Solvothermal synthesis of LiFe1/3Mn1/3Co1/3PO4 solid solution as lithium storage cathode materials

Wang, Yanming; Wang, Yajing; Liu, Xiaoyu; Zhu, Banghe; Wang, Fei

doi:10.1039/c7ra01396e

Cited by 12 publications

(2 citation statements)

References 41 publications

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“…A similar trend is observed when Mn y Fe 1– y PO 4 ( y = 0.0, 0.1, 0.2, 0.4, 0.6, and 0.8) is cycled vs Li/Li + (see Figures S3 and S4). This effect has been linked to kinetic issues and poorer Li diffusivity in the Mn regions compared to the Fe region due to Jahn–Teller distortion of the Mn. ,− This explanation is likely to extent to the behavior observed during Na-ion intercalation/extraction herein. Interestingly, CV also reveals pronounced changes in the Fe redox behavior with variation in the Mn content in Mn y Fe 1– y PO 4 .…”

Section: Resultsmentioning

confidence: 96%

Reducing Transformation Strains during Na Intercalation in Olivine FePO₄ Cathodes by Mn Substitution

Henriksen

Mathiesen

Chiang

et al. 2019

ACS Appl. Energy Mater.

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Sodium iron phospho-olivine, NaFePO 4 , is a promising cathode material for Na-ion batteries. However, Naion extraction and intercalation induce a large discontinuous volume change (>10 vol%), which leads to large transformation strains and may hamper the rate capability as well as the cyclic stability of NaFePO 4. In the Liion counterpart LiFePO 4 , the size of the discontinuous volume change can be effectively reduced by substitution of Mn onto the Fe-sites in the phospho-olivine structure, i.e. LiMn y Fe 1-y PO 4 solid solution. In this paper, we investigate the battery performance and phase evolution during Na-ion storage in a series of Mn y Fe 1y PO 4 (y = 0.0, 0.1, 0.2, 0.4, 0.6 and 0.8) cathode materials. Substitution of 10-20% of the Fe by Mn leads to enhance the capacity by >15%. Using operando powder X-ray diffraction, we discover in these materials, the charge-discharge transformation strains are significant reduced by stabilization of a Na z Mn y Fe 1-y PO 4 solid solution over a wide Na-compositional range. This effect even leads to a complete continuous solid solution transformation covering the entire charge process, which shows that the effect of Mn-substitution is a highly effective route for reducing intercalation strains even during intercalation of the relatively large Na-ion.

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Section: Resultsmentioning

confidence: 96%

Reducing Transformation Strains during Na Intercalation in Olivine FePO₄ Cathodes by Mn Substitution

Henriksen

Mathiesen

Chiang

et al. 2019

ACS Appl. Energy Mater.

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“…The following supporting information can be downloaded at: www.mdpi.com/xxx/s1, Figure S1 [27,36,45,[50][51][52][53][54][55] are cited in the supplementary materials.…”

Section: Supplementary Materialsmentioning

confidence: 99%

Freeze-Drying-Assisted Preparation of High-Compaction-Density LiMn0.69Co0.01Fe0.3PO4 Cathode Materials with High-Capacity and Long Life-Cycle for Lithium Ion Batteries

Liu,

Zheng,

Huang

et al. 2024

Batteries

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As a successor to LiFePO4, the research interest in LiMn1−yFeyPO4 has been sustained due to its higher working voltage and safety features. However, its further application is limited by the low compaction density caused by uncontrolled particle size. In this study, the high-quality LiMn0.69Co0.01Fe0.3PO4 (LMFP) materials were prepared using the freeze-drying method to process the LMFP precursor synthesized through a solvothermal crystallization method followed by a calcination process at different temperatures (400–550 °C). The results demonstrate that the obtained particles exhibit a spheroidal shape with a low specific surface area after secondary crystallization calcination at 700 °C. The compaction density increased from 1.96 g/cm3 for LMFP precursor (LMFP-M1) to 2.18, 2.27, 2.34, and 2.43 g/cm3 for samples calcined at 400, 450, 500 and 550 °C, respectively, achieving a maximum increase of 24%. The full cell constructed with the high-compaction-density material calcined at 500 °C displayed discharge capacities of 144.1, 143.8, and 142.6 mAh/g at 0.5, 1, and 3 C rates, respectively, with a retention rate of 99% at 3 C rate. After undergoing charging and discharging cycles at a rate of 1 C for up to 800 cycles, the capacity retention rate was found to be 90%, indicating an expected full cell life span exceeding 2500 cycles.

