Abstract
Owing to the progress in the field energy storage, new lithium insertion compounds are currently investigated as active cathode elements for high-voltage lithium-ion batteries to improve the technology of the electric transportation. After preliminary considerations dedicated to the principles governing LiBs and electron energies in the positive electrodes, this chapter addresses physico-chemical and electrochemical properties of the 5-V cathodes materials with various strutural frameworks. They are LiNi0.5Mn1.5O4 spinel oxides and their related doped parents and olivine, inverse spinel, fluorovanadate and fluorophosphate structures.
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References
Goodenough JB (2002) Oxides cathodes. In: Advances in lithium-ion batteries. Kluwer Academic/Plenum, New York pp 135–154
Goodenough JB, Kim Y (2010) Challenges for rechargeable Li batteries. Chem Mater 22:587–603
Zaghib K, Dubé J, Dallaire A, Galoustov K, Guerfi A, Ramanathan M, Benmayza A, Prakash J, Mauger A, Julien CM (2012) Enhanced thermal safety and high power performance of carbon-coated LiFePO4 olivine cathode for Li-ion batteries. J Power Sour 219:36–44
Mizushima K, Jones PC, Wiseman PJ, Goodenough JB (1980) LixCoO2 (0 < x<1): a new cathode material for batteries of high energy density. Mater Res Bull 15:783–789
Ohzuku T, Makimura Y (2001) Layered lithium insertion material of LiCo1/3Ni1/3Mn1/3O2 for lithium-ion batteries Chem Lett 30:642–643
Thackeray MM, David WIF, Bruce PG, Goodenough JB (1982) Lithium insertion into manganese spinels. Mater Res Bull 18:461–472
Padhi AK, Nanjundaswamy KS, Goodenough JB (1997) Phospho-olivines as positive-electrode materials for rechargeable lithium batteries. J Electrochem Soc 144:1188–1194
Whittingham MS (2004) Lithium batteries and cathode materials. Chem Rev 104:4271–4301
Ellis BL, Lee KT, Nazar LF (2010) Positive electrode materials for Li-ion and Li-batteries. Chem Mater 22:691–714
Fergus JW (2010) Recent developments in cathode materials for lithium ion batteries. J Power Sour 195:939–954
Zaghib K, Mauger A, Julien CM (2012) Overview of olivines in lithium batteries for green transportation and energy storage. J Solid State Electrochem 16:835–845
Santhanam R, Rambabu B (2010) Research progress in high voltage spinel LiNi0.5Mn1.5O4 material. J Power Sour 195:5442–5451
Liu GQ, Wen L, Liu YM (2010) Spinel LiNi0.5Mn1.5O4 and its derivatives as cathodes for high-voltage Li-ion batteries. J Solid State Electrochem 14:2191–2202
Kraytsberg A, Ein-Eli Y (2012) Higher, stronger, better. A review of 5 volt cathode materials for advanced lithium-ion batteries. Adv Energy Mater 2:922–939
Liu D, Han J, Dontigny M, Charest P, Guerfi A, Zaghib K, Goodenough JB (2010) Redox behaviors of Ni and Cr with different counter cations in spinel cathodes for Li-ion batteries. J Electrochem Soc 157:A770–A775
Shin Y, Manthiram A (2003) Origin of the high voltage (>4.5 V) capacity of spinel lithium manganese oxides. Electrochim Acta 48:3583–3592
Obrovac MN, Gao Y, Dahn JR (1998) Explanation for the 4.8-V plateau in LiCr x Mn2−x O4. Phys Rev B: Condens Matter 57:5728–5733
Gryffroy D, Vaudenberghe RE (1992) Cation distribution, cluster structure and ionic ordering of the spinel series LiNi0.5Mn1.5−xTixO4 and LiNi0.5−yMgyMn1.5O4. J Phys Chem Solids 53:777–784
Amdouni N, Zaghib K, Gendron F, Mauger A, Julien CM (2006) Structure and insertion properties of disordered and ordered LiNi0.5Mn1.5O4 spinels prepared by wet chemistry. Ionics 12:117–126
Strobel P, Ibarra-Palos A, Anne M, Poinsignon C, Crisci A (2003) Cation ordering in Li2Mn3MO8 spinels: structural and vibration spectroscopy studies. Solid State Sci 5:1009–1018
Ariyoshi K, Iwakoshi Y, Nakayama N, Ohzuku T (2004) Topotactic two-phase reactions of Li[Ni1/2Mn3/2]O4 (P4332) in nonaqueous lithium cells. J Electrochem Soc 151:A296–A303
Kanamura K, Hoshikawa W, Umegaki T (2002) Electrochemical characteristics of LiNi0.5Mn1.5O4 cathodes with Ti or Al current collectors. J Electrochem Soc 149:A339–A345
Ohzuku T, Takeda S, Iwanaga M (1999) Solid-state redox potentials for Li[Me1/2Mn3/2]O4 (Me: 3d-transition metal) having spinel-framework structures: a series of 5 volt materials for advanced lithium-ion batteries. J Power Sour 81–82:90–94
Okada M, Lee YS, Yoshio M (2000) Cycle characterizations of LiMxMn2-xO4 (M = Co, Ni) materials for lithium secondary battery at wide voltage region. J Power Sour 90:196–200
Dokko K, Mohamedi M, Anzue N, Itoh T, Uchida I (2002) In situ Raman spectroscopic studies of LiNixMn2−xO4 thin film cathode materials for lithium ion secondary batteries. J Mater Chem 12:3688–3693
