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. 2025 Jun 19;10(25):27415–27423. doi: 10.1021/acsomega.5c03130

Improved Electrochemical Performance of Lithium-Rich Manganese-Based Materials via a PI/MWCNT Composite Coating Layer

Yali Wang †,*, Peiqi Fan ‡, Bingxue Liu §, Xiaoyan Li †, Yunfeng Fu †, Guoshan Du †,*, Jun Liu †, Songxuan Chen †, Hangyu Sun †
PMCID: PMC12223913  PMID: 40620972

Abstract

Lithium-rich manganese-based (LRM) materials have emerged as leading contenders for next-generation LIBs, delivering exceptional energy densities (>900 W h kg-1), while maintaining cost advantages over cobalt-containing alternatives. However, the voltage decay, capacity loss, and life reduction have hindered their further commercialization. Herein, the strategy of using a polyimide/multi-walled carbon nanotubes (PI/MWCNTs) composite coating layer is proposed to optimize the microstructure and enhance the electrochemical properties. The novel PI is constructed with the highly polar and microbranched cross-linking network, which significantly enhances the interface structure stability. The MWCNTs in situ loaded on the LRM particles provide abundant electron transfer sites. Therefore, an initial discharge capacity of the coated-LRM is 238.7 mA h g–1 between 2 and 4.6 V at 0.1C @ 25 °C, which is slightly higher than that of LRM (217.5 mA h g–1). The coated LRM and LRM maintain 73% and 41% of their initial discharge capacities at 1C between 2 and 4.6 V after 200 cycles, respectively.

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1. Introduction

Lithium-rich manganese-based (LRM) cathode materials with the composition of x Li2MnO3·(1 – x)­LiTMO2 (TM = Mn, Ni, Co, etc.) have attracted more attention because of their high capacity (>250 mA h g–1), high voltage (>4.5 V), and reduced cost. − Related studies indicate that the remarkable capacity of LRM materials is due to the combined contributions of transition metal (TM) cationic redox reactions (TM n+/TM(n+1)+) and anionic redox activities involving oxygen species (O2–/O n–). , However, the lattice oxygen redox process (O2– → O2) occurs at the surface of particles and some irreversible Li+ ions are extracted from the lattice at the charge voltage of 4.5 V, resulting in cation rearrangement. , Besides, the reduction of Mn4+ to Mn3+ triggers a phase transition from a layered to a spinel structure during discharge, further compromising the material’s performance. , In general, lattice oxygen release and crystal phase transition are major factors of the continuous voltage and capacity fading.

In order to alleviate the problems caused by the oxygen release and phase transition, surface coating has been used to stabilize the LRM structure and improve the electrochemical performance. Researchers usually use the active materials such as LiFePO4, LiNiO2, and Li4Mn5O12 as coating layers, which possess lower capacities and voltage plateaus. Notably, their stability at high voltages needs to be verified. Some inactive materials, including Al2O3, , ZrO2, , AlF3, , and carbon, , show a stable structure, which can inhibit the electrolyte corrosion and oxygen release. However, most lattice structures of such materials cannot match well with LRM, thus increasing the ion/electron migration obstruction. Furthermore, novel strategies such as elemental doping, core–shell structure design, intrinsic defect repair, and synergistic modification of bulk and interface phases are employed to regulate the crystal structure, electronic states, and interfacial side reactions, thereby addressing defects like oxygen vacancies and cation mixing in cathode materials, ultimately achieving simultaneous improvements in energy density and cycle life. −

Recently, the high voltage endurance polymers were reported to enhance the cycle performance, rate performance, and safe performance of LIBs. Polymers were not only investigated as electrolytes to guarantee the ion transport, but also demonstrated as binders to enhance the electrode structure stability. − Moreover, polymers were used as a coating layer to interrupt the interface side reactions. , In this paper, we first prepared a polyimide/multi-walled carbon nanotubes (PI/MWCNTs) composite coating layer to well adapt the LRM cathode materials. A PI/MWCNTs composite coating layer is designed to give advanced properties; the soft and hard segment-modulated cross-linking polymer network with functional polar groups assists the uniform and strong interface structure at the LRM particles, and the MWCNTs guarantee abundant electron transfer sites. Benefiting from the unique architecture, the coated LRM material presents favorable electrochemical properties, including high reversible capacity, slight voltage fading, and excellent rate capability.

