2 layer effectively enhanced the thermal stability of LiNi0.7Co0.15Mn0.15O2 material. This electrostatic attraction forces method provides a relatively convenient and effective coating routine for SiO2 coating cathode materials.
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Funding
This study was financially supported by the Government of Chongzuo, Guangxi Zhuang Autonomous Region (GC Joint Special Fund No. FA2019015), and Science and Technology Department of Guangxi Zhuang Autonomous Region (Guangxi Special Fund for Scientific Center and Talent Resources, No. AD18281073).
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Li, W., Li, Y., Yang, L. et al. Enhancing high-voltage electrochemical performance of LiNi0.7Mn0.15Co0.15O2 cathode materials with SiO2 coatings via electrostatic attraction forces method. Ionics 26, 5393–5403 (2020). https://doi.org/10.1007/s11581-020-03657-8
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DOI: https://doi.org/10.1007/s11581-020-03657-8