Takahashi K, Saitoh M, Sano M, Fujita M, Kifune K (2004) Electrochemical and structural properties of a 4.7 V-class LiNi0.5Mn1.5O4 positive electrode material prepared with a self-reaction method. J Electrochem Soc 151:A173–A177
Ooms FGB, Kelder EM, Schoonman J, Wagemaker M, Mulder FM (2002) High-voltage LiMgδNi0.5−δMn1.5O4 spinels for Li-ion batteries. Solid State Ionics 152–153:143–153
Blasse G (1966) Ferromagnetism and ferrimagnetism of oxygen spinels containing tetravalent manganese. J Phys Chem Solids 27:383–389
Amdouni N, Zaghib K, Gendron F, Mauger A, Julien CM (2007) Magnetic properties of LiNi0.5Mn1.5O4 spinels prepared by wet chemical methods. J Magn Magn Mater 309:100–105
Mukai K, Sugiyama J (2010) An indicator to identify the Li[Ni1/2Mn3/2]O4 (P4332): dc-susceptibility measurements. J Electrochem Soc 157:A672–A676
Idemoto Y, Narai H, Koura N (2003) Crystal structure and cathode performance dependence on oxygen content of LiMn1.5Ni0.5O4 as a cathode material for secondary lithium batteries. J Power Sour 119–121:125–129
Park SH, Oh SW, Myung ST, Sun YK (2004) Mo6+-doped Li[Ni(0.5+x)Mn(1.5−2x)Mo x ]O4 spinel materials for 5 V lithium secondary batteries prepared by ultrasonic spray pyrolysis. Electrochem Solid-State Lett 7:A451–A454
Moorhead-Rosenberg Z, Shin DW, Chemelewski KR, Goodenough JB, Manthiram A (2012) Quantitative determination of Mn3+ content in LiMn1.5Ni0.5O4 spinel cathodes by magnetic measurements. Appl Phys Lett 100:213909-1–213909-5
Idemoto Y, Narai H, Koura N (2002) Oxygen content and electrode characteristics of LiMn1.5Ni0.5O4 as a 5 V class cathode material for lithium secondary battery. Electrochemistry 70:587–589
Rhodes K, Meisner R, Kim Y, Dudney N, Daniel C (2011) Evolution of phase transformation behavior in Li(Mn1.5Ni0.5)O4 cathodes studied by in situ XRD. J Electrochem Soc 158:A890–A897
Kim JH, Myung ST, Yoon CS, Kang SG, Sun YK (2004) Comparative study of LiNi0.5Mn1.5O4−δ and LiNi0.5Mn1.5O4 cathodes having two crystallographic structures: Fd-3 m and P4332. Chem Mater 16:906–914
Bhaskar A, Bramnik NN, Senyshyn A, Fuess H, Ehrenberg H (2010) Synthesis, characterization, and comparison of electrochemical properties of LiM0.5Mn1.5O4 (M = Fe Co, Ni) at different temperatures. J Electrochem Soc 157:A689–A695
Terada Y, Yasaka K, Nishikawa F, Konishi T, Yoshio M, Nakai I (2001) In situ XAFS analysis of Li(Mn, M)2O4 (M = Cr Co, Ni) 5 V cathode materials for lithium-ion secondary batteries. J Solid State Chem 156:286–291
Wen W, Kumarasamy B, Mukerjee S, Auinat M, Ein-Eli Y (2005) Origin of 5 V electrochemical activity observed in non-redox reactive divalent cation doped LiM0.5−xMn1.5+xO4 (0 ≤ x≤0.5) cathode materials in situ XRD and XANES spectroscopy studies. J Electrochem Soc 152:A1902–A1911
Mukerjee S, Yang XQ, Sunb X, Lee SJ, McBreen J, Ein-Eli Y (2004) In situ synchrotron X-ray studies on copper–nickel 5 V Mn oxide spinel cathodes for Li-ion batteries. Electrochim Acta 49:3373–3382
Liu D, Lu Y, Goodenough JB (2010) Rate properties and elevated-temperature performances of LiNi0.5−x Cr2x Mn1.5−x O4 (0 ≤ 2x ≤ 0.8) as 5 V cathode materials for lithium-ion batteries. J Electrochem Soc 157:A1269–A1273
Wang L, Li H, Huang X, Baudrin E (2011) A comparative study of Fd-3 m and P4332 LiNi0.5Mn1.5O4. Solid State Ionics 193:32–38
Julien CM, Gendron F, Amdouni N, Massot M (2006) Lattice vibrations of materials for lithium rechargeable batteries. VI: Ordered spinels. Mater Sci Eng B 130:41–48
Matsui M, Dokko K, Kanamura K (2010) Surface layer formation and stripping process on LiMn2O4 and LiNi1/2Mn3/2O4 thin film electrodes. J Electrochem Soc 157:A121–A129
Gao Y, Myrtle K, Zhang MJ, Reimers JN, Dahn JR (1996) Valence band of LiNi x Mn2-x O4 and its effects on the voltage profiles of LiNi x Mn2−x O4/Li electrochemical cells. Phys Rev B: Condens Matter 54:16670–16675
Shin Y, Manthiram A (2004) Factors influencing the capacity fade of spinel lithium manganese oxides. J Electrochem Soc 151:A204–A208
Patoux Q, Daniel L, Bourbon C, Lignier H, Pagano C, Le Cras F, Jouanneau S, Martinet S (2009) High voltage spinel oxides for Li-ion batteries: From the material research to the application. J Power Sour 189:344–352
Fang HS, Wang ZX, Li XH, Guo HJ, Peng WJ (2006) Exploration of high capacity LiNi0.5Mn1.5O4 synthesized by solid-state reaction. J Power Sources 153:174–176
Chen ZY, Ji S, Linkov V, Zhang JL, Zhu W (2009) Performance of LiNi0.5Mn1.5O4 prepared by solid-state reaction. J Power Sour 189:507–510
