Structural and electrochemical properties of layered manganese dioxides in relation to their synthesis: classical and sol–gel routes

Goff, Philippe Le; Baffier, N.; Bach, S.; Pereira-Ramos, J.P.

doi:10.1039/jm9940400875

Cited by 48 publications

(51 citation statements)

References 17 publications

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“…8,9) For investigations of two-dimen-sionally confined water, the title Na-birnessite (Na x MnO 2 yH 2 O) is a suitable system, which is a manganese dioxide (MnO 2 ) compound. 10,11) The Na-birnessite is one of common minerals found naturally in soils, ore deposits and ocean nodules. Moreover it has been paid much attention in the area like batteries and catalysts.…”

Section: Introductionmentioning

confidence: 99%

Two-Dimensionally Confined Water in between MnO₂Layers of Na-Birnessite

Matsui

Odaira

et al. 2009

J. Phys. Soc. Jpn.

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Two-dimensionally confined water in between the MnO 2 octahedral layers in Na-birnessite has been studied to clarify the physical properties and the structural arrangements. From the analysis employing an inductively coupled plasma (ICP) method and chemical titration, the chemical composition is determined to be Na 0:28 Mn 4þ 0:73 Mn 3þ 0:27 O 2 yH 2 O in our sample. According to the X-ray diffraction (XRD) experiments, the interlayer distance along the c axis is 7.17 Å at 293 K in atmosphere, though the distance shrinks to 5.77 Å when the sample is kept either at 333 K in atmosphere or at 293 K in vacuum. The weight loss obtained by thermogravimetry exhibits two steps caused by the dehydration in atmosphere. Together with the XRD data, we confirm that there are two contributions of the water in the interlayers; weakly hydrated water and strongly hydrated water. The latter is regarded as a structural water to maintain the layer structure. In the infrared spectra, three novel peaks are found to develop in evacuating the sample. These peaks are associated with three different distances in between oxygen atoms of water molecules identified by the precise X-ray studies so far. We consider that Na þ ion locates approximately at one MnO 2 unit with Mn 3þ among the four MnO 2 units to preserve charge valence, and the strongly hydrated water molecules surround Na þ in the form of a quasi-planer hexamer-like cluster reflecting the symmetry of MnO 2 layer. The strict restriction of water to the plane and the Coulomb repulsion between Na þ may induce a deformation of the cluster leading to the abovementioned three different distances.

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Section: Introductionmentioning

confidence: 99%

Two-Dimensionally Confined Water in between MnO₂Layers of Na-Birnessite

Matsui

Odaira

et al. 2009

J. Phys. Soc. Jpn.

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“…Birnessite can be synthesized by the oxidation of Mn 2+ in a highly alkaline medium (Giovanoli et al 1970a(Giovanoli et al , 1970bCornell and Giovanoli 1988;Kim et al 2000), leading, for example, to the topotactic transformation of Mn(OH) 2 when subjected to the action of different oxidizers. Other methods using MnO 4 -as starting reagent (Herbstein et al 1971;Ching et al 1995Ching et al , 1997aChing et al , 1997bChen et al 1996aChen et al , 1996bChing and Suib 1997;Kim et al 1999) include mild hydrothermal syntheses (Feng et al 1995;Chen et al 1996aChen et al , 1996b, sol-gel processes (Bach et al 1990(Bach et al , 1993Le Goff et al 1994;Ching et al 1995Ching et al , 1997aCho et al 1999), interactions of KMnO 4 with hydrochloric acid, and ion-exchange of the hydrogen form of birnessite to the Na-or K-forms (Tsuji et al 1992;Leroux et al 1995), and thermal decomposition of KMnO 4 at high temperature (Kim et al 1999). …”

Section: Introductionmentioning

confidence: 99%

“…Therefore, determination of birnessite structure was sometimes limited to a general description of the XRD patterns without any indexing or accurate determination of the unit-cell parameters (Feng et al 1997a(Feng et al , 1997bAronson et al 1999;Ma et al 1999;Yang and Wang 2001). In some cases indexing of hkl reflections was carried out without proper justification (e.g., Le Goff et al 1994, 1996Ching et al 1995;Aronson et al 1999). Significant progress was achieved recently in the structural characterization of birnessite (Post and Veblen 1990;Kuma et al 1994;Drits et al 1997aDrits et al , 1998Drits et al , 2002Manceau et al 1997Manceau et al , 2000cManceau et al , 2002Silvester et al 1997;Lanson et al 2000Lanson et al , 2002aLanson et al , 2002b and specifically in the determination of their unit-cell parameters (Chen et al 1996a(Chen et al , 1996bKim et al 1999;Lanson et al 2000Lanson et al , 2002aLanson et al , 2002b.…”