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A Uniform Conductive Carbon Coating of Nitrogen‐Doped Carbon Improves the Electrochemical Performance of LiMn_0.7Fe_0.3PO₄ Cathode Material for Lithium‐ion Batteries

Xiong,

Zhang,

Dai

et al. 2024

ChemElectroChem

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The practical application of LiMn1−xFexPO4 as a cathode material is hindered considerably by its poor electronic conductivity and slow lithium‐ion diffusion. In the present study, a uniform nitrogen‐doped carbon coating on LiMn0.7Fe0.3PO4 (LiMn0.7Fe0.3PO4@NC) was achieved using ethylene diamine tetraacetic acid (EDTA) as a chelating agent and carbon source. The nitrogen‐doped carbon layer enhanced the electronic conductivity and ionic diffusion of the LiMn0.7Fe0.3PO4 cathode. Furthermore, the uniform carbon layer prevented metal ion dissolution and stabilized the crystal structure. The resulting LiMn0.7Fe0.3PO4@NC‐2 sample demonstrated superior performance with a specific capacity of 152.5 mAh g−1 at 0.1 C and preserved 93.7 % of this capacity over 200 cycles at 1 C. Meanwhile, the LiMn0.7Fe0.3PO4@NC‐2 sample demonstrated a high Li+ diffusion coefficient (3.98×10−11 cm2 s−1) and electrical conductivity (1.47×10−2 S cm−1). This study presents a novel approach to designing high‐performance cathode materials using a cost‐effective and straightforward process.

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Solvothermal synthesis of LiFe_1/3Mn_1/3Co_1/3PO₄ solid solution as lithium storage cathode materials

Abstract: Monodisperse LiMn1/3Fe1/3Co1/3PO4 nanoparticles are synthesized by a solvothermal method, exhibiting outstanding rate capability and cycling stability.

Cited by 12 publications

References 41 publications

Reducing Transformation Strains during Na Intercalation in Olivine FePO₄ Cathodes by Mn Substitution

Reducing Transformation Strains during Na Intercalation in Olivine FePO₄ Cathodes by Mn Substitution

Freeze-Drying-Assisted Preparation of High-Compaction-Density LiMn0.69Co0.01Fe0.3PO4 Cathode Materials with High-Capacity and Long Life-Cycle for Lithium Ion Batteries

A Uniform Conductive Carbon Coating of Nitrogen‐Doped Carbon Improves the Electrochemical Performance of LiMn_0.7Fe_0.3PO₄ Cathode Material for Lithium‐ion Batteries

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Solvothermal synthesis of LiFe1/3Mn1/3Co1/3PO4 solid solution as lithium storage cathode materials

Abstract: Monodisperse LiMn1/3Fe1/3Co1/3PO4 nanoparticles are synthesized by a solvothermal method, exhibiting outstanding rate capability and cycling stability.

Cited by 12 publications

References 41 publications

Reducing Transformation Strains during Na Intercalation in Olivine FePO4 Cathodes by Mn Substitution

Reducing Transformation Strains during Na Intercalation in Olivine FePO4 Cathodes by Mn Substitution

Freeze-Drying-Assisted Preparation of High-Compaction-Density LiMn0.69Co0.01Fe0.3PO4 Cathode Materials with High-Capacity and Long Life-Cycle for Lithium Ion Batteries

A Uniform Conductive Carbon Coating of Nitrogen‐Doped Carbon Improves the Electrochemical Performance of LiMn0.7Fe0.3PO4 Cathode Material for Lithium‐ion Batteries

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Solvothermal synthesis of LiFe_1/3Mn_1/3Co_1/3PO₄ solid solution as lithium storage cathode materials

Reducing Transformation Strains during Na Intercalation in Olivine FePO₄ Cathodes by Mn Substitution

Reducing Transformation Strains during Na Intercalation in Olivine FePO₄ Cathodes by Mn Substitution

A Uniform Conductive Carbon Coating of Nitrogen‐Doped Carbon Improves the Electrochemical Performance of LiMn_0.7Fe_0.3PO₄ Cathode Material for Lithium‐ion Batteries