Preparation of layered LiMnxCr1−xO2 solid solution by emulsion drying method as lithium intercalation compounds

Komaba, Shinichi; Hirosaki, Norimitsu; Kumagai, Naoya

doi:10.1016/s1388-2481(02)00313-2

Cited by 26 publications

(19 citation statements)

References 19 publications

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“…The average radius, r, of an oxide particle was determined to be 0.15 m from the TEM observation. 10,11 As expected from the difference between the OCV and CCV, the chemical diffusivity was inversely proportional to the difference between the OCV and CCV as a function of the Li content in Fig. 15b.…”

Section: ͓1͔supporting

confidence: 60%

“…These results were due probably to the increased crystallinity and structural integrity by increasing the firing time. According to our previous TEM observations, 10,11 the powders fired for 12 h showed an average particle size of about 300 nm and the powders were uniformly dispersed. However, a longer firing produced a significant agglomeration of the powders, especially for the sample calcined for 24 h. From the XRD and TEM analyses, we determined the optimum calcination conditions to be 850°C for 12 h. Figure 4 shows the XRD patterns of LiMn x Cr 1Ϫx O 2 with varying Mn substitution amounts.…”

Section: Resultsmentioning

confidence: 66%

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Structural Investigation of Layered Li[sub 1−δ]Mn[sub x]Cr[sub 1−x]O[sub 2] by XANES and In Situ XRD Measurements

Komaba

Hirosaki

Kumagai

et al. 2003

J. Electrochem. Soc.

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A wide solid solution of lithium manganese chromium oxides, LiMn x Cr 1Ϫx O 2 (0 р x р 0.6), having the layered ␣-NaFeO 2 structure, was synthesized by employing the emulsion drying method, and the Mn and Cr oxidation states of the prepared powders were identified by combination of the Rietveld analysis of the X-ray diffraction ͑XRD͒ data and X-ray absorption near edge spectroscopic ͑XANES͒ analysis. A reversible structural change of LiMn 0.6 Cr 0.4 O 2 was observed using the in situ XRD technique after the first charge. With increasing Mn contents, the reversible capacity increased due to the redox couples of Mn 3ϩ/4ϩ and Cr 3ϩ/6ϩ , as observed by the XANES spectra measured as a function of the Li contents during the first cycle. The rechargeable capacity for LiMn 0.6 Cr 0.4 O 2 was about 140 mAh g Ϫ1 between 4.3 and 2.7 V vs. Li for 30 cycles. The measured chemical diffusion coefficient for LiMn 0.6 Cr 0.4 O 2 was much higher than those for LiAl x Mn 2Ϫx O 4 and LiAl x Co 1Ϫx O 2 . This emulsion drying synthesis is an excellent powder preparation alternative method of high capacity cathode materials to be used in a Li-ion secondary battery.The Li-Mn-Cr-O system has been studied extensively by several research groups. 1-7 Earlier studies have shown that the partial substitution of the Mn sites of the tetragonal spinel Li 2 Mn 2 O 4 by Cr produced a continuous solid solution of Li 2 Cr x Mn 2Ϫx O 4 . 1-3 The final products of this system depend on the Cr doping amount and calcination conditions; different Cr doping amounts resulted in different crystal systems, such as tetragonal (I4 1 /amd), distorted hexagonal (C2/m), and hexagonal (R3 m). 2,3 The corresponding electrochemical properties of the prepared powders were also quite different. For example, a lower Cr doping level in the tetragonal Li 2 Cr x Mn 2Ϫx O 4 showed a two-step Li ϩ deintercalation/intercalation during cycling with two potential plateaus at 3 and 4 V, which were mainly caused by the effect of the Jahn-Teller ion, Mn 3ϩ . A dilution of the effect was achieved by higher level Cr 3ϩ doping in Li 2 Cr x Mn 2Ϫx O 4 where crystallization occurred to produce a distorted hexagonal system. A much higher level doping led to increased symmetry from distorted hexagonal (C2/m) to hexagonal (R3 m) where the cooperative Jahn-Teller distortion was absent. Obviously, the layered compounds showed simple S-shaped charge/ discharge curves and stable cycling behavior. According to the obtained capacity, one is able to postulate that both the Mn 3ϩ and Cr 3ϩ elements were electrochemically active. Unfortunately, the pure hexagonal structured compound, LiCr 0.75 Mn 0.25 O 2 , delivered a capacity of about 100 mAh g Ϫ1 ͑current density: 3.6 mA g Ϫ1 at 25°C͒.Li 3 MnCrO 5 ͑can also be written as Li 1.2 Cr 0.4 Mn 0.4 O 2 ) is a solid solution series, Li 2 MnO 3 -LiCrO 2 . 4,5,7 Obviously, both compounds are famous as electrochemically inactive materials. Nonetheless, once Li 1.2 Cr 0.4 Mn 0.4 O 2 is formed, the hexagonal structured layer compound provides excellent cap...

