Alloy negative electrodes for Li-ion batteries.

Despite the impressive photovoltaic performances with power conversion efficiency beyond 22%, perovskite solar cells are poorly stable under operation, failing by far the market requirements. Various technological approaches have been proposed to overcome the instability problem, which, while delivering appreciable incremental improvements, are still far from a market-proof solution. Here we show one-year stable perovskite devices by engineering an ultra-stable 2D/3D (HOOC(CH2)4NH3)2PbI4/CH3NH3PbI3 perovskite junction. The 2D/3D forms an exceptional gradually-organized multi-dimensional interface that yields up to 12.9% efficiency in a carbon-based architecture, and 14.6% in standard mesoporous solar cells. To demonstrate the up-scale potential of our technology, we fabricate 10 × 10 cm2 solar modules by a fully printable industrial-scale process, delivering 11.2% efficiency stable for >10,000 h with zero loss in performances measured under controlled standard conditions. This innovative stable and low-cost architecture will enable the timely commercialization of perovskite solar cells. Up-scaling represents a key challenge for photovoltaics based on metal halide perovskites. Using a composite of 2D and 3D perovskites in combination with a printable carbon black/graphite counter electrode; Granciniet al., report 11.2% efficient modules stable over 10,000 hours.

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One-Year stable perovskite solar cells by 2D/3D interface engineering

Research to develop alternative electrode materials with high energy densities in Li-ion batteries has been actively pursued to satisfy the power demands for electronic devices and hybrid electric vehicles. This critical review focuses on anode materials composed of Group IV and V elements with their composites including Ag and Mg metals as well as transition metal oxides which have been intensively investigated. This critical review is devoted mainly to their electrochemical performances and reaction mechanisms (313 references).

Li-alloy based anode materials for Li secondary batteries.

Polyoxometalates (POMs) are discrete anionic metaloxygen clusters which can be regarded as soluble oxide fragments. They exhibit a great diversity of sizes, nuclearities, and shapes. They are built from the connection of {MOx} polyhedra, M being a d-block element in high oxidation state, usually VIV,V, MoVI, or WVI.1 While these species have been known for almost two centuries, they still attract much interest partly based on their large domains of applications. They play a great role in various areas ranging from catalysis,2 medicine,3 electrochemistry,4 photochromism,5 to magnetism.6 This palette of applications is intrinsically due to the combination of their added value properties (redox properties, large sizes, high negative charges, nucleophilicity...). Parallel to this domain, the organic-inorganic hybrids area has followed a similar expansion during the last 10 years. The concept of organic-inorganic hybrid materials * To whom correspondence should be addressed. E-mail: dolbecq@ chimie.uvsq.fr. Chem. Rev. 2010, 110, 6009–6048 6009

Hybrid Organic−Inorganic Polyoxometalate Compounds: From Structural Diversity to Applications

The hybrid two-dimensional (2D) halide perovskites have recently drawn significant interest because they can serve as excellent photoabsorbers in perovskite solar cells. Here we present the large scale synthesis, crystal structure, and optical characterization of the 2D (CH3(CH2)3NH3)2(CH3NH3)n−1PbnI3n+1 (n = 1, 2, 3, 4, ∞) perovskites, a family of layered compounds with tunable semiconductor characteristics. These materials consist of well-defined inorganic perovskite layers intercalated with bulky butylammonium cations that act as spacers between these fragments, adopting the crystal structure of the Ruddlesden–Popper type. We find that the perovskite thickness (n) can be synthetically controlled by adjusting the ratio between the spacer cation and the small organic cation, thus allowing the isolation of compounds in pure form and large scale. The orthorhombic crystal structures of (CH3(CH2)3NH3)2(CH3NH3)Pb2I7 (n = 2, Cc2m; a = 8.9470(4), b = 39.347(2) A, c = 8.8589(6)), (CH3(CH2)3NH3)2(CH3NH3)2Pb3I10 (...

http://pubs.acs.org/doi/pdf/10.1021/acs.chemmater.6b00847

Ruddlesden-Popper Hybrid Lead Iodide Perovskite 2D Homologous Semiconductors

The hydrothermal reaction of lead(II) carbonate with 3-sulfobenzoic acid, 3-HO3S−C6H4−CO2H, and isopropylimino-bis(methylenephosphonic acid), (CH3)2CHN(CH2PO3H2)2 (H4L1), gave a new layered lead(II) carboxylate-phosphonate, Pb7(3-O3S−C6H4−CO2)(L1)3(H2O)2·2H2O (1), whereas the hydrothermal reaction of lead(II) carbonate with 1, 3,5-benzenetricarboxylic acid (H3BTC) and N-cyclohexylimino-bis(methylenephosphonic acid), C6H11N(CH2PO3H2)2 (H4L2), afforded a layered complex, Pb3(HL2)(H2L2)(H2BTC)(H2O)·H3BTC·H2O (2). The structure of complex 1 contains lead(II) carboxylate-phosphonate hybrid layers, with the sulfonate group of the carboxylate-sulfonate ligand as the pendant group. In complex 2, the lead(II) ions are interconnected through bridging diphosphonate ligands, and results in the formation of a lead(II) diphosphonate slab, which are further interlinked via hydrogen bonds between non-coordinated phosphonate oxygen atoms to form a layer. The doubly protonated H2BTC anion is bidentately chelated to a lead(II) ion through a carboxylate group, whereas the neutral H3BTC ligand is intercalated between two layers, forming hydrogen bonds with the non-coordinated carboxylate groups of the H2BTC anion. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Novel Layered Lead(II) Aminodiphosphonates with Carboxylate‐Sulfonate and 1,3,5‐Benzenetricarboxylate Ligands as Pendant Groups or Intercalated Species