Section: Introductionmentioning

confidence: 99%

Birnessite polytype systematics and identification by powder X-ray diffraction

Drits

Lanson

Gaillot

2007

American Mineralogist

119

120

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The polytypes of birnessite with a periodic stacking along the c* axis of one-, two-, and three-layers are derived in terms of an anion close-packing formalism. Birnessite layers may be stacked so as to build two types of interlayers: P-type in which basal O atoms from adjacent layers coincide in projection along the c* axis, thus forming interlayer prisms; and, O-type in which these O atoms form interlayer octahedra. The polytypes can be categorized into three groups that depend on the type of interlayers: polytypes consisting of homogeneous interlayers of O-or P-type, and polytypes in which both interlayer types alternate. Ideal birnessite layers can be described by a hexagonal unit-cell (a h = b h ≈ 2.85 Å and γ = 120°) or by an orthogonal C-centered cell (a = √3 b, b h ≈ 2.85 Å and γ = 90°); and, hexagonal birnessite polytypes (1H, 2H 1 , 2H 2 , 3R 1 , 3R 2 , 3H 1 , and 3H 2 ) have orthogonal analogues (1O, 2O 1 , 2O 2 , 1M 1 , 1M 2 , 3O 1 , and 3O 2 ).X-ray diffraction (XRD) patterns from different polytypes having the same layer symmetry and the same number of layers per unit cell exhibit hkl reflections at identical 2θ positions. XRD patterns corresponding to such polytypes differ only by their hkl intensity distributions, thus leading to possible ambiguities in polytype identification. In addition, the characteristics of the birnessite XRD patterns depends not only on the layer stacking but also on the presence of vacant layer sites, and on the type, location and local environment of interlayer cations. Several structure models are described for birnessite consisting of orthogonal vacancyfree or of hexagonal vacancy-bearing layers. These models differ by their stacking modes and by their interlayer structures, which contain mono-, di-, or tri-valent cations. Calculated XRD patterns for these models show that the hkl intensity distributions are determined by the polytype, with limited influence of the interlayer structure. Actual structures of

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“…Conversely, for the corresponding classical birnessite obtained from the reaction of KMnO4 with HCI at 90'C the MnO 6 octahedra are not superposable ( figure 7). Thus, two types of sites appear: the trigonal antiprismatic (TAP) and the trigonal pyramidal (TPy) sites [11].…”

Section: Mn02 Birnessitementioning

confidence: 99%

“…: X-ray diffraction spectra of (a) the hexagonal ternary oxide Na0.7MnO2; (b) the solgel synthesized hexagonal sodium compound Nao.45MnO2.14, 0.76H20; and (c) the sol-gel synthesized hexagonal sodium-free compound MnO 1 .84, 0.7H20 A detailed structural and electrochemical investigation has been performed in order to elucidate the Li insertion process into sol gel birnessite [2,3,6,11,12]. Lithium easily enters trigonal prismatic sites in the potential range 4.2/2.85 V and then induces a monoclinic distortion from x = 0.05 to lead to a closely related monoclinic phase (a = 5.15 A; b = 2.86 A ; c = 14.29 A 03 = 102,10) which is pure for x > 0.25.…”

Section: Mn02 Birnessitementioning

confidence: 99%

Sol Gel Intercalation Materials for Lithium Batteries

et al. 1994

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This paper emphasizes the interest of sol-gel synthesis in obtaining high performance cathodic materials. New vanadium oxides, vanadium bronzes (MxV205) and manganese oxides (MnO 2 ) are prepared via the sol-gel process using inorganic precursors in aqueous medium. Their electrochemical behaviour (working potential, specific capacity, kinetics of Li transport, rechargeability, cycle life) is investigated and discussed in relation with their specific structural, chemical and physical features. In particular, the results are compared to that achieved for the corresponding classical compounds prepared via a synthesis route involving solid state reactions or precipitation reactions.

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Structural and electrochemical properties of layered manganese dioxides in relation to their synthesis: classical and sol–gel routes

Cited by 48 publications

References 17 publications

Two-Dimensionally Confined Water in between MnO₂Layers of Na-Birnessite

Two-Dimensionally Confined Water in between MnO₂Layers of Na-Birnessite

Birnessite polytype systematics and identification by powder X-ray diffraction

Sol Gel Intercalation Materials for Lithium Batteries

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Structural and electrochemical properties of layered manganese dioxides in relation to their synthesis: classical and sol–gel routes

Cited by 48 publications

References 17 publications

Two-Dimensionally Confined Water in between MnO2Layers of Na-Birnessite

Two-Dimensionally Confined Water in between MnO2Layers of Na-Birnessite

Birnessite polytype systematics and identification by powder X-ray diffraction

Sol Gel Intercalation Materials for Lithium Batteries

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Product

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Two-Dimensionally Confined Water in between MnO₂Layers of Na-Birnessite

Two-Dimensionally Confined Water in between MnO₂Layers of Na-Birnessite