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Section: ͓1͔supporting

confidence: 60%

Section: Resultsmentioning

confidence: 66%

Structural Investigation of Layered Li[sub 1−δ]Mn[sub x]Cr[sub 1−x]O[sub 2] by XANES and In Situ XRD Measurements

Komaba

Hirosaki

Kumagai

et al. 2003

J. Electrochem. Soc.

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“…[57] On the contrary, LiCrO 2 was electrochemically inactive as the Li + host due to irreversible migration of disproportioned oxidized Cr 6+ into interstitial tetrahedron sites occurs during charge/discharge. [58,59] But Cr 6+ can stay in the transition metal layer of NaCrO 2 after Na + extraction because of the size mismatch of Na + and Cr 6+ . [60,61] Ceder and co-workers revealed that the layered P′3-Na 0.4 CrO 2 to rock-salt CrO 2 phase transition occurs after full sodium extraction which accounts for the capacity decay observed in NaCrO 2 at the end of charge.…”

Section: Single-metal-based Oxides Peculiar To Sibsmentioning

confidence: 99%

Layered Oxide Cathodes for Sodium‐Ion Batteries: Phase Transition, Air Stability, and Performance

Wang

You

Yin

et al. 2017

Advanced Energy Materials

660

464

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sources into large-scale grids, inexpensive, efficient, and fast-responding electrical energy storage (EES) systems are essential to store the off-peak energy and releasing the stored energy during the onpeak period. Among various EES systems, rechargeable batteries represent one of the most competitive technologies because of their high conversion efficiency and environmental friendliness. [1][2][3][4] For stationary EES systems, batteries with low cost, high safety, high rate capability, and long cycle stability are highly desired.Lithium (Li)-ion batteries (LIBs) have achieved great success in the market of portable electronics and electric vehicles since their commercialization by Sony Company in 1991. However, the shortage of Li resources in nature gives rise to a concern about its sustainable development in grid scale. Compared with Li, sodium resource has rich natural abundance in the earth crust and a worldwide distribution, consequently leading to a low price of sodium-based raw materials (e.g., the cost of Na 2 CO 3 is about 25-30 times lower than that of Li 2 CO 3 ). Besides, sodium has a suitable redox potential (E 0 (Na + /Na) = −2.71 V versus standard hydrogen electrode (SHE), 0.3 V above that of Li + /Li) and similar physical and chemical properties with lithium. [5,6] Therefore, rechargeable sodium-ion batteries (SIBs), which have a similar "rockingchair" working principle of LIBs, are emerging as an appealing choice as alternatives for LIBs. Note that it is difficult for SIBs to bypass LIBs in terms of energy densities because of the much higher weight of Na and lower standard electrochemical potential. [7][8][9][10] Nevertheless, the use of low-cost materials, including inexpensive Na-based raw materials and Al current collectors for both cathodes and anodes in SIBs, could significantly reduce the cost. In this case, SIBs could be applied where cost-effectiveness rather than energy density is the most critical issue, e.g., in the field of large-scale EES. As a result, sodiumbased electroactive materials are enjoying renewed interest especially for very low cost systems for grid storage. [11,12] Given that cathode materials are the key component that determines energy density and cost, tremendous efforts have been devoted to exploring suitable positive electrode materials with high reversible capacity, rapid Na ions insertion/extraction, and good cycling stability in the past few years. [13,14] A broad range of compounds, including layered oxides, polyanionic frameworks, hexacyanoferrates, and organics, haveThe increasing demand for replacing conventional fossil fuels with clean energy or economical and sustainable energy storage drives better battery research today. Sodium-ion batteries (SIBs) are considered as a promising alternative for grid-scale storage applications due to their similar "rockingchair" sodium storage mechanism to lithium-ion batteries, the natural abundance, and the low cost of Na resources. Searching for appropriate electrode materials with acceptable electrochemical perfor...

