# Making cathode materials: NMC and LiFePO₄

> Cathode synthesis on one page: the Ni–Mn–Co hydroxide precursor co-precipitated in a stirred tank, lithiated and calcined in oxygen into layered NMC, polycrystalline against single-crystal particles, LiFePO₄ made hydrothermally and coated with carbon, and an Al₂O₃ coating grown by atomic layer deposition. Every step and number is quoted from the cited papers.

- Page: https://www.labcanvas.com/templates/energy-storage-guides/making-cathode-materials-nmc-lifepo4
- Open in the LabCanvas editor (LabCanvas account): https://www.labcanvas.com/editor.html?template=battery-cathode-synthesis
- Updated: 2026-10-14
- Category: Battery & energy storage guides
- Method: Cathode synthesis
- Starting materials: NiSO₄, MnSO₄ and CoSO₄ with NaOH and ammonia; LiOH or LiOH·H₂O; LiOH·H₂O, FeSO₄·7H₂O and H₃PO₄; trimethylaluminium and water
- Product: Ni–Mn–Co hydroxide precursors, layered NMC111 and NCM811 particles, LiFePO₄ platelets with a carbon coating, Al₂O₃-coated NCM811
- Key result: Equipment, particles and crystals drawn by LabCanvas from the cited procedures; vessel sizes, particle counts and colours that no paper fixes are settings, and no panel is a micrograph
- Figure: 1920 × 1080 px, 45 editable layers (6 generated objects with settings)

## Steps

1. **Co-precipitation**: Ni₁/₃Mn₁/₃Co₁/₃(OH)₂, the precursor of NMC111, by semi-batch reaction crystallization in a stirred tank with four baffles and a Rushton turbine (60 L in the lab, 600 L for scale-up), started at pH 12.6 with 5 g/L ammonia at 45 °C; mixed sulfates (2.3 M, 1 : 1 : 1) are fed from one, four or eight nozzles above the impeller while 8.0 M NaOH holds the pH and 13.3 M ammonia holds 5 g/L. Nucleation happens only at the very beginning; plate-like crystals form grape-like agglomerates that give way to rounded particles of even size (Tsuchioka 2024). In the usual batch process the transition-metal solution reacts with ammonia and NaOH at pH 11.5 and 60 °C; for NCM811 they are mixed 8 : 1 : 1, and ripening needed an inert atmosphere to prevent oxidation (Mou 2022)
2. **Lithiation and calcination**: The NCM811 hydroxide ground with stoichiometric LiOH for 10 min, heated in oxygen at 3 °C/min to 770 °C, held 10 h and furnace-cooled. The precursor loses absorbed water below 100 °C and bound water up to about 340 °C, then decomposes up to about 800 °C; an I(003)/I(104) ratio of 1.7 (usually 1.4–1.6) meant less cation mixing (Mou 2022). In another route LiOH·H₂O at 1.00 : 1.05 was ball-milled with the hydroxide and calcined at 750 °C for 12 h in pure oxygen; Ni²⁺ (0.69 Å) and Li⁺ (0.76 Å) have similar radii, so Ni can migrate to Li sites (Ahangari 2024)
3. **Polycrystals or single crystals**: Polycrystalline NMCs crack severely along the grain boundaries of their primary particles; single crystals eliminate intergranular cracking (Lu 2022). Growing single crystals often needs calcination at 900 °C or more, where NCM811 is less stable; a microblock-like precursor lithiated at 800 °C gave single crystals that, cycled between 2.8 and 4.5 V, still showed lattice gliding and intragranular cracks (Cao 2022)
4. **Hydrothermal LiFePO₄**: LiOH·H₂O, FeSO₄·7H₂O and H₃PO₄ (Fe : PO₄ : Li = 0.9 : 1.2 : 2.7, pH 7) in 180 mL of water in a 0.3 L autoclave purged with N₂, heated at 4 °C/min to 300 °C (103 bar) and held 5 min: Li₃PO₄ and Fe₃(PO₄)₂·8H₂O form first, then dissolve to LiFePO₄. Fe₃(PO₄)₂·8H₂O starts to dissolve at about 130 °C; fast heating gives magnetite and poorer crystals, slow heating through 130–150 °C gives pure, (010)-faced platelets, and Li⁺ diffuses several orders of magnitude faster along [010] (Ruiz-Jorge 2021)
5. **Carbon coating**: Coating LiFePO₄ with carbon, or doping it, improves its low electrical conductivity (Ruiz-Jorge 2021). With nanocellulose in a microwave-assisted hydrothermal synthesis, then heated under N₂, the cellulose was the reducing agent and a stabiliser; 12.6% carbon from cellulose nanofibres gave the most homogeneous coating (Kroff 2023). Prussian blue as both the iron and the carbon source, sintered in one step, formed a carbon layer in situ that conducts electrons and suppresses particle growth (Su 2026)
6. **Atomic layer deposition**: Sequential, self-limiting surface reactions: NCM811 powder in a rotary reactor at 120 °C, trimethylaluminium and water at 90 °C with N₂ purges; three cycles gave a 2 nm film, 6–7 times thicker than ALD alone would give, suggesting a CVD contribution (Ahangari 2024). Surface –OH groups react with trimethylaluminium (Negi 2020), and an optimised layer is thin enough to keep the surface conductive (Negi 2021). Ultrathin (< 5 nm) Al₂O₃ on NMC622 electrodes mitigated interfacial reactions and metal dissolution (Wang 2021), but on commercial-grade NMC811 electrodes it made no significant difference (Huang 2024)