The new cobalt diphosphonate compound with a 1D zig–zag chain structure is the first example of its kind that has been recognized to exhibit single-molecule magnets behavior. The slow paramagnetic relaxation of the magnetization is explained on the basis of Ising anisotropy resulting from spin canting of antiferromagnetically coupled Co ions. The energy gap is in accord with the predictions of Glauber’s theory for a one-dimensional Ising system.

New type of single chain magnet based on spin canting in an antiferromagnetically coupled Co(II) chain

Metal iodates with a lone-pair containing I(V) that is in an asymmetric coordination geometry can form a diversity of unusual structures and many of them are promising new second homonic generation (SHG) materials. They exhibit wide transparency wavelength regions, large SHG coefficients and high optical-damage thresholds as well as moderately high thermal stability. In this paper, the structures and properties of the metal iodates are reviewed. The combination of d0 transition-metal cations with the iodate groups afforded a large number of metal iodates, with cations covering alkali metal, alkaline earth and lanthanide elements. Many of them are noncentrosymmetric (NCS) and display excellent SHG properties due to the additive effects of polarizations from both types of the asymmetric units. Some lanthanide iodates are able to emit strong luminescence in the visible or near-IR regions. The use of transition metal ions with dn (n ≠ 0) electronic configuration into iodate systems can also induce the formation of NCS compounds when the lone pairs of the iodate groups are properly aligned. The dn transition metal cations are normally octahedrally coordinated or in a square-planar coordination geometry. Furthermore, the combination of two different types of lone-pair-containing cations is also an effective strategy to design new SHG materials.

Structures and properties of functional metal iodates

Hydrothermal reactions of lanthanide(III) salts with N-(2-pyridyl)-aminomethane-1,1-diphosphonic acid (H4L) led to five new lanthanide(III) phosphonates, namely, La4(H2L)4(H3L)4(H2O)4·20H2O (1) and Ln(H2L)(H3L)·4H2O (Ln = Eu (2), Gd (3), Dy (4), and Er (5)) Compound 1 features a 3D framework with rarely observed topology in which each lanthanum(III) ion is eight-coordinated by seven phosphonic oxygen atoms from four phosphonate ligands and an aqua ligand It possesses two types of tunnels running parallel to the a-axis, one formed by five La(III) ions and five organic moieties, the other by seven La(III) ions and seven organic moieties It shows noninterpenetrated three-connected topology Compounds 2−5 are isostructural and exhibit one-dimensional chain structures in which each pair of Ln(III) ions are bridged by two and four phosphonate groups, alternatively Compound 2 exhibits emission bands of the phosphonate ligand and the europium(III) ion in the visible region under 360 nm excitation, with a Eu (

Novel luminescent lanthanide(III) diphosphonates with rarely observed topology

The hydrothermal reaction of zinc(II) acetate with N,N-bis(phosphonomethyl)aminoacetic acid [(H2O3PCH2)2NCH2CO2H, H5L1] and nitrilotris(methylenephosphonic acid)
[N(CH2PO3H2)3, H6L2] at 180 °C afforded two new zinc coordination polymers with a similar 3D network structure. Zn2[(O3PCH2)2NHCH2CO2]
(complex 1) is hexagonal, P61, with a = 8.0677(12), c = 27.283(6)
A, u = 1537.9(5)
A3, Z = 6. In complex 1, the Zn(II)
atoms are tetrahedrally coordinated by three phosphonate oxygen atoms and one carboxylate oxygen atom from four ligands. The ZnO4 tetrahedra are further interconnected through bridging phosphonate and carboxylate groups into a three dimensional network. Zn2[HO3PCH2NH(CH2PO3)2]
(complex 2) is also hexagonal, P61 with a = 8.3553(8), c = 26.657(4)
A, u = 1611.6(3)
A3, Z = 6. The structure of complex 2 features a 3D network built from ZnO4 tetrahedra linked together by bridging phosphonate groups. One zinc and three phosphonate oxygen atoms are disordered. The two zinc atoms in the asymmetric unit are tetrahedrally coordinated by four phosphonate oxygen atoms of four ligands.
Each ligand connects with eight zinc atoms. The effect of the extent of deprotonation of phosphonic acids and substitution groups on the type of complexes formed are discussed.

Jiang-Gao Mao

Papers

Novel Layered Lead(II) Aminodiphosphonates with Carboxylate‐Sulfonate and 1,3,5‐Benzenetricarboxylate Ligands as Pendant Groups or Intercalated Species

New type of single chain magnet based on spin canting in an antiferromagnetically coupled Co(II) chain

Structures and properties of functional metal iodates

Novel luminescent lanthanide(III) diphosphonates with rarely observed topology

Hydrothermal synthesis, characterization and crystal structures of two new zinc(II) phosphonates: Zn2[(O3PCH2)2NHCH2CO2] and Zn2[HO3PCH2NH(CH2PO3)2]