2. Experimental Section

2.1. Materials

3,3′,4,4′-Biphenyltetracarboxylic dianhydride (BPDA, 99%), p-phenylenediamine (p-PDA, >98%), 2,3-diaminobenzoic acid (DABA, >98%), 1,3,5-tris­(4-aminophenoxy)­benzene (TAPOB, 99%), poly­(vinylidene fluoride) (PVDF), and MWCNTs (95%) were sourced from Macklin and employed without additional purification. N-Methyl-2-pyrrolidinone (NMP, 99%) and ethanol (>98%) were obtained from Energy Chemical. Li1.2Mn0.54Co0.13Ni0.13O2 (LRM) and Super-P were procured from the China Automotive Battery Research Institute.

2.2. Material Preparation

Preparation of the composite coating layer: MWCNTs (0.25 g) were added to the NMP solvent (60 g) to obtain the mixed solution. The mPDA (1.311 g), DABA (0.790 g), and ODPA (5.391 g) were gradually added to the mixed solution to obtain linear PAA/MWCNTs glue. Then the dissolved TAPOB solution (0.217 g in the 5 mL NMP solvent) was slowly dropped into the linear PAA/MWCNTs glue to obtain branched cross-linking PAA/MWCNTs glue and strongly stirred for 6 h. LRM (4 g) was added in dissolved PAA/MWCNTs (10 wt %) and stirred strongly for 4 h. The mixed solution was added to the ethanol solution (100 g) and uniformly dispersed for 2 h. After vacuum filtration and drying, PI/MWCNTs-LRM was obtained by thermal processing at 300 °C for 3 h. The proportion of PI/MWCNTs coating in LRM material was 8 wt %.

Preparation of the LRM cathode: The LRM active material (2.2 g), SP carbon black (0.275 g), and PVDF binder (0.275 g) were mixed in NMP at an 80:10:10 mass ratio to prepare the uniform viscous cathode slurry. The well-mixed slurry was cast onto aluminum foil current collectors, resulting in an cathode with an areal loading of 3–4 mg cm–2 for the active material.

2.3. Material Characterizations

Structure characterization was performed via FT-IR (Thermo Scientific Nicolet 8700). Thermal property was evaluated by DSC (Q20) under N2 flow. Microscopic features and elemental mapping were obtained by FE-SEM (Hitachi S-4700) and HRTEM, and phase identification was carried out by XRD (Cu-Kα source).

2.4. Electrochemical Measurements

CR2032-type coin cells were fabricated in an Ar-filled glovebox using a lithium foil anode, 1 M LiPF6 in dimethyl carbonate (DMC)/ethylene carbonate (EC)/ethyl methyl carbonate (EMC) (1:1:1 v/v) electrolyte, and Celgard 2400 separator. The electrochemical tests were performed between 2 and 4.6 V versus Li+/Li with different current densities (0.1–10C, 1C = 200 mA g–1). Cyclic voltammetry (CV) was conducted on an electrochemical workstation (CHI660D, Chenhua) between 2 and 4.6 V at a scanning rate of 0.01 mV s–1. AC impedance spectra were recorded on an electrochemical workstation with frequency sweeps between 10–2 and 105 Hz.

