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LiFePO₄: the olivine cathode

Lithium iron phosphate is cheap, non-toxic and very stable: iron and phosphate build a rigid olivine framework, and lithium sits in one-dimensional channels running through it. Lithium leaves at about 3.5 V by turning LiFePO₄ into FePO₄, two phases sharing one framework, which gives the famously flat voltage. Making the particles small and coating them with carbon was what unlocked nearly all of the 170 mAh g⁻¹.

Updated 4 cited papers57 editable layers

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At a glance

Category
Battery materials
Method
Olivine cathode
Starting materials
Iron(II), lithium and phosphate sources, mixed homogeneously and sintered at a moderate temperature
Product
Olivine LiFePO₄ (Pnma): FeO₆ octahedra and PO₄ tetrahedra with Li in channels along b
Key result
Pattern computed from the refined structure: strongest line (311) near 35.6°, then (111) near 25.6° and (211)/(020) near 29.7° (Cu Kα)
Figure
1920 × 1080 px (16:9), 57 editable layers, 4 generated objects

Step by step

  1. StructurePnma, a = 10.33, b = 6.01, c = 4.69 Å: corner-sharing FeO₆ octahedra linked by PO₄ tetrahedra
  2. 1D channelsLithium sites form chains along b, the only easy direction
  3. Two phasesLiFePO₄ → FePO₄ (heterosite) + Li⁺ + e⁻ at 3.5 V; the framework is kept (Padhi et al. 1997)
  4. Small and coatedModerate sintering and a homogeneous precursor gave > 95 % of 170 mAh g⁻¹ (Yamada et al. 2001); carbon composites approach it at high rates (Huang, Yin & Nazar 2001)

Strengths

  • Iron and phosphate: cheap, non-toxic, abundant
  • Very stable framework: safe and long-lived
  • Flat voltage

Limitations

  • Low electronic conductivity: needs small particles and carbon
  • Lower voltage and density than layered oxides

Uses

  • Electric buses and cars
  • Stationary storage
  • Power tools

Papers this template follows

  1. Padhi, Nanjundaswamy & Goodenough, “Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries”, J. Electrochem. Soc. 1997. doi:10.1149/1.1837571primary
  2. Yamada, Chung & Hinokuma, “Optimized LiFePO4 for Lithium Battery Cathodes”, J. Electrochem. Soc. 2001. doi:10.1149/1.1348257primary
  3. Huang, Yin & Nazar, “Approaching Theoretical Capacity of LiFePO4 at Room Temperature at High Rates”, Electrochem. Solid-State Lett. 2001. doi:10.1149/1.1396695primary
  4. Whittingham, “Lithium Batteries and Cathode Materials”, Chem. Rev. 2004. doi:10.1021/cr020731creview

After Padhi et al., J. Electrochem. Soc. 1997 (doi:10.1149/1.1837571) and Yamada et al., J. Electrochem. Soc. 2001 (doi:10.1149/1.1348257). Structure from refined positions; pattern computed; voltage curve schematic.

How templates are written and checked: editorial guidelines.

Questions

What does the “LiFePO₄: the olivine cathode” template show?

Lithium iron phosphate is cheap, non-toxic and very stable: iron and phosphate build a rigid olivine framework, and lithium sits in one-dimensional channels running through it. Lithium leaves at about 3.5 V by turning LiFePO₄ into FePO₄, two phases sharing one framework, which gives the famously flat voltage. Making the particles small and coating them with carbon was what unlocked nearly all of the 170 mAh g⁻¹.

What are the steps shown in “LiFePO₄: the olivine cathode”?

1. Structure: Pnma, a = 10.33, b = 6.01, c = 4.69 Å: corner-sharing FeO₆ octahedra linked by PO₄ tetrahedra. 2. 1D channels: Lithium sites form chains along b, the only easy direction. 3. Two phases: LiFePO₄ → FePO₄ (heterosite) + Li⁺ + e⁻ at 3.5 V; the framework is kept (Padhi et al. 1997). 4. Small and coated: Moderate sintering and a homogeneous precursor gave > 95 % of 170 mAh g⁻¹ (Yamada et al. 2001); carbon composites approach it at high rates (Huang, Yin & Nazar 2001).

What are the starting materials and the product?

Starting materials: Iron(II), lithium and phosphate sources, mixed homogeneously and sintered at a moderate temperature. Product: Olivine LiFePO₄ (Pnma): FeO₆ octahedra and PO₄ tetrahedra with Li in channels along b.

Which papers is “LiFePO₄: the olivine cathode” based on?

Padhi, Nanjundaswamy & Goodenough, “Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries”, J. Electrochem. Soc. 1997 (doi:10.1149/1.1837571); Yamada, Chung & Hinokuma, “Optimized LiFePO4 for Lithium Battery Cathodes”, J. Electrochem. Soc. 2001 (doi:10.1149/1.1348257); Huang, Yin & Nazar, “Approaching Theoretical Capacity of LiFePO4 at Room Temperature at High Rates”, Electrochem. Solid-State Lett. 2001 (doi:10.1149/1.1396695); Whittingham, “Lithium Batteries and Cathode Materials”, Chem. Rev. 2004 (doi:10.1021/cr020731c).

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LiFePO4LFPlithium iron phosphateolivinePnmacathodephospho-olivineFePO4heterositetwo-phase reactionflat voltage plateaucarbon coating1D diffusion channelXRDlithium-ion battery

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