Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries

Thackeray, Michael M.; Johnson, Christopher; Vaughey, John T.; Li, N.; Hackney, S.A.

doi:10.1039/b417616m

Cited by 1,073 publications

(921 citation statements)

References 48 publications

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“…2,9,10 However, recent work has reinvigorated interest in the material. Both mesoporous 2,11,12 and needle-like 13,14 nanostructured rutile MnO 2 have demonstrated good intercalation of lithium ions.…”

Section: ■ Introductionmentioning

confidence: 99%

Rutile (β-)MnO₂ Surfaces and Vacancy Formation for High Electrochemical and Catalytic Performance

2014

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MnO 2 is a technologically important material for energy storage and catalysis. Recent investigations have demonstrated the success of nanostructuring for improving the performance of rutile MnO 2 in Li-ion batteries and supercapacitors and as a catalyst. Motivated by this we have investigated the stability and electronic structure of rutile (β-)MnO 2 surfaces using density functional theory. A Wulff construction from relaxed surface energies indicates a rod-like equilibrium morphology that is elongated along the c-axis, and is consistent with the large number of nanowire-type structures that are obtainable experimentally. The (110) surface dominates the crystallite surface area. Moreover, higher index surfaces than considered in previous work, for instance the (211) and (311) surfaces, are also expressed to cap the rod-like morphology. Broken coordinations at the surface result in enhanced magnetic moments at Mn sites that may play a role in catalytic activity. The calculated formation energies of oxygen vacancy defects and Mn reduction at key surfaces indicate facile formation at surfaces expressed in the equilibrium morphology. The formation energies are considerably lower than for comparable structures such as rutile TiO 2 and are likely to be important to the high catalytic activity of rutile MnO 2 . ■ INTRODUCTIONEnergy storage for hybrid electric vehicles and renewable energy sources is a pressing technological challenge for which Li-ion batteries and supercapacitors are key candidate systems. The conventional Li-ion intercalation cathode, LiCoO 2 , faces challenges of toxicity and high cost. Current supercapacitors based on carbon cathodes are limited by their storage capacity. The demand for higher capacity and higher power energy storage has led to a surge in interest in nanostructured electrodes. 1 Nanostructuring has been shown to improve the energy storage properties of rutile MnO 2 for both Li-ion batteries 2,3 and supercapacitors. 4−6 However, the mechanisms for this improvement are not fully understood on the atomic-scale. In addition to its role as an electrode material, nanostructured rutile MnO 2 has been shown to give good performance as a catalyst, 7 with much recent interest in its potential role in the Li−O 2 battery. 8 Knowledge of the surface features of rutile MnO 2 at the atomic and electronic level would provide valuable information regarding its energy storage and catalytic mechanisms. With the clear impetus to better understand the performance of rutile MnO 2 in three technologies, Li-ion batteries, supercapacitors and catalysis, in this work we apply first-principles simulations to understand surface phenomena in this promising material.Rutile MnO 2 is the subject of extensive research for its applications in Li-ion batteries, but early work indicated that bulk samples did not allow significant Li-ion intercalation. 2,9,10

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Section: ■ Introductionmentioning

confidence: 99%

Rutile (β-)MnO₂ Surfaces and Vacancy Formation for High Electrochemical and Catalytic Performance

2014

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“…The existence of an Li 2 MnO 3 impurity phase cannot strongly affect the electrochemical properties of the Li-doped sample because of the poor electrochemical activity of Li 2 MnO 3 , especially at high rates. 23 Therefore, the superior electrochemical performance appears to be related to the increase of Ni/Mn disordering in the Li-doped sample; that is, the electrochemical property of the spinel is strongly affected by the disordering of Ni/Mn and not by the presence of Mn 3+ ions.…”

Section: Resultsmentioning

confidence: 99%

High electrochemical performance of high-voltage LiNi0.5Mn1.5O4 by decoupling the Ni/Mn disordering from the presence of Mn3+ ions