Miao C, Shi L, Chen G, Dai D (2012) Preparation of precursor of LiNi0.5Mn1.5O4 with high density. Adv Mater Res 463–464:881–884
Liu G, Qi L, Wen L (2006) Synthesis and electrochemical performance of LiNixMn2−xO4 spinel as cathode material for lithium ion batteries. Rare Met Mater Eng 35:299–302
Fang HS, Wang ZX, Yin ZL, Li XH, Guo HJ, Peng WJ (2005) Effect of ball milling and electrolyte on properties of high-voltage LiNi0.5Mn1.5O4 spinel. Trans Nonferrous Met Soc Chin (English) 15:1429–1432
Fang HS, Li LP, Li GS (2007) A low-temperature reaction route to high rate and high capacity LiNi0.5Mn1.5O4. J Power Sour 167:223–227
Xu HY, Xie S, Ding N, Liu BL, Shang Y, Chen CH (2006) Improvement of electrochemical properties of LiNi0.5Mn1.5O4 spinel prepared by radiated polymer gel method. Electrochem Acta 51:4352–4357
Arunkumar TA, Manthiram A (2005) Influence of lattice parameter differences on the electrochemical performance of the 5 V spinel LiMn1.5 − yNi0.5 − zMy + zO4 (M = Li, Mg, Fe Co, and Zn). Electrochem Solid-State Lett 8:A403–A405
Aklalouch M, Amarilla JM, Saadoune I, Rojo JM (2011) LiCr0.2Ni0.4Mn1.4O4 spinels exhibiting huge rate capability at 25 and 55 C: analysis of the effect of the particle size. J Power Sour 196:10222–10227
Kim JH, Myung ST, Sun YK (2004) Molten salt synthesis of LiNi0(5Mn1(5O4 spinel for 5 V class cathode material of Li-ion secondary battery. Electrochim Acta 49:219–227
Chen G, Hai B, Shukla AK, Duncan H (2012) Impact of LiMn1.5Ni0.5O4 crystal surface facets. ECS Symp Abstr700
Lim SJ, Ryu WH, Kim WK, Kwon HS (2012) Electrochemical performance of LiNi0.5Mn1.5O4 cathode material fabricated from nanothorn sphere structured MnO2. ECS Symp Abstr953
Zhao ZQ, Ma JF, Tian H, Xie LJ, Zhou J, Wu PW, Wang YG, Tao JT, Zhu XY (2005) Preparation and characterization of nano-crystalline LiNi0.5Mn1.5O4 cathode material by the soft combustion reaction method. J Am Ceram Soc 88:3549–3552
Chen J, Cheng F (2009) Combination of lightweight elements and nanostructured materials for batteries. Acc Chem Res 42:713–723
Fan YK, Wang JM, Ye XB, Zhang JQ (2007) Physical properties and electrochemical performance of LiNi0.5Mn1.5O4 cathode material prepared by a co-precipitation method. Mater Chem Phys 103:19–23
Yi TF, Hu XG (2007) Preparation and characterization of sub-micro LiNi0.5−x Mn1.5+x O4 for 5 V cathode materials synthesized by an ultrasonic-assisted co-precipitation method. J Power Sour 167:185–191
Ohzuku T, Ariyoshi K, Yamamoto S (2002) Synthesis and characterization of Li[Ni1/2Mn3/2]O4 by two-step solid state reaction. J Ceram Soc Jpn 110:501–505
Myung ST, Komaba S, Kumagai N, Yashiro H, Chung HT, Cho TH (2002) Nano-crystalline LiNi0.5Mn1.5O4 synthesized by emulsion drying method. Electrochim Acta 47:2543–2549
Zhao Q, Ye N, Li L, Yan F (2010) Oxalate coprecipitation process synthesis of 5 V cathode material LiNi0.5Mn1.5O4 and its performance. Rare Met Mater Eng 39:1715–1718
Liu D, Han J, Goodenough JB (2010) Structure, morphology, and cathode performance of Li1−x[Ni0.5Mn1.5]O4 prepared by coprecipitation with oxalic acid. J Power Sour 195:2918–2923
Yang K, Su J, Zhang L, Long Y, Lv X, Wen Y (2012) Urea combustion synthesis of LiNi0.5Mn1.5O4 as a cathode material for lithium ion batteries. Particuology 10:765–770
Cao A, Manthiram A (2012) Controlled synthesis of high tap density LiMn1.5Ni0.5O4 with tunable shapes. ECS Symp Abstr699
Kunduraci M, Amatucci GG (2006) Synthesis and characterization of nanostructured 4.7 V Li x Mn1.5Ni0.5O4 spinels for high-power lithium-ion batteries. J Electrochem Soc 153:A1345–A1352
Yamada M, Dongying B, Kodera T, Myoujin K, Ogihara T (2009) Mass production of cathode materials for lithium ion battery by flame type spray pyrolysis. J Ceram Soc Jpn 117:1017–1020
Wu HM, Tu JP, Chen XT, Shi DQ, Zhao XB, Cao GS (2006) Synthesis and characterization of abundant Ni-doped LiNi x Mn2−x O4 (x = 0.1–0.5) powders by spray-drying method. Electrochim Acta 51:4148–4152
Park SH, Oh SW, Yoon CS, Myung ST, Sun YK (2005) LiNi0.5Mn1.5O4 showing reversible phase transition on 3 V region. Electrochem Solid-State Lett 8:A163–A167
Ogihara T, Kodera T, Myoujin K, Motohira S (2009) Preparation and electrochemical properties of cathode materials for lithium ion battery by aerosol process. Mater Sci Eng, B 161:109–114
Kojima M, Mukoyama I, Myoujin K, Kodera T, Ogihara T (2009) Mass production and battery properties of LiNi0.5Mn 1.5O4 powders prepared by internal combustion type spray pyrolysis. Key Eng Mater 388:85–88
Sigala C, Guyomard D, Verbaere A, Piffard Y, Tournoux M (1995) Positive electrode materials with high operating voltage for lithium batteries: LiCryMn2-yO4 (0 < y<1). Solid State Ionics 81:167–170