## Strengths

- Co-precipitation mixes the metals much more uniformly than solid-state routes, with simpler equipment (Mou 2022)
- Hydrothermal synthesis gives very pure, crystalline LiFePO₄ at relatively low temperatures, 115–400 °C (Ruiz-Jorge 2021)
- Single crystals eliminate intergranular cracking (Lu 2022)

## Limitations

- Mn deficiency is common, as Mn is more soluble than Ni and Co (Mou 2022)
- Residual lithium on Ni-rich cathodes reacts with moisture in air to Li₂CO₃ and LiOH (Ahangari 2024)
- Too thick a coating hinders Li⁺ insertion and extraction, too thin a one fails to protect against the electrolyte (Ahangari 2024)

## References

1. Tsuchioka et al., “Method for predicting the size of Ni₁/₃Mn₁/₃Co₁/₃(OH)₂ particles precipitated in a stirred-tank semi-batch crystallizer using CFD and particle agglomeration models”, Heliyon 2024. https://doi.org/10.1016/j.heliyon.2024.e28710 (primary)
2. Mou et al., “Scalable Advanced Li(Ni₀.₈Co₀.₁Mn₀.₁)O₂ Cathode Materials from a Slug Flow Continuous Process”, ACS Omega 2022. https://doi.org/10.1021/acsomega.2c05521 (primary)
3. Ahangari et al., “Advancing Lithium-Ion Batteries’ Electrochemical Performance: Ultrathin Alumina Coating on Li(Ni₀.₈Co₀.₁Mn₀.₁)O₂ Cathode Materials”, Micromachines 2024. https://doi.org/10.3390/mi15070894 (primary)
4. Lu et al., “Single-Crystal LiNiₓMnᵧCo₁₋ₓ₋ᵧO₂ Cathodes for Extreme Fast Charging”, Small 2022. https://doi.org/10.1002/smll.202105833 (primary)
5. Cao et al., “Controlled Synthesis of Single-Crystalline Ni-Rich Cathodes for High-Performance Lithium-Ion Batteries”, ACS Appl. Mater. Interfaces 2022. https://doi.org/10.1021/acsami.2c13832 (primary)
6. Ruiz-Jorge et al., “Effect of the Heating Rate to Prevent the Generation of Iron Oxides during the Hydrothermal Synthesis of LiFePO₄”, Nanomaterials 2021. https://doi.org/10.3390/nano11092412 (primary)
7. Kroff et al., “Lithium Iron Phosphate/Carbon (LFP/C) Composite Using Nanocellulose as a Reducing Agent and Carbon Source”, Polymers 2023. https://doi.org/10.3390/polym15122628 (primary)
8. Su et al., “A Prussian Blue-Derived Dual-Functional Precursor for High-Performance LFP/C Cathodes”, Langmuir 2026. https://doi.org/10.1021/acs.langmuir.5c06492 (primary)