Lee¹,

Kim²,

Kang³

2015

NPG Asia Mater

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Electrochemical activity in high-voltage spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) is strongly affected by the disordering of Ni/Mn and the presence of Mn 3+ ions. However, understanding the effect of the Ni/Mn disordering or the presence of Mn 3+ ions on electrochemical properties is not trivial because disordering is typically coupled with the presence of Mn 3+ ions. Here, we demonstrate for the first time that the doping of Li instead of Ni increases Ni/Mn disordering, which is decoupled from the presence of Mn 3+ ions. The resultant material has a particle size of~1-2 μm and can achieve 120 mAh g − 1 at 10 C for 50 cycles and further deliver about 60 mAh g − 1 even at a rate of~60 C (1 min discharge). Superior electrochemical performance is achieved by increased solid-solution phase transition behavior, which is caused by increased Ni/Mn disordering during delithiation. By decoupling, we find that the electrochemical properties in LNMO strongly depend on the phase transformation behavior and that the Ni/Mn disordering, rather than Mn 3+ ions, affects the phase transformation by increasing the solid-solution reaction. The fundamental understanding gained from this work could be applied to the development of other phase-separating compounds to improve their electrochemical performance. INTRODUCTIONFor a lithium-ion battery, a high energy density is an essential requirement for novel applications such as plug-in hybrid electric vehicles and electric vehicles. Increasing the redox potential of cathode materials is an effective way to achieve high energy density in the cell. For this purpose, high-voltage spinel LiNi 0.5 Mn 1.5 O 4 is a promising cathode material for LIBs 1-3 because it has a high redox potential of about 4.7 V, which makes its energy density (650 W h kg − 1 ) 20% higher than that of the conventional LiCoO 2 . However, the electrochemical properties of LNMO spinel depend on several factors, such as its structure, 3,4 the quantity of Mn 3+ ions, 5,6 the particle size 2,7 and the morphology of particles. 8 Among these factors, the structure of the spinel has a critical influence on its electrochemical performance. 9-11 The LNMO structure is dictated by the ordering of Ni and Mn at two octahedral sites, which results in two spinel forms: disordered and ordered. The Ni and Mn in the ordered spinel are well ordered in two distinct octahedral sites, 4b sites for Ni and 12d sites for Mn, whereas the Ni and Mn in the disordered spinel are randomly distributed in 16d octahedral sites. 1,12 In the ordered spinel, the ordering of Ni/Mn exists without Mn 3+ ions because a second annealing process at o700°C simultaneously leads to the ordering of Ni/Mn on two distinct octahedral sites and the oxidation of Mn 3+ ions into Mn 4+ ions. However, the disordered spinel shows both the disordering of Ni/Mn and the presence of Mn 3+ ions. The correlation

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“…[39,40] Among them, Li and Mn-rich layered cathode materials, xLi 2 MnO 3 •(1-x)LiMO 2 (M = Mn, Ni, Co) show much higher specific capacity of ~ 250 mAh g -1 than that of conventional transition metal oxide cathodes. [41][42][43] Basically, Li 2 MnO 3 by itself cannot deliver high capacity, but a composite with LiMO 2 on a nanometric scale induces a reversible reaction of the excess Li. However, these Li and Mn-rich layered cathodes must still overcome drawbacks such as a large irreversible capacity at the first charging and a gradual decrease of the lithiation voltage during cycling.…”

Section: Layered Lithium Metal Oxidesmentioning

confidence: 99%

Li‐Ion Batteries and Beyond: Future Design Challenges

Hwa

Cairns

2015

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Light metals have been widely used as electrode materials for batteries owing to their low standard redox potential, their low equivalent weight, large specific capacity, and great abundance. Both primary and secondary cells including light metals as electrode material have influenced all aspects of our lives, e.g., electrically operated toys, power tools, and portable electronics such as cell phones, smart pads, and laptop computers. Among all battery systems, rechargeable lithium (Li) ion cells have been used most widely in recent years owing to their high specific power, high energy density, and ambient temperature operation. However, Li‐ion cells are facing difficult challenges in satisfying the emerging market for advanced applications demanding high‐performance rechargeable batteries for applications such as electric vehicles, high‐performance portable electronics, and large‐scale electrical energy storage systems. Unfortunately, current Li‐ion cells cannot satisfy demands such as low cost, much improved safety, larger energy density, faster charge/discharge rates, and longer service life, so intensive effort is necessary to develop the next generation of cells. In this article, the limitations of current Li‐ion cells and various advanced materials for each component of the Li‐ion cell, in addition to other promising candidates for cells beyond Li ion, such as the Li/S cell and Na‐ and Mg‐based rechargeable cells, and metal/air cells are discussed.

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Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries

Cited by 1,073 publications

References 48 publications

Rutile (β-)MnO₂ Surfaces and Vacancy Formation for High Electrochemical and Catalytic Performance

Rutile (β-)MnO₂ Surfaces and Vacancy Formation for High Electrochemical and Catalytic Performance

High electrochemical performance of high-voltage LiNi0.5Mn1.5O4 by decoupling the Ni/Mn disordering from the presence of Mn3+ ions

Li‐Ion Batteries and Beyond: Future Design Challenges

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Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries

Cited by 1,073 publications

References 48 publications

Rutile (β-)MnO2 Surfaces and Vacancy Formation for High Electrochemical and Catalytic Performance

Rutile (β-)MnO2 Surfaces and Vacancy Formation for High Electrochemical and Catalytic Performance

High electrochemical performance of high-voltage LiNi0.5Mn1.5O4 by decoupling the Ni/Mn disordering from the presence of Mn3+ ions

Li‐Ion Batteries and Beyond: Future Design Challenges

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Rutile (β-)MnO₂ Surfaces and Vacancy Formation for High Electrochemical and Catalytic Performance

Rutile (β-)MnO₂ Surfaces and Vacancy Formation for High Electrochemical and Catalytic Performance