Arrebola JC, Caballero A, Hernan L, Morales J (2008) PMMA-assisted synthesis of Li1−x Ni0.5Mn1.5O4−δ for high-voltage lithium batteries with expanded rate capability at high cycling temperatures. J Power Sources 180:852–858
Kalyani P, Kalaiselvi N, Muniyandi N (2003) An innovative soft-chemistry approach to synthesize LiNiVO4. Mater Chem Phys 77:662–668
Liu J, Manthiram A (2009) Understanding the improved electrochemical performances of Fe-substituted 5 V spinel cathode LiMn1.5Ni0.5O4. J Phys Chem C 113:15073–15079
Zhong GB, Wang YY, Yu YQ, Chen CH (2012) Electrochemical investigations of the LiNi0.45M0.10Mn1.45O4 (M = Fe Co, Cr) 5 V cathode materials for lithium ion batteries. J Power Sour 205:385–393
Park SB, Eom WS, Cho WI, Jang H (2006) Electrochemical properties of LiNi0.5Mn1.5O4 cathode after Cr doping. J Power Sour 159:679–684
Amatucci GG, Pereira N, Zheng T, Tarascon JM (2001) Failure mechanism and improvement of the elevated temperature cycling of LiMn2O4 compounds through the use of the LiAl x Mn2−x O4−z F z solid solution. J Electrochem Soc 148:A171–A182
Oh SW, Park SH, Kim JH, Bae YC, Sun YK (2006) Improvement of electrochemical properties of LiNi0.5Mn1.5O4 spinel material by fluorine substitution. J Power Sour 157:464–470
Xu XX, Yang J, Wang YQ, Wang JL (2007) LiNi0.5Mn1.5O3.975F0.05 as novel 5-V cathode material. J Power Sour 174:1113–1116
Du GD, NuLi Y, Yang J, Wang J (2008) Fluorine-doped LiNi0.5Mn1.5O4 for 5 V cathode materials of lithium-ion battery. Mater Res Bull 43:3607–3613
Wu X, Zong X, Yang Q, Jin Z, Wu H (2001) Electrochemical studies of substituted spinel LiAlyMn2−yO4−zFz for lithium secondary batteries. J Fluorine Chem 107:39–44
Sun YK, Park GS, Lee YS, Yoshio M, Nahm KS (2001) Structural changes (degradation) of oxysulfide LiAl0.24Mn1.76O3.98S0.02 spinel on high-temperature cycling. J Electrochem Soc 148:A994–A998
Sun YK, Oh SW, Yoon CS, Bang HJ, Prakash J (2006) Effect of sulfur and nickel doping on morphology and electrochemical performance of LiNi0.5Mn1.5O4−x S x spinel material in 3-V region. J Power Sour 161:19–26
Xi N, Zhong B, Chen M, Yin K, Li L, Liu H, Guo X (2013) Synthesis of LiCr0.2Ni0.4Mn1.4O4 with superior electrochemical performance via a two-step thermo polymerization technique. Electrochim Acta 97:184–191
Zheng J, Xiao J, Yu X, Kovarik L, Gu M, Omenya F, Chen X, Zhang JG (2012) Enhanced Li+ ion transport in LiNi0.5Mn1.5O4 through control of site disorder. Phys Chem Chem Phys 14:13515–13521
Amine K, Tukamoto H, Yasuda H, Fujita Y (1996) A New three-volt spinel Li1+x Mn1.5Ni0.5O4 for secondary lithium batteries. J Electrochem Soc 143:1607–1613
Liu D, Hamel-Paquet J, Trottier J, Barray F, Gariépy V, Hovington P, Guerfi A, Mauger A, Julien CM, Goodenough JB, Zaghib K (2012) Synthesis of pure phase disordered LiMn1.45Cr0.1Ni0.45O4 by a post-annealing method. J Power Sour 217:400–406
Shin DW, Bridges CA, Huq A, M. Paranthaman MP, Manthiram A (2012) Role of cation ordering and surface segregation in high-voltage spinel LiMn1.5Ni0.5−xMxO4 (M = Cr, Fe, and Ga) cathodes for lithium-ion batteries. Chem Mater 24:3720–3731
Takahashi Y, Sasaoka H, Kuzuo R, Kijima N, Akimoto J (2006) A low-temperature synthetic route and electrochemical properties of micrometer-sized LiNi0.5Mn1.5O4 single crystals. Electrochem Solid-State Lett 9:A203–A206
Kanamura K, Hoshikawa W, Umegaki T (2001) Preparation and evaluation of new cathode materials for rechargeable lithium battery with 5 V. J Japn Soc Powder Met 48:283–287
Maeda Y, Ariyoshi K, Kawai T, Sekiya T, Ohzuku T (2009) Effect of deviation from Ni/Mn stoichiometry in Li[Ni1/2Mn3/2]O4 upon rechargeable capacity at 4.7 V in nonaqueous lithium cells. J Ceram Soc Jpn 117:1216–1220
Yoshio M, Konishi T, Todorov YM, Noguchi H (2000) Electrochemical behavior of nonstoichiometric LiMn2−xNixO4 as a 5-V cathode material. Electrochemistry 68:412–414
Xia H, Meng YS, Lu L, Ceder G (2007) Electrochemical properties of nonstoichiometric LiNi0.5Mn1.5O4−δ thin-film electrodes prepared by pulsed laser deposition. J Electrochem Soc 154:A737–A743
Pasero D, Reeves N, Pralong V, West AR (2008) Oxygen nonstoichiometry and phase transitions in LiMn1.5Ni0.5O4−δ . J Electrochem Soc 155:A282–A291
Jin YC, Lin CY, Duh JG (2012) Improving rate capability of high potential LiNi0.5Mn1.5O4−x cathode materials via increasing oxygen non-stoichiometries. Electrochim Acta 69:45–50
Wu X, Kim SB (2002) Improvement of electrochemical properties of LiNi0.5Mn1.5O4 spinel. J Power Sour 109:53–57
