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. 2021 Nov 10;6(46):31330–31338. doi: 10.1021/acsomega.1c05176

Cost-Efficient Film-Forming Additive for High-Voltage Lithium–Nickel–Manganese Oxide Cathodes

Zekai Ma †, Huiyang Chen †, Hebing Zhou †,‡,*, Lidan Xing †,‡,*, Weishan Li †,‡
PMCID: PMC8613853  PMID: 34841176

Abstract

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The operating voltage of lithium–nickel–manganese oxide (LiNi0.5Mn1.5O4, LNMO) cathodes far exceeds the oxidation stability of the commercial electrolytes. The electrolytes undergo oxidation and decomposition during the charge/discharge process, resulting in the capacity fading of a high-voltage LNMO. Therefore, enhancing the interphasial stability of the high-voltage LNMO cathode is critical to promoting its commercial application. Applying a film-forming additive is one of the valid methods to solve the interphasial instability. However, most of the proposed additives are expensive, which increases the cost of the battery. In this work, a new cost-efficient film-forming electrolyte additive, 4-trifluoromethylphenylboronic acid (4TP), is adopted to enhance the long-term cycle stability of LNMO/Li cell at 4.9 V. With only 2 wt % 4TP, the capacity retention of LNMO/Li cell reaches up to 89% from 26% after 480 cycles. Moreover, 4TP is effective in increasing the rate performance of graphite anode. These results show that the 4TP additive can be applied in high-voltage LIBs, which significantly increases the manufacturing cost while improving the battery performance.

1. Introduction

Lithium-ion batteries (LIBs) have become an integral part of human life as energy storage and power batteries due to their portability, long-term cycling lifetime, and high energy density.1−5 With the intelligence and versatility of all kinds of electrical appliances, there is huge demand to further increase the energy density of LIBs.6,7 It is the most valid method to increase the battery energy density by applying the cathode materials that possess high operating voltage and specific capacity.8 On account of its high operating voltage, 4.9 V (vs Li+/Li), lithium–nickel–manganese oxide (LNMO) stands out among many novel cathode materials that have been proposed.6

However, the application of high-voltage LNMO material requires overcoming its interphasial instability in carbonate-based electrolytes. The traditional organic electrolyte (carbonate-based) oxidative decomposition occurring on the surface of LNMO not only increases the interphasial impedance but also induces transition-metal ions in the electrode material dissolving into an electrolyte, which leads to the rapid capacity decay of LNMO.9 Such electrolyte oxidation can be effectively inhibited by coating the high-voltage electrode surface with inert oxides,10−14 or using film-forming electrolyte additives,15−20 which isolate the transmission of electrons between electrodes and electrolytes while allowing ion transport. So far, various film-forming electrolyte additives, including tris(trimethylsilyl) phosphate (TMSP), trimethoxy(3,3,3-trifluoropropyl)silane (TTS), pentafluorophenyltriethoxysilane (TPS), boric acid tris(trimethylsilyl) ester (TMSB), tris(pentafluorophenyl)silane (TPFPS), 1,10-sulfonyldiimidazole (SDM), and (pentafluorophenyl)diphenylphosphine (PFPDPP),16,17,21−26 have been put forward to enhance the high-voltage LNMO cycling performances. In our recent work, a film-forming additive TTS has been demonstrated to effectively improve the capacity retention of LNMO/Li cell up to 92% from 48% after 500 cycles by generating a stable cathode/electrolyte interphase (CEI) film on the surface of LNMO.16 However, in addition to the effect of additive, its price is also a concern. Therefore, it is of great significance to develop an efficient and economical electrolyte additive to achieve the industrial application of a high-voltage LNMO.

Herein, a cost-efficient 4TP additive is presented to enhance the cycling performance of LNMO. The performance and price of this additive and other reported film-forming additives were compared, as shown in Table S1. Density functional theory (DFT) calculations show that the oxidation activity of the 4TP additive is higher in comparison with that of baseline electrolyte, which was confirmed by the subsequent electrochemical characterizations. Importantly, the preferential oxidation of 4TP generates a high-stability CEI film on the LNMO surface, leading to a significantly increased capacity retention of the LNMO/Li cell up to 80% from 26% after 480 cycles.