3. Results and Discussion

The SEM images of the LRM and coated-LRM materials are shown in Figure a–d. There is no obvious difference between the bare particles and coated particles. Compared with the bare LRM particles in the magnified image, it is clear that the coiled MWCNTs shuttled in the PI transparent thin film, which formed the rough surface on coated-LRM particles. The chemical structure of PI and PI/MWCNTs was characterized by FTIR shown in Figure S1 (Supporting Information). The typical features at 1775 (asymmetric CO), 1720 (symmetric CO), 1350 (C–N stretching), and 730 (CO bending) are assigned to the imide groups of PI. PI/MWCNTs exhibits identical characteristic peaks as well as PI, indicating that the introduction of MWCNTs has no influence on the structure of PI. As illustrated in Figure S2 (Supporting Information), the onset exothermic temperature peak of the PI/MWCNTs is higher than that of the PI (617 °C vs 566 °C), demonstrating the improved thermal stability of the PI compared with the MWCNTs. Additionally, the total heat release is significantly lower for the PI/MWCNTs (3022 mJ mg–1) compared to the PI (4191 mJ mg–1), highlighting the advantageous role of the PI/MWCNTs in enhancing the thermal stability.

1.

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(a) SEM image of LRM. (b) SEM image of coated-LRM. (c) Magnified SEM image of LRM. (d) Magnified SEM image of coated-LRM. (e) XRD spectra of LRM and coated-LRM. (f) FITR spectra of LRM and coated-LRM.

To clarify the influence of composite PI/MWCNTs on LRM particles, FTIR and XRD spectra were measured to analyze the chemical characteristics. Two separated peaks at 618 and 537 cm–1 representing the M–O (M = Mn, Co, Ni) asymmetrical stretching of LRM are shown in FTIR (Figure e), which remained unchanged after surface coating. XRD patterns in Figure f confirm that LRM particles coated with PI/MWCNTs maintain a hexagonal α-NaFeO2 layered structure with space group R3̅m. The distinct splitting (006)/(102) and (108)/(110) peaks in the LRM and coated LRM particles indicate a well-defined layered structure. The slight increase in the I(003)/I(104) ratio from 1.3 to 1.5 following coating suggests a potential reduction in Li/Ni mixing, which could contribute to improved electrochemical performance in terms of rate response and cycle life. No peaks of MWCNTs and PI were observed due to the low concentration.

TEM was employed to determine the microscopic morphology and surface coating of the LRM material. As clearly shown in Figure a–c, the surface of LRM particles is wrapped with a continuous PI/MWCNTs layer. Such continuous PI/MWCNTs that are 15–20 nm thick are present on the majority of imaged particles (Figure S3, Supporting Information). Besides, about 20 nm long MWCNTs through the PI film are noted in which the lattice stripe is 0.34 nm (Figure d). There are the distinct lattice fringes of the LRM structure given as the inset in Figure e, exhibiting (003) lattice fringes at 0.47 nm spacing, demonstrating preservation of LRM’s rhombohedral layered structure after PI/MWCNTs modification (Figure f). The observed results originate from the controlled coating synthesis procedure and a well-designed PI molecular structure. The PI/MWCNTs were added in their initial PAA/MWCNTs forms during the coated-LRM process and converted into their final PI/MWCNTs forms at a high-temperature treatment of 300 °C. The high density of polar moieties (−CONH, –COOH) in PAA drives the PAA-to-MWCNTs and LRM-to-PAA/MWCNTs interaction by establishing simultaneous hydrogen bonding and chemical bonding. As displayed in Figure f, the PI with the strong polar –COOH group can induce the formation of the hydrogen bond, facilitating the strong binding interaction.

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(a) HRTEM image of coated-LRM. (b) Magnified HRTEM image of the region b in (a). (c) Magnified HRTEM morphology of the region c in (b). (d) Morphology structure of MWCNTs. (e) FFT patterns of LRM for coated-LRM. (f) Structure diagrams of PI, MWCNTs, and LRM.

