Self-propagating Combustion Synthesis and Sodium Storage Performance of Manganese-rich P2/P3 Biphasic Na0.67Mn0.9Ni0.1O2

doi:10.6023/A25080290

Abstract

The P2-type manganese-rich layered oxides have emerged as highly promising cathode materials for sodium-ion batteries owing to their exceptional advantages including high specific capacity and low cost. However, huge challenges remain for their practical applications, particularly the capacity degradation under deep desodiation conditions and the structural sensitivity to calcination temperatures during material synthesis. In this study, we successfully fabricated a P2/P3 biphasic Na_0.67Mn_0.9Ni_0.1O₂ (designated as NMNO-800) cathode material through a carefully controlled self-propagating combustion synthesis method with precise temperature regulation. Comprehensive X-ray diffraction characterization revealed that the calcination temperature plays a critical role in phase formation. NMNO-700 (calcined at 700 ℃) exhibited a pure P3-phase structure with R3m space group, while NMNO-900 (calcined at 900 ℃) showed a pure P2-phase structure with P63/mmc space group. Remarkably, the NMNO-800 sample calcined at the optimal temperature of 800 ℃ demonstrated a well-defined and stable P2/P3 biphasic structure, with the phase ratio quantitatively determined to be 42.4% P2-phase and 57.6% P3-phase through Rietveld refinement analysis. Scanning electron microscope (SEM) observations further confirmed that the NMNO-800 possesses a unique hierarchical nano-micro composite architecture, consisting of well-dispersed micron-sized particles ranging from 1.94 to 2.57 μm in diameter, with numerous nanoparticles distributed on the surface of these micron-scale sheet-like particles. This ingenious designed biphasic Na_0.67Mn_0.9Ni_0.1O₂ successfully combines the advantageous features of both P2 and P3 phases, maintaining the excellent structural stability characteristic of P2-phase while preserving the high initial capacity inherent to P3-phase, thereby achieving superior electrochemical performance. Specifically, the NMNO-800 delivers an outstanding reversible capacity of 165.44 mAh/g at 0.2 C rate, maintains a respectable capacity of 89.18 mAh/g even at an extremely high rate of 10 C, and shows excellent cycling stability with 84.2% capacity retention after 100 cycles at 0.5 C rate, significantly outperforming all single-phase counterparts. All the results indicate that the P2/P3 biphasic structure enhances the rate performance of manganese-rich layered oxide cathode materials, improves sodium ion diffusion efficiency, and maintains good cycling stability.

Key words: sodium ion battery, cathode materials, layered oxides, P2/P3 biphase, Mn-rich materials

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Qingtang Zhang, Chunyang Du, Pengfei Gao, Xiaomei Wang. Self-propagating Combustion Synthesis and Sodium Storage Performance of Manganese-rich P2/P3 Biphasic Na_0.67Mn_0.9Ni_0.1O₂[J]. Acta Chimica Sinica, 2026, 84(1): 64-72.

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Fig. & Tab. 12

Figure 1. (a) XRD spectra of NMNO-700, NMNO-800 and NMNO-900; (b) Schematic diagram of the crystal structure of NMNO-700, NMNO-800 and NMNO-900; XRD Rietveld refinement of (c) NMNO-700, (d) NMNO-800 and (e) NMNO-900

Sample	P2-Na_0.67Mn_0.9Ni_0.1O₂				P3-Na_0.67Mn_0.9Ni_0.1O₂
Sample	a/nm	b/nm	c/nm	V/nm³	a/nm	b/nm	c/nm	V/nm³
NMNO-700	—	—	—	—	0.285	0.285	1.679	0.11879
NMNO-800	0.287	0.287	1.122	0.08051	0.287	0.287	1.675	0.12027
NMNO-900	0.288	0.288	1.129	0.08126	—	—	—	—

Table 1. Unit cell parameters of NMNO-700, NMNO-800 and NMNO-900

Figure 2. SEM images of (a) NMNO-700, (b) NMNO-800 and (c) NMNO-900; (d) EDS element mapping of NMNO-800

Figure 3. (a) TEM image of NMNO-800; (b) HRTEM image of NMNO-800; (c) SAED image of NMNO-800

Figure 4. (a) XPS profile of NMNO-800; (b) Mn 2p and (c) Ni 2p spectra of NMNO-800

测试元素	样品质量m₀/g	元素含量w/%	元素物质的量/mol	物质的量比
Na	0.1030	14.3005%	6.407×10^-4	0.65
Mn		47.0286%	8.817×10^-4	0.89
Ni		5.6639%	9.940×10^-5	0.1

Table 2. Element content of NMNO-800 determined by inductively coupled plasma optical emission spectrometer (ICP-OES)

Figure 5. (a) First, (b) third and (c) fifth charges and discharges of NMNO-700, NMNO-800, and NMNO-900 at 0.2 C

Figure 6. (a) Rate performance of NMNO-700, NMNO-800 and NMNO-900; (b) Cycling performance of NMNO-700, NMNO-800 and NMNO-900 at 0.5 C

Figure 7. (a) SEM images of the NMNO-800 electrode sheet before cycling; (b) SEM images of the NMNO-800 electrode sheet after 48 cycles at 0.5 C

Figure 8. The CV curves of NMNO-700, NMNO-800, and NMNO-900 for (a) the second cycle and (b) the third cycle

Figure 9. (a) ΔEt and ΔEs during charge process of NMNO-800; (b) the third charge-discharge GITT curves of three NMNO at 0.2 C rate; (c) reaction resistance calculated by GITT; sodium diffusion coefficient of NMNO: (d) charge, (e) discharge; (f) EIS plot of NMNO material after 100 cycles

	R_e/Ω	R_f/Ω	R_ct/Ω
NMNO-700	21.15	696.6	1540
NMNO-800	22.42	494.5	739
NMNO-900	24.72	1129.0	1129

Table 3. EIS parameters of NMNO

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富锰P2/P3双相Na_0.67Mn_0.9Ni_0.1O₂自蔓延燃烧合成与储钠性能

Self-propagating Combustion Synthesis and Sodium Storage Performance of Manganese-rich P2/P3 Biphasic Na_0.67Mn_0.9Ni_0.1O₂

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富锰P2/P3双相Na0.67Mn0.9Ni0.1O2自蔓延燃烧合成与储钠性能