2. Experimental and Theoretical Calculation Methods

2.1. DFT Calculation

Oxidation activity of a 4TP additive was predicted via DFT calculation and compared with that of carbonate solvent molecule, including ethylene carbonate (EC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). The structures of the above molecules were optimized on Gaussian 09 software with the 6-311++G(d) basis set and the B3LYP level.27−29 Polarizable continuum model was used to consider the influence of the liquid environment, with a dielectric constant of 20.5. The frequency analyses were conducted in the same method to verify the obtained structure of solvents. The oxidation activity of solvent is estimated by the highest occupied molecular orbital (HOMO) energy level. The higher (more positive) the energy level of HOMO, the more likely a molecule is to be oxidized.30−33

2.2. Electrode and Electrolyte Preparations

The baseline electrolyte is obtained by adding 1.0 M LiPF6 (>99.8%) into the ternary solvent EC/EMC/DEC, provided by Guangzhou Tinci Materials Technology Co. Ltd., China, in the volume ratio of 3/5/2. The 1, 2, and 3 wt % (>98%, Aladdin) 4TP were added into the baseline electrolyte to obtain additive-containing electrolytes.

The LiNi0.5Mn1.5O4 powder (LNMO, Sichuan Xingneng Co. Ltd.), polyvinylidene fluoride (PVDF, Ofluorine Chemical Tech Co. Ltd., China), and acetylene black (AB, TIMCAL Ltd., Switzerland), in a mass ratio of 8:1:1, were mixed in 1-methyl-2-pyrrolidone (NMP) solvent to prepare the LNMO cathode slurry. The LNMO cathode slurry was then coated on an Al current collector to obtain the LNMO cathode electrode. The graphite slurry consists of 80 wt % artificial graphite (Guangzhou Tinci Materials Technology Co. Ltd., China), 10 wt % acetylene black, and 10 wt % PVDF mixed in the NMP solvent. The graphite anode electrode is prepared by coating the above graphite slurry on the Cu current collector. The above obtained LNMO cathode and graphite anode were dried in a vacuum oven under 80 °C for 1 h and 120 °C for 12 h and then cut into pieces 1.1 cm.

Electrolyte preparation and cell assembly (CR2025) were conducted in the filling with high purity argon glove box (MBraun, Germany), where the contents of oxygen and water are less than 0.1 ppm. Fifty microliters of the electrolyte was added to each cell. Celgard 2400 was adopted as the separator in the cells. The area of Li metal anode is around 1.22 cm2 and the loading mass of the LNMO material was around 2.48–2.83 mg cm–2 in the LNMO/Li half-cells.

2.3. Electrochemical Measurements

The cycle performances of LNMO/Li, Li/Li cells, and graphite/Li were recorded by a LAND test system (CT2001A, China) at room temperature (25 °C). The LNMO/Li cells were cycled in the voltage range of 3.0–4.9 V at the current rate of 1C (1C = 148 mA g–1) for 480 cycles after the initial three cycles at 0.2C. Each charging process included a constant voltage step at 4.9 V for 15 min. The LNMO/Li cells were tested at 0.5, 1, 2, 3, 4, and 5C after the initial three cycles at 0.2C to obtain the rate capability. The graphite/Li cells were discharged/charged at 0.2C (1C = 372 mAh g–1) between 0.005 and 2.5 V after the initial three cycles at 0.1C. Galvanostatic Li stripping/plating tests (100 mAh areal capacity) of Li/Li cells were carried out on a capacity of 1 mAh cm–2 with a current density of 1 mA cm–2.

Linear sweep voltammetry (LSV), cyclic voltammetry (CV), and chronoamperometry (CA) measurements were conducted on a Solartro-1480 electrochemical workstation (Solartron Mobrey, England) at a scan rate of 0.5 mV s–1 for the CV of LNMO/Li cells and 1 mV s–1 for LSV of a two-electrode device, using Li and Pt metals as the reference/counter and the working electrode, respectively. The chronoamperometry results were obtained at 100% state-of-the-charge of LNMO/Li cells after three cycles in the voltage range of 3.0 and 4.9 V at 0.2C and then charged to 4.9 V with the current rate of 1C. The electrochemical impedance spectroscopy (EIS) of LNMO/Li cells at the third cycle and 300th cycle was measured by a PGSTAT302 electrochemical workstation (Metrohm, Netherlands) with a frequency range of 105–0.01 Hz, where the voltage amplitude was 5 mV.

