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.

/pdf/one-year-stable-perovskite-solar-cells-by-2d-3d-interface-3uapzy45tv.pdf

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

Hydrothermal reactions of manganese(II) salts with m-sulfophenylphosphonic acid (m-HO3S-Ph-PO3H2, H3L) and 1,10-phenanthroline (phen) led to six novel manganese(II) sulfonate-phosphonates, namely, [Mn-2(HL)(2)(phen)(4)][Mn-2(HL)(2)(phen)(4)(H2O)](2)center dot 6H(2)O (1), [Mn-4(L)(2)(phen)(8)(H2O)(2)][ClO4](2)center dot 3H(2)O (2), [Mn(phen)(H2O)(4)](2)[Mn-4(L)(4)(phen)(4)]center dot 10H(2)O (3), [Mn-6(L)(4)(phen)(8)(H2O)(2)]center dot 4H(2)O (4), [Mn-6(L)(4)(phen)(8)(H2O)(2)]center dot 24H(2)O (5), and [Mn-6(L)(4)(Phen)(6)(H2O)(4)]center dot 5H(2)O (6). The structure of 1 contains two types of dinuclear manganese(II) clusters, and 2-3 exhibit two types of tetranuclear manganese(II) cluster units. 4-5 feature two different types of isolated hexanuclear manganese(II) clusters, whereas the hexanuclear manganese(II) clusters in 6 are bridged by sulfonate-phosphonate ligands into a 1D chain. Magnetic property measurements indicate that there exist weak antiferromagnetic interactions between magnetic centers in all six compounds.

Novel manganese(II) sulfonate-phosphonates with dinuclear, tetranuclear, and hexanuclear clusters.

Three novel rubidium borogermanates with three types of noncentrosymmetric structures, namely, RbGeB3O7, Rb2GeB4O9, and Rb4Ge3B6O17, have been synthesized by high-temperature solid-state reactions ...

New second-order NLO materials based on polymeric borate clusters and GeO4 tetrahedra: a combined experimental and theoretical study.

Two novel alkali(I) borogermanates with noncentrosymmetric structures, namely, CsB3GeO7 and K2B2Ge3O10, have been synthesized by high-temperature solid-state reactions in a platinum crucible. The structure of CsB3GeO7 features a novel three-dimensional (3D) framework composed of cyclic B3O75− groups that are interconnected by Ge(IV) cations, whereas the structure of K2B2Ge3O10 is a new 3D network based on cap-shaped [Ge3B2O14]10− clusters that are interconnected via Ge−O−B bridges. CsB3GeO7 exhibits a second-harmonic generation (SHG) response that is about 1.5 times that of KDP (KH2PO4), whereas the SHG signal of K2B2Ge3O10 is very weak. Both compounds are insulators and transparent in the range of 300−5000 nm. The electronic structure calculations for both compounds also have been performed.

CsB3GeO7 and K2B2Ge3O10: explorations of new second-order nonlinear optical materials in the borogermanate systems.

Large blue-green, transparent crystalline needles of [K-(2,2)diaza-[18]-crown-6]KGe(9).3en are prepared, in high yield, from the reaction of (2,2)diaza[18]-crown-6 in toluene with a solution of "KGe(4)" in ethylenediamine (en). The compound crystallizes in the orthorhombic space group Pnma (a = 10.9763(12) A, b = 27.265(3) A, c = 13.880(1) A; Z = 4). The crystal structure of [K-(2,2)diaza-[18]-crown-6]KGe(9).2en features one-dimensional [KGe(9)](-) bare intermetallic chains formed from the linking, via exo-bonds, of nido-Ge(9)(2-) clusters. Uncomplexed K atoms effectively cap the square bases of the monocapped square antiprismatic [Ge(9)](2-) clusters. The optical band gap of the title compound is 1.25 eV. The use of weaker sequestering agents in the isolation of Ge cluster anions from en solutions provides an additional handle in a controlled molecular route to preparing new low-dimensional Zintl phases.

The role of sequestering agents in the formation and structure of germanium anion cluster polymers.

Hydrothermal reactions of lead(II) acetate with 1,3,5-benzenetricarboxylic acid (H3BTC) and a new aminodiphosphonic acid, [3-pyridyl-CH2N(CH2PO3H2)2] (H4L1), or a new aminotriphosphonic acid, [1-{(H2O3PCH2)2NCH2CH2-}-piperazine-4-CH2PO3H2] (H6L2), afforded two novel porous carboxylate−phosphonate hybrids, [Pb4(BTC)(HBTC)(HL1)]·3H2O (1) and [Pb6(BTC)2(HBTC)(H2L2)]·4.5H2O (2). The structure of 1 is built from a 3D porous network of lead(II) tricarboxylate and 1D double chains of lead(II) aminodiphosphonate. The structure of 2 contains lead(II) carboxylate−phosphonate hybrid layers, which are cross-linked by 1D double chains of lead(II) phosphonate through the organic groups of both types of ligands, resulting in the formation of a complex 3D porous network. The lattice water molecules in both compounds are located at the micropores of the structures. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

Jiang-Gao Mao

Papers

Novel manganese(II) sulfonate-phosphonates with dinuclear, tetranuclear, and hexanuclear clusters.

New second-order NLO materials based on polymeric borate clusters and GeO4 tetrahedra: a combined experimental and theoretical study.

CsB3GeO7 and K2B2Ge3O10: explorations of new second-order nonlinear optical materials in the borogermanate systems.

The role of sequestering agents in the formation and structure of germanium anion cluster polymers.

Novel Hybrid Porous 3D Networks of Lead(II) Diphosphonate and Triphosphonate Containing 1,3,5-Benzenetricarboxylate