9. Negi et al., “Enhancing the Electrochemical Performance of LiNi₀.₇₀Co₀.₁₅Mn₀.₁₅O₂ Cathodes Using a Practical Solution-Based Al₂O₃ Coating”, ACS Appl. Mater. Interfaces 2020. https://doi.org/10.1021/acsami.0c06484 (primary)
10. Negi et al., “Optimized atomic layer deposition of homogeneous, conductive Al₂O₃ coatings for high-nickel NCM containing ready-to-use electrodes”, Phys. Chem. Chem. Phys. 2021. https://doi.org/10.1039/d0cp06422j (primary)
11. Wang et al., “Atomic-scale constituting stable interface for improved LiNi₀.₆Mn₀.₂Co₀.₂O₂ cathodes of lithium-ion batteries”, Nanotechnology 2021. https://doi.org/10.1088/1361-6528/abd127 (primary)
12. Huang et al., “Efficacy of atomic layer deposition of Al₂O₃ on composite LiNi₀.₈Mn₀.₁Co₀.₁O₂ electrode for Li-ion batteries”, Sci. Rep. 2024. https://doi.org/10.1038/s41598-024-69330-6 (primary)
13. Laine et al., “Co-precipitation of Mg-doped Ni₀.₈Co₀.₁Mn₀.₁(OH)₂: effect of magnesium doping and washing on the battery cell performance”, Dalton Trans. 2023. https://doi.org/10.1039/d2dt02246j (further reading)
14. Ahmed et al., “Dual-Functional Surface Engineering of Single-Crystal NMC Cathodes via Residue-to-Coating Conversion for Enhanced Interface Stability”, Small 2025. https://doi.org/10.1002/smll.202506613 (further reading)
15. Wang et al., “Enhanced electrochemical properties of Ni-rich layered cathode materials via Mg²⁺ and Ti⁴⁺ co-doping for lithium-ion batteries”, J. Colloid Interface Sci. 2021. https://doi.org/10.1016/j.jcis.2021.05.167 (further reading)

Credit: Drawn by LabCanvas after Tsuchioka et al., Heliyon 2024 (doi:10.1016/j.heliyon.2024.e28710), Mou et al., ACS Omega 2022, Ahangari et al., Micromachines 2024, Lu et al., Small 2022 and Ruiz-Jorge et al., Nanomaterials 2021, and the papers in the details.

## Questions

**What does the “Making cathode materials: NMC and LiFePO₄” template show?** Cathode synthesis on one page: the Ni–Mn–Co hydroxide precursor co-precipitated in a stirred tank, lithiated and calcined in oxygen into layered NMC, polycrystalline against single-crystal particles, LiFePO₄ made hydrothermally and coated with carbon, and an Al₂O₃ coating grown by atomic layer deposition. Every step and number is quoted from the cited papers.