2.4. Physical Characterizations

Physical characterizations were carried for the fresh and cycled LNMO electrodes. The latter were stripped down from the LNMO/Li cells after cycling and rinsed with a DMC solvent three times to wipe off the residual electrolyte. The surface morphology of LNMO was investigated using a scanning electron microscope (SEM, JEM-6510, Japan) and a transmission electron microscope (TEM, JEM-2100HR). X-ray diffraction (XRD, Bruker D8 Advance, Germany) and X-ray photoelectron spectroscopy (XPS, Shimadzu, Japan) were used to analyze the crystal structure and the interphasial composition of LNMO, respectively. The deposited amount of transition-metal ions on the Li counter/reference electrode is tested by an inductively coupled plasma atomic emission spectrometer (ICP-AES, Optima 8300). For the ICP-AES test, the disassembled cycled Li electrode was rinsed with DMC solvent three times and then dissolved in 25 ml of 3% nitric acid solution prepared in advance.

3. Results and Discussion

3.1. Oxidation Activity of 4TP

An effective cathode film-forming additive should oxidize prior to the bulk electrolyte to form a passivation (CEI) film so as to achieve the purpose of inhibiting the subsequent oxidation decomposition of the bulk electrolyte.18,34,35 Therefore, oxidative activity is an important parameter to evaluate the effectiveness of a film-forming electrolyte additive. Herein, the oxidation activity of 4TP was initially evaluated by DFT calculation and shown in Figure 1A. Distinctly, the HOMO energy level of 4TP (−7.49 eV) is the highest amount among the investigated molecules in Figure 1A, suggesting that 4TP would oxidize previous to the baseline electrolyte. The LSV tests using a Pt working electrode confirmed the DFT prediction that the electrolyte containing 4TP additive had a higher oxidation activity than the baseline electrolyte, as shown in Figure 1B. Higher oxidation current was detected in the 4TP-containing electrolyte especially when the potential was beyond 5 V. It needs to be mentioned that the Pt electrode with a smooth surface is difficult to passivate by a 4TP-derived interphase and thus the responsive current in the LSV measurement only indicates the redox reactivity but not the passivation capability of electrolytes.36 Subsequently, the influence of the 4TP additive on the electrochemical behavior of the LNMO cathode was understood by CV measurement. As shown in Figure 1C, preferential oxidation of 4TP was not detected on the initial CV curve of the LNMO electrode, which could be ascribed to the overlap between the oxidation current of 4TP and the oxidation reaction current of Mn3+/Mn4+. Instead, subsequent de-lithiation reaction (accompanying the oxidation of Ni2+/Ni3+ and Ni3+/Ni4+) peaks of the LNMO electrodes in a 4TP-containing electrolyte appear at higher voltage, which was caused by the increased interphasial impedance due to the formation of the CEI film. Fortunately, such behavior almost disappeared and both electrolytes showed no visible difference in the second CV curve (Figure 1D), as the CEI film was gradually completed with the ongoing electrode reactions.

Figure 1.

Figure 1

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(A) Calculated HOMO energy of EC, EMC, DEC, and 4TP molecules. (B) Oxidation linear sweep voltammetry (LSV, 1 mV s–1) with the Pt/Li system in baseline and 2 wt % 4TP-containing electrolytes. (C) Initial and (D) second cyclic voltammograms (CV, 0.1 mV s–1) with LNMO/Li system in baseline and 2 wt % 4TP-containing electrolytes.

The above DFT calculation and electrochemical test results show that 4TP has high oxidation activity, which may allow it to become an effective film-forming additive passivating the high-voltage LNMO electrode, thus improving its interphasial stability and cycling performance.