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“…In addition, the facile interconversion and low energy separation between the different structural polytypes often leads to stacking faults in the ion-exchanged material. For example, ion-exchange of P2-Na 5/6 [ 2 and Na x CrO 2 crystallize in the same structural polytype, the former has been found to be electrochemically inactive, 41 while the latter has demonstrated a reversible capacity of 120 mAh/g when cycled in a Na cell, 42 and a recent study showed that the capacity retention of carbon-coated Na x CrO 2 is excellent. 43 ) unless CC License in place (see abstract The metastable layered phase, LiFeO 2 , can be prepared from ionexchanged α-NaFeO 2 .…”

Section: The Different Crystal Chemistries Of Intercalated LImentioning

confidence: 99%

Review—Manganese-Based P2-Type Transition Metal Oxides as Sodium-Ion Battery Cathode Materials

Clément

Bruce

Grey

2015

J. Electrochem. Soc.

438

388

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Sodium transition metal oxides (NaMO 2 ) with a P2 structure exhibit good Na + ion conductivity and are promising sodium-ion battery cathode materials. Manganese-based compounds have a high working potential vs. Na + /Na, and high capacity. Yet, the layered nature of these materials means that they are prone to structural rearrangements at high voltage/low Na contents, the phase transformations and Na + ion/vacancy ordering transitions resulting in capacity fade and poor reversibility. This review discusses the latest advances in the field and focuses mainly on recent work on Na y Mn 1-x M x O 2 (x, y ≤ 1, M = Ni, Mg, Li) compounds. We compare the different lithium and sodium transition metal layered oxides (P2, O3, etc.) and describe the structures and mechanisms observed on alkali (de)intercalation. The strategies used to enhance the electrochemical properties and stabilize the structural framework of sodium transition metal oxides are reviewed. We show how X-ray diffraction and 7 Li/ 23 Na solid-state Nuclear Magnetic Resonance can be combined to provide a detailed insight into the structural and electronic processes occurring upon electrochemical cycling of these materials. Why Are We Interested in Na-Ion Battery Cathodes?Together, the increasing demand for energy and the threat from Global Warming make electrical energy storage (EES) a world wide strategic priority. EES is expected to play a key role in the decarbonization of electric power sources. The two billion people worldwide not currently served by a reliable electricity supply are likely to be connected via local grids, for which EES is essential. While Li-ion batteries (LIBs) will play a role, a key challenge is to develop lower cost batteries that deliver safe, reliable storage with high cycle and calendar life. In this regard, Na-ion batteries (NIBs) are potentially important. NIBs operate in a similar fashion to LIBs, offering both advantages and disadvantages. Concerning the former, the ability to use Al instead of Cu as a current collector at the anode could substantially reduce cost. Na is also far more abundant in the Earth's crust than Li, and more widely distributed geographically. Regarding the disadvantages, the standard operating potential of Na metal is 300 mV more positive than Li metal. This generally translates into lower operating potentials for Na-ion systems, although the potential of a full cell depends on the difference in the chemical potentials of Na in the anode and cathode materials. There are considerable opportunities for scientists to develop new combinations of anode, electrolyte and cathode that are optimized for a variety of applications with different criteria such as high energy density, high power, and high operating potential. This has encouraged a rapid growth of interest in research into NIB components. Hard carbons show some promise as anodes, [1][2][3] but more must be done to improve performance. The cathode remains a major challenge and it is to this that we direct the current review. A comparative plot sho...

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Preparation of layered LiMnxCr1−xO2 solid solution by emulsion drying method as lithium intercalation compounds

Cited by 26 publications

References 19 publications

Structural Investigation of Layered Li[sub 1−δ]Mn[sub x]Cr[sub 1−x]O[sub 2] by XANES and In Situ XRD Measurements

Structural Investigation of Layered Li[sub 1−δ]Mn[sub x]Cr[sub 1−x]O[sub 2] by XANES and In Situ XRD Measurements

Layered Oxide Cathodes for Sodium‐Ion Batteries: Phase Transition, Air Stability, and Performance

Review—Manganese-Based P2-Type Transition Metal Oxides as Sodium-Ion Battery Cathode Materials

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