**What are the steps shown in “Making cathode materials: NMC and LiFePO₄”?** 1. Co-precipitation: Ni₁/₃Mn₁/₃Co₁/₃(OH)₂, the precursor of NMC111, by semi-batch reaction crystallization in a stirred tank with four baffles and a Rushton turbine (60 L in the lab, 600 L for scale-up), started at pH 12.6 with 5 g/L ammonia at 45 °C; mixed sulfates (2.3 M, 1 : 1 : 1) are fed from one, four or eight nozzles above the impeller while 8.0 M NaOH holds the pH and 13.3 M ammonia holds 5 g/L. Nucleation happens only at the very beginning; plate-like crystals form grape-like agglomerates that give way to rounded particles of even size (Tsuchioka 2024). In the usual batch process the transition-metal solution reacts with ammonia and NaOH at pH 11.5 and 60 °C; for NCM811 they are mixed 8 : 1 : 1, and ripening needed an inert atmosphere to prevent oxidation (Mou 2022). 2. Lithiation and calcination: The NCM811 hydroxide ground with stoichiometric LiOH for 10 min, heated in oxygen at 3 °C/min to 770 °C, held 10 h and furnace-cooled. The precursor loses absorbed water below 100 °C and bound water up to about 340 °C, then decomposes up to about 800 °C; an I(003)/I(104) ratio of 1.7 (usually 1.4–1.6) meant less cation mixing (Mou 2022). In another route LiOH·H₂O at 1.00 : 1.05 was ball-milled with the hydroxide and calcined at 750 °C for 12 h in pure oxygen; Ni²⁺ (0.69 Å) and Li⁺ (0.76 Å) have similar radii, so Ni can migrate to Li sites (Ahangari 2024). 3. Polycrystals or single crystals: Polycrystalline NMCs crack severely along the grain boundaries of their primary particles; single crystals eliminate intergranular cracking (Lu 2022). Growing single crystals often needs calcination at 900 °C or more, where NCM811 is less stable; a microblock-like precursor lithiated at 800 °C gave single crystals that, cycled between 2.8 and 4.5 V, still showed lattice gliding and intragranular cracks (Cao 2022). 4. Hydrothermal LiFePO₄: LiOH·H₂O, FeSO₄·7H₂O and H₃PO₄ (Fe : PO₄ : Li = 0.9 : 1.2 : 2.7, pH 7) in 180 mL of water in a 0.3 L autoclave purged with N₂, heated at 4 °C/min to 300 °C (103 bar) and held 5 min: Li₃PO₄ and Fe₃(PO₄)₂·8H₂O form first, then dissolve to LiFePO₄. Fe₃(PO₄)₂·8H₂O starts to dissolve at about 130 °C; fast heating gives magnetite and poorer crystals, slow heating through 130–150 °C gives pure, (010)-faced platelets, and Li⁺ diffuses several orders of magnitude faster along [010] (Ruiz-Jorge 2021). 5. Carbon coating: Coating LiFePO₄ with carbon, or doping it, improves its low electrical conductivity (Ruiz-Jorge 2021). With nanocellulose in a microwave-assisted hydrothermal synthesis, then heated under N₂, the cellulose was the reducing agent and a stabiliser; 12.6% carbon from cellulose nanofibres gave the most homogeneous coating (Kroff 2023). Prussian blue as both the iron and the carbon source, sintered in one step, formed a carbon layer in situ that conducts electrons and suppresses particle growth (Su 2026). 6. Atomic layer deposition: Sequential, self-limiting surface reactions: NCM811 powder in a rotary reactor at 120 °C, trimethylaluminium and water at 90 °C with N₂ purges; three cycles gave a 2 nm film, 6–7 times thicker than ALD alone would give, suggesting a CVD contribution (Ahangari 2024). Surface –OH groups react with trimethylaluminium (Negi 2020), and an optimised layer is thin enough to keep the surface conductive (Negi 2021). Ultrathin (< 5 nm) Al₂O₃ on NMC622 electrodes mitigated interfacial reactions and metal dissolution (Wang 2021), but on commercial-grade NMC811 electrodes it made no significant difference (Huang 2024).

**What are the starting materials and the product?** Starting materials: NiSO₄, MnSO₄ and CoSO₄ with NaOH and ammonia; LiOH or LiOH·H₂O; LiOH·H₂O, FeSO₄·7H₂O and H₃PO₄; trimethylaluminium and water. Product: Ni–Mn–Co hydroxide precursors, layered NMC111 and NCM811 particles, LiFePO₄ platelets with a carbon coating, Al₂O₃-coated NCM811.