3.2. Effect of 4TP on the Cycling Performances of LNMO

The cycling stability and the corresponding coulombic efficiency of LNMO/Li cells with electrolytes containing different contents of 4TP additive are presented in Figure 2A,B. The discharge capacity of LNMO in the baseline electrolyte drops dramatically after around 300 cycles, which is similar to our previous works showing the poor cycle stability of LNMO in an additive-free electrolyte.16−18,21,35,37 Application of a 2 wt % 4TP additive prominently enhances the long-term cycle stability of the LNMO/Li cell, which achieves a capacity retention of 89% after 480 cycles at the current rate of 1C in comparison with that of only 26% achieved by without additive. It can be also found that the capacity retention of LNMO with 1 wt % 4TP additive is not as high as that of LNMO with 2 wt % 4TP, which might be due to the insufficient content of additive to form an integral CEI film. Further increasing the content of additive to 3 wt % leads to a slight decrease in the initial discharge capacity. This may be due to too much 4TP additive involved in the film formation reaction, resulting in an increase in the interphasial reaction impedance, which in turn reduces the capacity of the cell. The coulombic efficiency of the cell at the first cycle decreases with the increase in the additive content, which further confirms our above speculation. In addition, the ion conductivity of electrolytes was also considered as one of the factors of choosing the optimal concentration of the additive, as shown in Figure S1. As the concentrations of additives increase, the conductivity of electrolytes decreases. Herein, combining the cycling stability and coulombic efficiency of the LNMO and ion conductivity, 2 wt % 4TP is determined to be the best proportion for the application in the high-voltage LNMO cathode. Meanwhile, a contact angle between the LNMO cathode and the electrolyte was also formed after confirming the optimal concentration of the additive, as shown in Figure S2. The results show that the capability of 4TP on the immersion of electrolyte with the LNMO electrode has been improved as compared with that of baseline electrolyte.

Figure 2.

Figure 2

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(A) Cycling stability and (B) coulombic efficiency of LNMO/Li cells operated in electrolytes at 0.2C for initial three cycles and 1C for subsequent cycles in the voltage range of 3.0–4.9 V; discharge profile of selected cycles in (C) baseline and (D) 2 wt % 4TP-containing electrolytes.

Figure 2C,D exhibits the representative discharging curves of the LNMO cycle with baseline and 2 wt % 4TP-containing electrolytes, respectively. Differently from that of the baseline electrolyte, the discharging voltage platform of the LNMO/Li cell in a 2 wt % 4TP-containing electrolyte maintained well at around 4.6 V during cycling. In addition, the conversion reaction of Mn3+/Mn4+ at around 3.8 V still can be detected at the 400th cycle with 2 wt % 4TP additive, which disappears completely in the one with baseline electrolyte. These results reveal that the application of a 2 wt % 4TP improves the structural and interphasial stability of LNMO during cycling at high voltage.

As shown in Figure 3A, the chronoamperometric currents of LNMO/Li cells at 4.9 V after the initial three cycles at 0.2C were recorded to evaluate the passivation ability of the 4TP additive. A lower value of the residue current represents better passivation capability since the de-lithium reaction of the LNMO electrode is complete and the recorded current mainly reflects the oxidation reaction of the interfacial electrolyte. Obviously, the recorded current of LNMO/Li with a 2 wt % 4TP additive is lower in comparison with that of LNMO/Li without an additive, indicating the effective suppression of the subsequent electrolyte decomposition by the 4TP-derived CEI film.

Figure 3.

Figure 3

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(A) Chronoamperometric responses of LNMO/Li V-type cells in baseline and 2 wt % 4TP-containing electrolytes. Electrochemical impedance spectra (EIS) of LNMO/Li cells after (B) 3 and (C) 300 cycles in baseline and 2 wt % 4TP-containing electrolytes. (D) Rate capability of LNMO/Li cells operated in baseline and 2 wt % 4TP-containing electrolytes in the voltage range of 3.0–4.9 V.

