Abstract
Lithium iron phosphate (LiFePO4) is recognized as being less stable and easily dissolvable in aqueous suspensions, particularly when the suspension pH is adjusted to be more alkaline or acidic. In this investigation, an unexpected and interesting finding is revealed, which contradicts the conventional understanding of the dissolution of LiFePO4. As most of the surface of commercial LiFePO4 is coated with carbon, the key factor determining its dissolution behavior is the chemical quality of the surface carbon. With more sp2-bonded carbon on the surface, both the dissolution and electrochemistry of LiFePO4 are independent of pH variations in aqueous suspensions. When the surface carbon is mainly sp3-bonded, LiFePO4 exhibits distinct dissolution and electrochemical properties at different pH levels and, under alkaline conditions, shows greater dissolution and poorer cell performance than that characterized mainly by sp2-bonded carbon.
Graphical Abstract
Similar content being viewed by others
References
Padhi AK, Nanjundaswamy KS, Goodenough JB (1997) Phospho-olivines as positive-electrode materials for rechargeable lithium batteries. J Electrochem Soc 144:1188–1194
Yamada A, Chung SC, Hinokuma K (2001) Optimized LiFePO4 for lithium battery cathodes. J Electrochem Soc 148:A224–A229
Iltchev N, Chen Y, Okada S, Yamaki JI (2003) LiFePO4 storage at room and elevated temperatures. J Power Sources 119–121:749–754
Arnold G, Garche J, Hemmer R, Ströbele S, Vogler C, Wohlfahrt-Mehrens M (2003) Fine-particle lithium iron phosphate LiFePO4 synthesized by a new low-cost aqueous precipitation technique. J Power Sources 119–121:247–251
MacNeil DD, Lu Z, Chen Z, Dahn JR (2002) A comparison of the electrode/electrolyte reaction at elevated temperatures for various Li-ion battery cathodes. J Power Sources 108:8–14
Patoux S, Rousse G, Leriche JB, Masquelier C (2003) Structural and electrochemical studies of rhombohedral Na2TiM(PO4)3 and Li1.6Na0.4TiM(PO4)3 (M = Fe, Cr) phosphates. Chem Mater 15:2084–2093
Yin SC, Strobel PS, Grondey H, Nazar LF (2004) Li2.5V2(PO4)3: a room-temperature analogue to the fast-ion conducting high-temperature gamma-phase of Li3V2(PO4)3. Chem Mater 16:1456–1465
Yang HQ, Li DP, Han S, Li N, Lin BX (1995) Vanadium-manganese complex oxides as cathode materials for aqueous solution secondary batteries. J Power Sources 58:221–224
Lux SF, Schappacher F, Balducci A, Passerini S, Winter M (2010) Low cost, environmentally benign binders for lithium-ion batteries. J Electrochem Soc 157:A320–A325
Lee JH, Kim HH, Zang DS, Choi YM, Kim H, Yi DK, Sigmund WM, Paik U (2010) Evaluation of surface acid and base properties of LiFePO4 in aqueous medium with pH and its electrochemical properties. J Phys Chem C 114:4466–4472
Porcher W, Lestriez B, Jouanneau S, Guyomard D (2010) Optimizing the surfactant for the aqueous processing of LiFePO4 composite electrodes. J Power Sources 195:2835–2843
Li J, Armstrong BL, Daniel C, Kiggans J, Wood DL (2013) Optimization of multicomponent aqueous suspensions of lithium iron phosphate (LiFePO4) nanoparticles and carbon black for lithium-ion battery cathodes. J Colloid Interf Sci 405:118–124
Li CC, Wang YH, Yang TY (2011) Effects of surface-coated carbon on the chemical selectivity for water-soluble dispersants of LiFePO4. J Electrochem Soc 158:A828–A834
Li CC, Peng XW, Lee JT, Wang FM (2010) Using poly (4-styrene sulfonic acid) to improve the dispersion homogeneity of aqueous-processed LiFePO4 cathodes. J Electrochem Soc 157:A517–A520
Alias N, Mohamad AA (2015) Advances of aqueous rechargeable lithium-ion battery: a review. J Power Sources 274:237–251
Delacourt C, Poizot P, Levasseur S, Masquelier C (2006) Size effects on carbon-free LiFePO4 powders the key to superior energy density. Electrochem Solid-State Lett 9:A352–A355
Zaghib K, Dontigny M, Charest P, Labrecque JF, Guerfi A, Kopec M, Mauger A, Gendron F, Julien CM (2008) Aging of LiFePO4 upon exposure to H2O. J Power Sources 185:698–710
Denis YW, Donoue K, Kadohata T, Murata T, Matsuta S, Fujitani S (2008) Impurities in LiFePO4 and their influence on material characteristics impurities in LiFePO4 and their influence on material characteristics. J Electrochem Soc 155:A526–A530
Porcher W, Moreau P, Lestriez B, Jouanneau S, Le Cras F, Guyomard D (2008) Stability of LiFePO4 in water and consequence on the Li battery behavior. Ionics 14:583–587
Tsai JC, Tsai FY, Tung CA, Hsieh HW, Li CC (2013) Gelation or dispersion of LiFePO4 in water-based slurry? J Power Sources 241:400–403
Tsai FY, Jhang JH, Hsieh HW, Li CC (2016) Dispersion, agglomeration, and gelation of LiFePO4 in water-based slurry. J Power Sources 310:47–53
Prosini PP, Lisi M, Scaccia S, Carewska M, Cardellini F, Pasquali M (2002) Synthesis and characterization of amorphous hydrated FePO4 and its electrode performance in lithium batteries. J Electrochem Soc 149:A297–A301
Andersson AS, Thomas JO (2001) The source of first-cycle capacity loss in LiFePO4. J Power Sources 97:498–502
Casey WH, Ludwig C (1996) The mechanism of dissolution of oxide minerals. Nature 381:506
Odzak N, Kistler D, Behra R, Sigg L (2014) Dissolution of metal and metal oxide nanoparticles in aqueous media. Environ Pollut 191:132–138
Neubrand A, Lindner R, Hoffmann P (2000) Room-temperature solubility behavior of barium titanate in aqueous media. J Am Ceram Soc 83:860–864
Robert CW, Melvin JA (2003) CRC handbook of chemistry and physics. CRC Press, Florida
Li CC, Jean JH (2002) Interaction between dissolved Ba2+ and PAA-NH4 dispersant in aqueous barium titanate suspensions. J Am Ceram Soc 85:1449–1455
Jean JH, Wang HR (2000) Effects of solids loading, pH, and polyelectrolyte addition on the stabilization of concentrated aqueous BaTiO3 suspensions. J Am Ceram Soc 83:277–280
Acknowledgements
The authors appreciate material supports from the Advanced Lithium Electrochemistry Co.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare no conflict of interest or competing financial interest.
Rights and permissions
About this article
Cite this article
Li, CC., Chang, SJ. & Chen, CA. Effects of sp2- and sp3-carbon coatings on dissolution and electrochemistry of water-based LiFePO4 cathodes. J Appl Electrochem 47, 1065–1072 (2017). https://doi.org/10.1007/s10800-017-1105-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10800-017-1105-y