Wu HM, Tu JP, Yuan YF, Li Y, Zhao XB, Cao GS (2005) Electrochemical and ex situ XRD studies of a LiMn1.5Ni0.5O4 high-voltage cathode material. Electrochim Acta 50:4104–4108
Kim JH, Yoon CS, Myung ST, Prakash J, Sun YK (2004) Phase transitions in Li1−δ Ni0.5Mn1.5O4 during cycling at 5 V. Electrochem Solid-State Lett 7:A216–A220
Alcántara R, Jaraba M, Lavela P, Tirado JL (2002) Optimizing preparation conditions for 5 V electrode performance, and structural changes in Li1−x Ni0.5Mn1.5O4 spinel. Electrochim Acta 47:1829–1835
Zhu W, Liu D, Trottier J, Gagnon C, Mauger A, Julien CM, Zaghib K (2013) In-situ XRD study of the phase evolution in un-doped and Cr-doped LixMn1.5Ni0.5O4 (0.1 ≤ x≤0.1) 5-volt cathode materials. J Power Sour 242:236–243
Kim JH, Pieczonka NPW, Li Z, Wu Y, Harris S, Powell BR (2013) Understanding the capacity fading mechanism in LiNi0.5Mn1.5O4/graphite Li-ion batteries. Electrochim Acta 90:556–562
Hai B, Shukla AK, Duncan H, Chen G (2013) The effect of particle surface facets on the kinetic properties of LiMn1.5Ni0.5O4 cathode materials. J Mater Chem A 1:759–769
Sun YK, Yoon CS, Oh IH (2003) Surface structural change of ZnO-coated LiNi0.5Mn1.5O4 spinel as 5 V cathode materials at elevated temperatures. Electrochim Acta 48:503–506
Aurbach D, Markovsky B, Talyosef Y, Salitra G, Kim HJ, Choi S (2006) Studies of cycling behavior, ageing, and interfacial reactions of LiNi0.5Mn1.5O4 and carbon electrodes for lithium-ion 5-V cells. J Power Sour 162:780–789
Mun J, Yim T, Park K, Ryu JH, Kim YG, Oh SM (2011) Surface film formation on LiNi0.5Mn1.5O4 electrode in an ionic liquid solvent at elevated temperature. J Electrochem Soc 158:A453–A457
Wu W, Li X, Wang Z, Guo H, Wang J, Xue P (2013) Comprehensive reinvestigation on the initial coulombic efficiency and capacity fading mechanism of LiNi0.5Mn1.5O4 at low rate and elevated temperature. J Solid State Electrochem. doi: 10.1007/s10008-012-1963-5
Fu LJ, Liu H, Li C, Wu YP, Rahm E, Holze R, Wu HQ (2006) Surface modifications of electrode materials for lithium ion batteries. Solid State Sci 8:113–128
Liu J, Manthiram A (2009) Understanding the improvement in the electrochemical properties of surface modified 5 V LiMn1.42Ni0.42Co0.16O4 spinel cathodes in lithium-ion cells. Chem Mater 21:1695–1707
Liu J, Manthiram A (2009) Kinetics study of the 5 V spinel cathode LiMn1.5Ni0.5O4 before and after surface modifications. J Electrochem Soc 156:A833–A838
Kobayashi Y, Miyashiro H, Takei K, Shigemura H, Tabuchi M, Kageyama H, Iwahori T (2003) 5 V class all-solid-state composite lithium battery with Li3PO4 coated LiNi0.5Mn1.5O4. J Electrochem Soc 150:A1577–A1582
Arrebola J, Caballero A, Hernan L, Morales J, Castellon ER, Ramos-Barrado JR (2007) Effects of coating with gold on the performance of nanosized LiNi0.5Mn1.5O4 for lithium batteries. J Electrochem Soc 154:A178–A184
Fan Y, Wang J, Tang Z, He W, Zhang J (2007) Effects of the nanostructured SiO2 coating on the performance of LiNi0.5Mn1.5O4 cathode materials for high-voltage Li-ion batteries. Electrochim Acta 52:3870–3875
Cho J, Kim YJ, Kim TJ, Park B (2001) Zero-strain intercalation cathode for rechargeable Li-ion cell. Ang Chem Int Ed 40:3367–3369
Chen Z, Dahn JR (2002) Effect of a ZrO2 Coating on the structure and electrochemistry of Li x CoO2 when cycled to 4.5 V. Electrochem Solid-State Lett 5:A213–A216
Appapillai AT, Mansour AN, Cho J, Shao-Horn Y (2007) Microstructure of LiCoO2 with and without “AlPO4” nanoparticle coating: combined STEM and XPS studies. Chem Mater 19:5748–5757
Fey GTK, Li W, Dahn JR (1994) LiNiVO4: A 4.8 volt electrode material for lithium cells. J Electrochem Soc 141:2279–2282
Fey GTK, Dahn JR, Zhang M, Li W (1997) The effects of the stoichiometry and synthesis temperature on the preparation of the inverse spinel LiNiVO4 and its performance as a new high voltage cathode material. J Power Sour 68:549–552
Prabaharan SRS, Michael MS, Radhakrishna S, Julien C (1997) Novel low-temperature synthesis and characterization of LiNiVO4 for high-voltage Li-ion batteries. J Mater Chem 7:1791–1796
Fey GTK, Perng WB (1997) A new preparation method for a novel high voltage cathode material: LiNiVO4. Mater Chem Phys 47(1997):279–282
Rissouli K, Benkhouja K, Touaiher M, Ait-Salah A, Jaafari K, Fahad M, Julien C (2005) Structure and conductivity of lithiated vanadates LiMVO4 (M = Mn Co, Ni). J Phys IV France 123:265–269
Lu CH, Liou SJ (1998) Preparation of submicrometer LiNiVO4 powder by solution route for lithium ion secondary batteries. J Mater Sci Lett 17:733–735