The EIS results of LNMO/Li cells during cycling are given in Figure 3B,C. A depressed semicircle can be visually seen at high frequency after three cycles, while two depressed semicircles appear at high and mid frequencies after 300 cycles due to the resistance of Li+ migration through the CEI film (Rf) and the charge transfer (Rct), respectively.38−40 After three cycles, the diameter of the depressed semicircle of LNMO/Li cycling with the 4TP additive is longer than that of the baseline electrolyte, indicating that the 4TP film-forming reaction would slightly increase the interphasial resistance of LNMO, which is in line with the initial CV result (Figure 1C) and the lower initial discharge capacity of LNMO/Li with an additive (Figure 2A). After 300 cycles, no obvious change can be observed on the interphasial resistance of LNMO/Li cycling with an additive, which well explains the great cycling stability of LNMO/Li shown in Figure 2A. In contrast, the one cycle with baseline electrolyte increases significantly after 300 cycles, which becomes larger than that of electrolyte with an additive. This result confirms that 2 wt % 4TP indeed improves the interphasial stability of LNMO during cycling at high voltage.

The rate capability of LNMO was further evaluated as presented in Figure 3D. The initial discharging capacity of the LNMO/Li cell is slightly lower in comparison with that of the baseline electrolyte, which is ascribed to the larger interphasial resistance caused by 4TP. After that, with the increase in the discharging current and cycle numbers, the discharge capacity of LNMO in an additive-containing electrolyte becomes larger than that of LNMO without an additive, showing that the CEI film created by 4TP is beneficial for the subsequent rate capability of the LNMO cathode. It reveals that despite the loss of initial capacity, 4TP is favorable to long-term charge/discharge capability under high current density due to its outstanding interphasial stability.

3.3. Interphasial Morphology and Composition of LNMO

Next, the interphasial morphology and composition of LNMO before and after cycling were investigated to further understand the causes of capacity fading of the LNMO cathode and the improvement mechanism of the 4TP additive. Figure 4 exhibits the SEM and TEM images of LNMO electrodes. Obviously, in comparison with the smooth and clean interface of fresh LNMO (Figure 4A,D,G), the LNMO surface after cycling in a baseline electrolyte is covered with the products of a nonuniform decomposition of the electrolyte (Figure 4B,E,H), which results in lower electrochemical reaction kinetics and an inferior interphasial stability. In contrast, a uniform and thin (∼10 nm) CEI film can be found on the LNMO surface cycling in a 4TP-containing electrolyte (Figure 4C,F,I), which efficiently restrains the oxidation reaction of electrolyte on a high-voltage cathode surface (Figure 3A).

Figure 4.

Figure 4

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SEM and TEM images of fresh LNMO electrode (A, D, G) and LNMO electrodes taken from the LNMO/Li cells after 100 cycles in baseline (B, E, H) and in 2 wt % 4TP-containing electrolytes (C, F, I).

XPS characterizations were used to further examine the composition of LNMO electrodes surface, as shown in Figure 5. For fresh LNMO, −CF2 (290.8 eV), C–C (284.8 eV), and C–H (286.2 eV) species in the C 1s spectrum (Figure 5A) are assigned to the PVDF binder and acetylene black.17 The M–O (529.8 eV) and C=O (531.9 eV) species in the O 1s spectrum (Figure 5B) are attributed to Li2CO3 (derived from raw materials) and LNMO, respectively.41 Meanwhile, the −CF2 (687.8 eV) peak shown in F 1s spectrum (Figure 5C) comes from PVDF.13 The vanishing of the M–O peak in the O 1s spectrum (Figure 5B) indicates that the LNMO surface is indeed covered with electrolyte decomposition products after cycling.18 The appearance of B–F (194 eV) and B–O (191.5 eV)42−46 in the B 1s spectrum on LNMO after cycling with the 4TP additive confirms the film-forming reaction of 4TP. The C=O, LiF (685 eV in F 1s spectrum), LiPxFy (137 eV), and LixPOyFz (134.8 eV) species are mainly yielded from the decomposition of carbonate solvents and LiPF6 salts. The peak intensity of these compounds shown in LNMO after cycling with 4TP additive is lower than that of the baseline electrolyte, demonstrating again that application of 4TP effectively prevents the decomposition of baseline electrolyte.

Figure 5.

Figure 5

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(A) C 1s, (B) O 1s, (C) F 1s, (D) P 2p, and (E) B 1s XPS patterns of fresh LNMO and the LNMO electrodes taken from LNMO/Li cells after 200 cycles in baseline and 2 wt % 4TP-containing electrolytes.