To assess the electrochemical performance of LRM before and after coating, the initial charge/discharge, rate capability, and cycling performance were assessed at various current densities within a 2.0–4.6 V (versus Li/Li+) operating window at 25 °C. Figure a shows the initial charge–discharge profiles at 0.1C (1C = 200 mA h g–1) of LMR and coated-LRM. The LRM shows a typical charge/discharge profile with a slope region below 4.5 V and a platform above 4.5 V. The slope region represents the extraction of Li+ from the lithium layer with an oxidation reaction of Ni2+/Ni4+, while the platform is ascribed to the activation process of the Li2MnO3 component along with simultaneous oxygen evolution. The initial discharge capacities of LRM and coated-LRM are 217.5 mA h g–1 and 238.7 mA h g–1, with related Coulombic efficiencies of 72.3% and 81.1%, respectively. The rate capabilities of LRM and coated-LRM are compared in Figure b. Both the LRM and coated-LRM exhibit comparable discharge capacities when cycled at low current densities (≤0.5C). The discharge capacities of coated-LRM are 165.4, 146.4, 120.9, and 54.1 mA h g–1 respectively, at 1C, 2C, 5C, and 10C, whereas the LRM gives low discharge capacities of 144.1, 114.6, 59.1, and 12.6 mA h g–1 at same currents. Significantly, the LRM coated by PI/MWCNTs composite material presents outstanding rate performance. The improved Coulombic efficiency and enhanced rate capability may be mainly attributed to two aspects. One is that PI provides abundant lithium-ion transport pathways through coordination complexes formed between Li+ ions and its oxygen-containing functional groups (–O–, –COOH), and the other is the good conductivity provided by the in situ loaded MWCNTs. The PI/MWCNTs composite coating layer, which possesses the ability to boost the ion/electron mobility, is beneficial to facilitate the electrochemical kinetics of the LRM.

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Electrochemical performances for the LRM and coated-LRM: (a) initial charge–discharge profiles. (b) Rate performance at different currents in a 2.0–4.6 V operation window. (c) Long-term cycling performance at 0.5C in a 2.0–4.6 V operation window. (d) Long-term cycling performance at 1C in a 2.0–4.6 V operation window.

The long-term cycle performance of coated-LRM was operated at different current densities in a 2.0–4.6 V operation window. As described in Figure c, the coated-LRM delivers an initial discharge capacity of 192.5 mA h g–1 with a capacity retention of 68% after 100 cycles at 0.5C, while the LRM delivers a lower initial discharge capacity of 182.2 mA h g–1 with a capacity retention of 57%. When the current density reaches 1C, the discharge capacity of coated-LRM after 200 cycles is maintained at 106.9 mA h g–1 with 73% capacity retention, while the LRM maintains lower capacity retentions (56.6 mA h g–1, 41%). Obviously, the LRM coated by PI/MWCNTs can realize the long-term cyclability under the large current density, demonstrating the positive effect of the PI/MWCNTs composite material.

To further analyze the PI/MWCNTs composite material impact as a coating layer for LRM at large current density, the discharge profiles of the LRM and coated-LRM at 1C in a 2.0–4.6 V operation window are depicted in Figure a,b. The color of the curves transitions (black → blue → green → purple) represents the first, 50th, 100th, ..., 200th cycles of the samples. Not only the discharge profiles of LRM rapidly declined, but also the voltage dramatically attenuated. Contrarily, the discharge profiles of coated-LRM show slow fading as well as a slight voltage attenuation. Slower voltage decay means fewer harmful phase transitions, indicating that the layered crystal structure of coated-LRM is more stable due to the PI/MWCNTs modification. The dQ/dV plots (Figure c,d) at variable cycles are depicted to deeply understand the electrochemical reaction. The anodic peak located between 2.5 and 3.5 V indicates reduction of Mn4+ to Mn3+, while the anodic peak located at 3.5 V to 4.5 V indicates reduction of Co4+ to Co3+ and Ni4+ to Ni3+. , The peak shift of Mn4+ to Mn3+ toward the low voltage indicates that the structure changes from the layer to the spinel, which is caused by migration of the transition metal ions. With the increase of cycle numbers, the anodic peak (Mn4+ → Mn3+) of LRM moved rapidly toward 2.6 V, while this anodic peak of coated-LRM gradually stabilized around 3.0 V after 200 cycles. It is obvious that the voltage decay of coated-LRM is suppressed by PI/MWCNTs coating modification to a certain extent.