Fey GTK, Huang DL (1999) Synthesis, characterization and cell performance of inverse spinel electrode materials for lithium secondary batteries. Electrochim Acta 45:295–314
Cao X, Xie L, Zhan H, Zhou Y (2008) Rheological phase synthesis and characterization of LiNiVO4 as a high voltage cathode material for lithium ion batteries. J New Mater Electrochem Syst 11:193–198
Vivekanandhan S, Venkateswarlu M, Satyanarayana N (2004) Glycerol-assisted gel combustion synthesis of nano-crystalline LiNiVO4 powders for secondary lithium batteries. Mater Lett 58:1218–1222
Chitra S, Kalyani P, Yebka B, Mohan T, Haro-Poniatowski E, Gangadharan R, Julien C (2000) Synthesis, characterization and electrochemical studies of LiNiVO4 cathode material in rechargeable lithium batteries. Mater Chem Phys 65:32–37
Subramania A, Angayarkanni N, Karthick SN, Vasudevan T (2006) Combustion synthesis of inverse spinel LiNiVO4 nano-particles using gelatine as the new fuel. Mater Lett 60:3023–3026
Li X, Wei YJ, Ehrenberg H, Liu DL, Zhan SY, Wang CZ, Chen G (2009) X-ray diffraction and Raman scattering studies of Li+/e−-extracted inverse spinel LiNiVO4. J Alloys Compd 471:L26–L28
Lai QY, Lu JZ, Liang XL, Yan FY, Ji XY (2001) Synthesis and electrochemical characteristics of Li-Ni vanadates as positive materials. Intern J Inorg Mater 3:381–385
Palanichamy K (2011) On the modified inverse spinel-LiCo(PO4)x(VO4)1−x as cathode for rechargeable lithium batteries. Ionics 17:391–397
Fey GTK, Chen KS (1999) Synthesis, characterization, and cell performance of LiNiVO4 cathode materials prepared by a new solution precipitation method. J Power Sour 81–82:467–471
Lu CH, Liou SJ (2000) Hydrothermal preparation of nanometer lithium nickel vanadium oxide powder at low temperature. Mater Sci Eng, B 75:38–42
Phuruangrat A, Thongtem T, Thongtem S (2007) Preparation and characterization of nano-crystalline LiCoVO4 and LiNiVO4 used as cathodes for lithium ion batteries. J Ceram Proc Res 8:450–452
Phuruangrat A, Thongtem T, Thongtem S (2007) Characterization of nano-crystalline LiNiVO4 synthesized by hydrothermal process. Mater Lett 61:3805–3808
Wang GX, Zhong S, Bradhurst DH, Dou SX, Liu HK (1999) Rare earth element (La) doped LiNiVO4 as cathode material for secondary lithium ion cells. Mater Sci Forum 315–317:105–112
Reddy MV, Pecquenard B, Vinatier P, Levasseur A (2007) Cyclic voltammetry and galvanostatic cycling characteristics of LiNiVO4 thin films during lithium insertion and re/de-insertion. Electrochem Commun 9:409–415
Kalyani P, Kalaiselvi N, Renganathan NG (2005) LiNiMxV1−xO4 (M = Co, Mg and Al) solid solutions—prospective cathode materials for rechargeable lithium batteries. Mater Chem Phys 90:196–202
Zaghib K, Mauger A, Goodenough JB, Gendron F, Julien CM (2009) Positive electrode: lithium iron phosphate. In: Garche J (ed) Encyclopedia of electrochemical power sources. Elsevier Science Amsterdam 5:264–296
Julien CM, Mauger A, Ait-Salah A, Massot M, Gendron F, Zaghib K (2007) Nanoscopic scale studies of LiFePO4 as cathode material in lithium-ion batteries for HEV application. Ionics 13:395–411
Bramnik NN, Nikolowski K, Trots DM, Ehrenberg H (2008) Thermal stability of LiCoPO4 cathodes. Electrochem Solid-State Lett 11:A89–A93
Herle PS, Ellis B, Coombs N, Nazar LF (2004) Nano-network electronic conduction in iron and nickel olivine phosphates. Nat Mater 3:147–152
Wolfenstine J, Allen J (2005) Ni3+/Ni2+ redox potential in LiNiPO4. J Power Sour 142:389–390
Minakshi M, Sharma N, Ralph D, Appadoo D, Nallathamby K (2011) Synthesis and characterization of Li(Co0.5Ni0.5)PO4 cathode for Li-ion aqueous battery applications. Electrochem Solid-State Lett 14:A86–A89
Bramnik NN, Bramnik KG, Baehtz C, Ehrenberg H (2005) Study of the effect of different synthesis routes on Li extraction–insertion from LiCoPO4. J Power Sour 145:74–81
Bramnik NN, Bramnik KG, Buhrmester T, Baehtz C, Ehrenberg H, Fuess H (2004) Electrochemical and structural study of LiCoPO4-based electrodes. J Solid State Electrochem 8:558–564
Nakayama M, Goto S, Uchimoto Y, Wakihara M, Kitayama Y (2004) Changes in electronic structure between cobalt and oxide ions of lithium cobalt phosphate as 4.8-V positive electrode material. Chem Mater 16:3399–3401
Bramnik NN, Nikolowski K, Baehtz C, Bramnik KG, Ehrenberg H (2007) Phase transition occurring upon lithium insertion-extraction of LiCoPO4. Chem Mater 19:908–915
Okada S, Sawa S, Egashira M, Yamaki JI, Tabuchi M, Kageyama H, Konishi T, Yoshino A (2001) Cathode properties of phospho-olivine LiMPO4 for lithium secondary batteries. J Power Sour 97–98:430–432