The structural stability of LNMO after cycling with baseline and additive-containing electrolyte was also investigated, as exhibited in Figure 6. The XRD patterns of the fresh LNMO electrode and that after cycling with the 4TP additive are quite similar, see Figure 6A,B. However, the peak intensity of the electrode after cycling in a baseline electrolyte decreases obviously, especially for the (111) and (311) planes, which even shift to a higher angle, see Figure 6B.47 It can be ascribed to the dissolution of transition metals from the lattice of LNMO particles,48−50 which is confirmed by the higher amounts of Ni and Mn ions detected from the Li counter electrode in the additive-free electrolyte (Figure 6C). This indicates that the CEI film created by the 4TP additive can not only prevent the electrolyte from oxidation decomposition at high voltage but also improve the structural stability of LNMO. This is in line with the disappearance of the Mn3+/Mn4+ redox reaction at around 3.8 V of LNMO after 400 cycles in a baseline electrolyte shown in Figure 2D.

Figure 6.

Figure 6

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(A) XRD patterns of fresh and cycled LNMO electrodes taken from the LNMO/Li cells after 200 cycles in baseline and 2 wt % 4TP-containing electrolytes and magnified between 18 and 37.5° for 2θ (B). (C) Contents of transition-metal ions on Li anodes, which are taken from LNMO/Li after 200 cycles in baseline and 2 wt % 4TP-containing electrolytes.

3.4. Effect of 4TP on Li and Graphite Electrodes

It has been well accepted that film-forming additives might also affect the Li electrode, leading to the difference in the cycling stability of the investigated cells using Li as the counter/reference electrode.17,21,35 Therefore, the effect of the 4TP additive on the Li/Li cell was investigated, as presented in Figure 7A. No obvious difference can be observed from the lithium stripping plating test, indicating that the enhanced cycle stability of the LNMO/Li battery shown in Figure 2A is ascribed to the improved performance of the LNMO cathode. The remarkable potential polarization of both Li/Li symmetric cells appearing after 200 h of Li depositing/stripping is ascribed to the generation of dendritic Li.17,21,35

Figure 7.

Figure 7

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(A) Voltage profiles of the Li/Li symmetric cells during the stripping plating test with a current density of 1 mA cm–2 and a plating/stripping capacity of 1 mAh cm–2. (B) Specific discharge capacity of graphite/Li cells in baseline and 2 wt % 4TP-containing electrolytes.

The cycle stability of graphite/Li battery with 4TP was also studied because most commercial LIBs use graphite as the anode material, as shown in Figure 7B. Interestingly, the application of 2 wt % 4TP improves the initial capacity of graphite anode. The one with additive delivers higher discharge capacity at 0.1 and 0.2C but shows negligible influence on capacity retention. This contribution of 4TP is similar to that of most of the B-containing film-forming additives, which show great capability of enhancing the rate performance of LIBs.35,36 In this work, we primarily focus on the influence of the film-forming electrolyte additive 4TP on the high-voltage LNMO cathode, and we will further investigate its impact on the graphite anode and LNMO/graphite full cell performances in the future.

4. Conclusions

In this work, a cost-efficient film-forming additive 4TP is proposed to enhance the long-term cycling stability of LNMO/Li at 4.9 V. DFT calculations and electrochemical characterizations show that a thin, uniform, and protective CEI film is obtained during the initial charging process of LNMO with a 4TP-containing electrolyte due to its higher oxidation activity, decomposing prior to the baseline electrolyte. The induced CEI film not only restrains the succesive oxidation of baseline electrolyte but also improves the LNMO electrode structural stability, resulting in greatly improved capacity retention of LNMO after 480 cycles. Beyond that, the graphite anode rate performance can be also enhanced by 4TP, indicating that this additive can be applied in high-voltage LIBs consisting of a LNMO cathode and a graphite anode.

Acknowledgments

This work is supported by the National Natural Science Foundation of China (21972049).

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.1c05176.

  • Comparison of additives on Li/LNMO half-cells in this work with other reported work. The ion conductivity test of different electrolytes and contact angles between the LNMO cathode and electrolyte with different electrolyte (PDF)

Author Contributions

§ Z.M. and H.C. contributed equally to this work.

The authors declare no competing financial interest.

Supplementary Material

ao1c05176_si_001.pdf (188.7KB, pdf)

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