**Which papers is “Making cathode materials: NMC and LiFePO₄” based on?** Tsuchioka et al., “Method for predicting the size of Ni₁/₃Mn₁/₃Co₁/₃(OH)₂ particles precipitated in a stirred-tank semi-batch crystallizer using CFD and particle agglomeration models”, Heliyon 2024 (doi:10.1016/j.heliyon.2024.e28710); Mou et al., “Scalable Advanced Li(Ni₀.₈Co₀.₁Mn₀.₁)O₂ Cathode Materials from a Slug Flow Continuous Process”, ACS Omega 2022 (doi:10.1021/acsomega.2c05521); Ahangari et al., “Advancing Lithium-Ion Batteries’ Electrochemical Performance: Ultrathin Alumina Coating on Li(Ni₀.₈Co₀.₁Mn₀.₁)O₂ Cathode Materials”, Micromachines 2024 (doi:10.3390/mi15070894); Lu et al., “Single-Crystal LiNiₓMnᵧCo₁₋ₓ₋ᵧO₂ Cathodes for Extreme Fast Charging”, Small 2022 (doi:10.1002/smll.202105833); Cao et al., “Controlled Synthesis of Single-Crystalline Ni-Rich Cathodes for High-Performance Lithium-Ion Batteries”, ACS Appl. Mater. Interfaces 2022 (doi:10.1021/acsami.2c13832); Ruiz-Jorge et al., “Effect of the Heating Rate to Prevent the Generation of Iron Oxides during the Hydrothermal Synthesis of LiFePO₄”, Nanomaterials 2021 (doi:10.3390/nano11092412); Kroff et al., “Lithium Iron Phosphate/Carbon (LFP/C) Composite Using Nanocellulose as a Reducing Agent and Carbon Source”, Polymers 2023 (doi:10.3390/polym15122628); Su et al., “A Prussian Blue-Derived Dual-Functional Precursor for High-Performance LFP/C Cathodes”, Langmuir 2026 (doi:10.1021/acs.langmuir.5c06492); Negi et al., “Enhancing the Electrochemical Performance of LiNi₀.₇₀Co₀.₁₅Mn₀.₁₅O₂ Cathodes Using a Practical Solution-Based Al₂O₃ Coating”, ACS Appl. Mater. Interfaces 2020 (doi:10.1021/acsami.0c06484); Negi et al., “Optimized atomic layer deposition of homogeneous, conductive Al₂O₃ coatings for high-nickel NCM containing ready-to-use electrodes”, Phys. Chem. Chem. Phys. 2021 (doi:10.1039/d0cp06422j); Wang et al., “Atomic-scale constituting stable interface for improved LiNi₀.₆Mn₀.₂Co₀.₂O₂ cathodes of lithium-ion batteries”, Nanotechnology 2021 (doi:10.1088/1361-6528/abd127); Huang et al., “Efficacy of atomic layer deposition of Al₂O₃ on composite LiNi₀.₈Mn₀.₁Co₀.₁O₂ electrode for Li-ion batteries”, Sci. Rep. 2024 (doi:10.1038/s41598-024-69330-6); Laine et al., “Co-precipitation of Mg-doped Ni₀.₈Co₀.₁Mn₀.₁(OH)₂: effect of magnesium doping and washing on the battery cell performance”, Dalton Trans. 2023 (doi:10.1039/d2dt02246j); Ahmed et al., “Dual-Functional Surface Engineering of Single-Crystal NMC Cathodes via Residue-to-Coating Conversion for Enhanced Interface Stability”, Small 2025 (doi:10.1002/smll.202506613); Wang et al., “Enhanced electrochemical properties of Ni-rich layered cathode materials via Mg²⁺ and Ti⁴⁺ co-doping for lithium-ion batteries”, J. Colloid Interface Sci. 2021 (doi:10.1016/j.jcis.2021.05.167).

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