Jang IC, Lim HH, Lee SB, Karthikeyan K, Aravindan V, Kang KS, Yoon WS, Cho WI, Lee YS (2010) Preparation of LiCoPO4 and LiFePO4 coated LiCoPO4 materials with improved battery performance. J Alloys Compd 497:321–324
Aravindan V, Cheah YL, Chui Ling WC, Madhavi S (2012) Effect of LiBOB additive on the electrochemical performance of LiCoPO4. J Electrochem Soc 159:A1435–A1439
Rabanal ME, Gutierrez MC, Garcia-Alvarado F, Gonzalo EC, Arroyoy de Dompablo ME (2006) Improved electrode characteristics of olivine–LiCoPO4 processed by high energy milling. J Power Sour 160:523–528
Koleva V, Zhecheva E, Stoyanova R (2010) Ordered olivine-type lithium-cobalt and lithium-nickel phosphates prepared by a new precursor method. Eur J Inorg Chem 26:4091–4099
Kandhasamy S, Pandey A, Minakshi M (2012) Polyvinyl-pyrrolidone assisted sol-gel route LiCo1/3Mn1/3Ni1/3PO4 composite cathode for aqueous rechargeable battery. Electrochim Acta 60:170–176
Eftekhari A (2004) Surface modification of thin-film based LiCoPO4 5 V cathode with metal oxide. J Electrochem Soc 151:A1456–A1460
Deniard P, Dulac AM, Rocquefelte X, Grigorova V, Lebacq O, Pasturel A, Jobic S (2004) High potential positive materials for lithium-ion batteries: transition metal phosphates. J Phys Chem Solids 65:229–233
Prabu M, Selvasekarapandian S, Kulkarni AR, Karthikeyan S, Hirankumar G, Sanjeeviraja C (2011) Structural, dielectric, and conductivity studies of yttrium-doped LiNiPO4 cathode materials. Ionics 17:201–207
Karthickprabhu S, Hirankumar G, Maheswaran A, Sanjeeviraja C, Daries-Bella RS (2013) Structural and conductivity studies on LiNiPO4 synthesized by the polyol method. J Alloys Compd 548:65–69
Lloris JM, Pérez-Vicente C, Tirado JL (2002) Improvement of the electrochemical performance of LiCoPO4 5 V material using a novel synthesis procedure. Electrochem Solid-State Lett 5:A234–A237
Yang J, Xu JJ (2006) Synthesis and characterization of carbon-coated lithium transition metal phosphates LiMPO4 (M = Fe, Mn Co, Ni) prepared via a nonaqueous sol-gel route batteries, fuel cells, and energy conversion. J Electrochem Soc 153:A716–A723
Gangulibabu N, Bhuvaneswari D, Kalaiselvi N, Jayaprakash N, Periasamy P (2009) CAM sol-gel synthesized LiMPO4 (M = Co, Ni) cathodes for rechargeable lithium batteries. J Sol-Gel Sci Technol 49:137–144
Zhou F, Cococcioni M, Kang K, Ceder G (2004) The Li intercalation potential of LiMPO4 and LiMSiO4 olivines with M = Fe, Mn Co, Ni. Electrochem Commun 6:1144–1148
Howard WF, Spotnitz RM (2007) Theoretical evaluation of high-energy lithium metal phosphate cathode materials in Li-ion batteries. J Power Sour 165:887–891
Rissouli K, Benkhouja K, Ramos-Barrado JR, Julien C (2003) Electrical conductivity in lithium orthophosphates. Mater Sci Eng B 98:185–189
Goñi A, Lezama L, Barberis GE, Pizarro JL, Arriortua MI, Rojo T (1996) Magnetic properties of the LiMPO4 (M = Co, Ni) compounds. J Magn Magn Mater 164:251–255
Santoro RP, Segal DJ, Newnham RE (1966) Magnetic properties of LiCoPO4 and LiNiPO4. J Phys Chem Solids 27:1192–1193
Kornev I, Bichurin M, Rivera JP, Gentil S, Schmid H, Jansen AGM, Wyder P (2000) Magnetoelectric properties of LiCoPO4 and LiNiPO4. Phys Rev B Condens Matter 62:12247–12253
Yamauchi K, Picozzi S (2010) Magnetic anisotropy in Li-phosphates and origin of magnetoelectricity in LiNiPO4. Phys Rev B: Condens Matter 81:024110
Julien CM, Mauger A, Zaghib K, Veillette R, Groult H (2012) Structural and electronic properties of the LiNiPO4 orthophosphate. Ionics 18:625–633
Fomin VI, Gnezdilov VP, Kurnosov VS, Peschanskii AV, Yeremenko AV, Schmid H, Rivera JP, Gentil S (2002) Raman scattering in a LiNiPO4 single crystal. Low Temp Phys 28:203–209
Shang SL, Wang Y, Mei ZG, Hui XD, Liu ZK (2012) Lattice dynamics, thermodynamics, and bonding strength of lithium-ion battery materials LiMPO4 (M = Mn, Fe Co, and Ni): a comparative first-principles study. J Mater Chem 22:1142–1149
Dimesso L, Jacke S, Spanheimer C, Jaegermann W (2012) Investigation on LiCoPO4 powders as cathode materials annealed under different atmospheres. J Solid State Electrochem 16:3911–3919
Dimesso L, Spanheimer C, Jaegermann W (2013) Effect of the Mg-substitution on the graphitic carbon foams—LiNi1-yMgyPO4 composites as possible cathodes materials for 5 V applications. Mater Res Bull 48:559–565
Amine K, Yasuda H, Yamachi M (2000) Olivine LiCoPO4 as 4.8-V electrode material for lithium batteries. Electrochem Solid-State Lett 3:178–179
Wolfenstine J, Allen J (2004) LiNiPO4–LiCoPO4 solid solutions as cathodes. J Power Sour 136:150–153
Ni J, Gao L, Lu L (2013) Carbon coated lithium cobalt phosphate for Li-ion batteries: Comparison of three coating techniques. J Power Sour 221:35–41