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(a) Discharge profiles of LRM corresponding to long-term cycling performance at 1C in a 2.0–4.6 V operation window. (b) Discharge profiles of coated-LRM corresponding to long-term cycling performance at 1C in a 2.0–4.6 V operation window. (c) dQ/dV profiles of (a). (d) dQ/dV profiles of (b).

XRD was performed to examine the LRM structure change before and after 200 cycles at 1C. As displayed in Figure a, the characteristic (003), (006)/(102), and (018)/(110) diffraction peaks of the hexagonal α-NaFeO2-type layered structure remain sharp and unchanged in both LRM and coated-LRM, with no detectable impurity phases. However, the significant peak shift (0.3°) in pristine LRM suggests lattice expansion, whereas the near-zero shift (0.04°) in coated-LRM confirms effective structural stabilization by the coating layer. The shift at 2θ to a lower angle of (003) peak expresses an enlargement in the c-axis and volume, accompanied by a kinetic barrier to Li+ diffusion. , PI/MWCNTs coating with electronic/ionic conductivity can stabilize the layered structure and promote the electrochemical reaction. The active particle deposition as well as Mn metal precipitation of LRM and coated-LRM after 200 cycles at 1C are analyzed in Figure b–g. Compared with the coated-LRM, there are much more active particles and lithium compounds deposited on the separator of LRM. In addition, more Mn (0.8 wt %) dissolved into the electrolyte and deposited on the separator of LRM, while the Mn deposition ratio on the separator of coated-LRM is 0.3 wt %. Accordingly, PI/MWCNTs coating acts as a protective layer which suppresses metal dissolution, thus increasing the electrochemical performance of LRM at long-term cycling. ICP–MS measurements were conducted to analyze the amount of the Mn element of the cathodes at initial state and cycled state (Supporting Information, Table S1). Both the initial samples and cycled samples were dissolved in the hydrochloric acid (HCl), respectively. The Mn retention ratios for the initial LRM and initial coated-LRM are 28.23% and 27.95 wt %, suggesting that the coating has a negligible impact on Mn dissolution in the initial state. The coated sample exhibits higher Mn retention (23.78 wt %) compared to the uncoated one (21.93 wt %), indicating that the coating mitigates Mn loss during cycling. ICP–MS results corroborate the EDX observations and further strengthen our conclusions.

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(a) XRD patterns of LRM and coated-LRM before and after 200 cycles at 1C in a 2.0–4.6 V operation window. Surface attachments of the LRM separator in (b) and coated-LRM separator in (e) after 200 cycles. SEM morphologies of the LRM separator in (c) and coated-LRM separator in (f) after 200 cycles. (g) EDX elemental mapping of Mn corresponding (d) and (g) in the region (c) and (f), respectively (photograph courtesy of “Yali WANG”. Copyright 2025).

SEM images of LRM and coated-LRM particles at 1C after 200 cycles were characterized (Figure a,b), and the LRM has obvious particle breakage of the secondary crystal, which is caused by the volume change in the process of charging and discharging. On the contrary, the coated-LRM has almost no structural damage and secondary cracking, demonstrating that PI/MWCNTs with good mechanical properties can stabilize the interface structure and avoid secondary particle cracking. It is noted that there is a discontinuous and rough layer on cycled samples in the enlarged image (Figure c,d), which refers to the organic species from the electrolyte decomposition reactions. Sensibly, the byproduct of coated-LRM is less than LRM, manifesting the PI/MWCNTs can inhibit side reaction on the surface of LRM. This result is also supported by EIS. Figure e,f shows the initial and 200th cycled Nyquist plots. The simulated EIS curve, generated from the equivalent circuit (Figure.S4, Supporting Information), revealed the ohmic resistance (R s), charge-transfer resistance (R ct), and Warburg diffusion impedance (W), respectively. The detailed values of R ct are listed in Table S2, Supporting Information. The R ct of the initial LRM (53 Ω) is lower than that of the initial coated-LRM (59 Ω), which is induced by the high polarization of the PI material itself. The R ct of cycled LRM is much higher than that of cycled coated-LRM (609 Ω vs 298 Ω). Due to the solid ion/electron PI/MWCNTs coating layer, the resistance of cycled coated-LRM is reduced to some extent. This is because the PI/MWCNTs coating layer on the surface of LRM, which isolates the direct contact between active particles and electrolytes, finally inhibits the serious side reactions and protects the LMR structure.