Wolfenstine J, Read J, Allen J (2007) Effect of carbon on the electronic conductivity and discharge capacity LiCoPO4. J Power Sour 163:1070–1073
Wolfenstine J, Lee U, Poese B, Allen J (2005) Effect of oxygen partial pressure on the discharge capacity of LiCoPO4. J Power Sour 144:226–230
Wolfenstine J, Poese B, Allen J (2004) Chemical oxidation of LiCoPO4. J Power Sour 138:281–282
Wolfenstine J (2006) Electrical conductivity of doped LiCoPO4. J Power Sour 158:1431–1435
Wang F, Yang J, Li YN, Wang J (2011) Novel hedgehog-like 5 V LiCoPO4 positive electrode material for rechargeable lithium battery. J Power Sour 196:4806–4810
Nakayama M, Goto S, Uchimoto Y, Wakihara M, Kitayama Y, Miyanaga T, Watanabe I (2005) X-ray absorption spectroscopic study on the electronic structure of Li1-x CoPO4 electrodes as 4.8 V positive electrodes for rechargeable lithium ion batteries. J Phys Chem B 109:11197–11203
Dimesso L, Spanheimer C, Jaegermann W, Zhang Y, Yarin AL (2013) LiCoPO4—3D carbon nanofiber composites as possible cathode materials for high voltage applications. Electrochim Acta 97:38–42
Devaraju MK, Rangappa D, Honma I (2012) Controlled synthesis of plate-like LiCoPO4 nanoparticles via supercritical method and their electrode property. Electrochim Acta 85:548–553
Reddy MV, Subba-Rao GV, Chowdari BVR (2010) Long-term cycling studies on 4 V-cathode lithium vanadium fluorophosphates. J Power Sour 195:5768–5774
Okada S, Ueno M, Uebou Y, Yamaki JI (2005) Fluoride phosphate Li2CoPO4F as a high-voltage cathode in Li-ion batteries. J Power Sour 146:565–569
Khasanova NR, Gavrilov AN, Antipov EV, Bramnik KG, Hibst H (2011) Structural transformation of Li2CoPO4F upon Li-deintercalation. J Power Sour 196:355–360
Stroukoff KR, Manthiram A (2011) Thermal stability of spinel Li1.1Mn1.9−yMyO4−zFz (M = Ni, Al, and Li, 0 ≤ y ≤ 0.3, and 0 ≤ z≤0.2) cathodes for lithium ion batteries. J Mater Chem 21:10165–10170
Koyama Y, Tanaka I, Adachi H (2000) New fluoride cathodes for rechargeable lithium batteries. J Electrochem Soc 147:3633–3636
Dutreilh M, Chevalier C, El-Ghozzi M, Avignant D, Montel JM (1999) Synthesis and crystal structure of a new lithium nickel fluorophosphates Li2NiFPO4 with an ordered mixed anionic framework. J Solid State Chem 142:1–5
Nagahama M, Hasegawa N (2010) Okada S (2010) High voltage performances of Li2NiPO4F cathode with dinitrile-based electrolytes. J Electrochem Soc 157:A748–A752
Amaresh S, Karthikeyan K, Kim KJ, Kim MC, Chung KY, Cho BW, Lee YS (2013) Facile synthesis of ZrO2 coated Li2CoPO4F cathode materials for lithium secondary batteries with improved electrochemical properties. J Power Sour. doi:10.1016/j.jpowsour.2012.12.010
Barpanda P, Recham N, Chotard JN, Djellab K, Walker W, Armand M, Tarascon JM (2010) Structure and electrochemical properties of novel mixed Li(Fe1−xMx)SO4F (M = Co, Ni, Mn) phases fabricated by low temperature ionothermal synthesis. J Mater Chem 20:1659–1668
Kim H, Lee S, Park YU, Kim H, Kim J, Jeon S, Kang K (2011) Neutron and X-ray diffraction study of pyrophosphate-based Li2−xMP2O7 (M = Fe, Co) for lithium rechargeable battery electrodes. Chem Mater 23:3930–3937
Xu KC, Cresce AVW (2012) Electrolytes in support of 5 V Li-ion chemistry. Patent appl number: 20120225359
La Mantia F, Huggins RA, Cui Y (2013) Oxidation processes on conducting carbon additives for lithium-ion batteries. J Appl Electrochem 43:1–17
Fang HS, Wang ZX, Li XH, Guo HJ, Peng WJ (2006) Low temperature synthesis of LiNi0.5Mn1.5O4 spinel. Mater Lett 60:1273–1275
Liu YJ, Liu ZY, Chen XH, Chen L (2012) Synthesis and performance of LiNi0.5Mn1.5O4 cathodes. J Central South Univ (Sci and Technol) 43:4248–4252
Julien C, Massot M, Pérez-Vicente C (2000) Structural and vibrational studies of LiNi1−yCoyVO4 (0 ≤ y≤1) cathodes materials for Li-ion batteries. Mater Sci Eng B 75:6–12
Minakshi M, Singh P, Appadoo D, Martin DE (2011) Synthesis and characterization of olivine LiNiPO4 for aqueous rechargeable battery. Electrochim Acta 56:4356–4360
Chevrier VL, Ong SP, Armiento R, Chan MKY, Ceder G (2010) Hybrid density functional calculations of redox potentials and formation energies of transition metal compounds. Phys Rev B 82:075122
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Julien, C.M., Mauger, A., Zaghib, K., Liu, D. (2015). High Voltage Cathode Materials. In: Zhang, Z., Zhang, S. (eds) Rechargeable Batteries. Green Energy and Technology. Springer, Cham. https://doi.org/10.1007/978-3-319-15458-9_17
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