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SEM morphologies of LRM in (a) and coated-LRM in (b) after 200 cycles. Enlarged SEM morphologies of LRM in (c) and coated-LRM in (d) after 200 cycles. (e) Initial Nyquist plots of two different half-cells. (f) Cycled Nyquist plots of two different half-cells.

To investigate the impact of the PI/MWCNTs coating layer on enhancing the long-term cycle life and stabilizing the LRM structure, cycling performance tests were conducted at a cutoff voltage of 4.8 V. As displayed in Figure , the initial discharge capacities of the LRM and the coated-LRM at 0.1C are 293.3 and 303.4 mA h g–1, respectively, corresponding to initial coulombic efficiencies of 72% and 80%. The coated-LRM maintains a capacity retention of ≈57% after 200 cycles at 1C, whereas the LRM exhibits a significant capacity fade with 40% capacity retention. These results clearly demonstrate that the coated-LRM exhibits superior cycling performance compared to the LRM, highlighting the effectiveness of the PI/MWCNTs coating layer in improving both the initial discharge capacity and long-term cycling stability under high-voltage conditions.

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Long-term cycle performance of LRM and coated-LRM at different current densities in a 2.0–2.8 V operation window.

As described in Figure , the electrochemical improvements can stem from the coating’s multifunctionality: (i) PI/MWCNT composite coating layer serves as a robust protective barrier, mitigating electrolyte-induced side reactions (e.g., transition metal dissolution and oxygen release) by physically blocking direct contact between the cathode and electrolyte. (ii) The conductive MWCNTs embedded in the PI matrix establish 3D electron pathways, reducing interfacial charge-transfer resistance, while the porous PI structure facilitates Li+ diffusion.

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Diagram of improvement mechanism for coated-LRM (photograph courtesy of “Yali WANG”. Copyright 2025).

4. Conclusion

A 15–20 nm thick PI/MWCNTs layer was successfully coated on the surface of LRM by a PAA/MWCNTs coating after the thermal imidization process, of which the combined structures were confirmed by SEM and HRTEM images. The coated-LRM exhibits a higher initial Coulombic efficiency (81.1%), higher rate capability (120.9 mA h g–1 at 5C), and higher capacity retention of 73% at 1C current after 200 cycles at 4.6 V discharge voltage, as well as higher capacity retention of 57% at 1C current after 200 cycles at 4.8 V discharge voltage. The enhanced performance originates from the engineered PI/MWCNTs coating, which simultaneously ensures structural integrity and establishes dual-conductive (ionic/electronic) pathways throughout the cathode matrix. As confirmed by dQ/dV, XRD, SEM, EDS, and EIS results, the PI/MWCNTs coating layer reduces the formation of interface byproducts, relieves the Mn precipitation, suppresses the voltage attenuation, eventually improving LRM electrochemical performance. This work can be extended to fabricate multifunctional coating layer to obtain high efficiency lithium-rich manganese-based materials.

Supplementary Material

ao5c03130_si_001.pdf (300.5KB, pdf)

Acknowledgments

We thank financial support by the China Postdoctoral Science Foundation (2023M743911).

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.5c03130.

  • Structure characterization of PI and PI/MWCNTs (FTIR), thermal gravimetric analysis of PI and PI/MWCNTs (TGA-DSC analyzer), HRTEM images of coated-LRM (surface coating morphology), equivalent circuit of the EIS curves (electrochemical workstation), Mn retention of cathodes at initial and cycled stations (ICP–MS), and charge transfer resistance of LRM and coated-LRM (initial and cycled conditions) (PDF)

The authors declare no competing financial interest.

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