Magmatic-hydrothermal ore deposits in collisional orogens are new targets for modern mineral exploration, yet it is unclear why they preferentially occur in some specific tectonic environments within these orogenic belts. We integrate geologic and geochemical data (especially zircon U-Pb dating and Lu-Hf isotope data) for Mesozoic-Cenozoic magmatic rocks and associated ore deposits in the Lhasa terrane, a highly endowed tectonic unit within the Himalayan-Tibetan orogen, and provide the first example in a continental collision terrane of the application of zircon Hf isotope data to image the lithospheric architecture and its relationship with ore deposits.Three crustal blocks are identified within the Lhasa terrane by the Hf isotope mapping method. They include a central long-lived Precambrian microcontinent with local reworking and two surrounding juvenile Phanerozoic crustal blocks with significant mantle contributions to constituent magmatic rocks. The three crustal blocks are bounded by two E-W-trending terrane-boundary faults, and each block is cut by two N-S-striking concealed faults. Isotopic signatures of zircons from the juvenile crustal blocks indicate that the Phanerozoic continental crust grew from several Mesozoic volcanic-plutonic arcs and by underplating of mantle-derived magmas generated during Mesozoic accretion and Cenozoic collision.Mesozoic subduction-related porphyry Cu-Au deposits and Cenozoic collision-related Cu-Mo deposits are exclusively located in regions with high eHf (>5) juvenile crust. Cu enrichment during differentiation of high fO 2 arc magmas is the key for the formation of Mesozoic subduction-related porphyry Cu-Au. By contrast, remelting of the lower crustal Cu sulfide-rich magmatic cumulates within the juvenile crust is interpreted to have played a key role in the formation of Cenozoic collision-related Cu-Mo deposits.Granite-related Pb-Zn deposits cluster in the oldest crustal regions or developed along the margin of the old crustal block bounded by lithospheric faults. The porphyry Mo deposits are localized along the reworked margins of the old crustal block. It is suggested that crustal reworking released Mo from the old crust to form porphyry Mo deposits, whereas leaching of Pb and Zn from the Paleozoic carbonate cover strata by felsic intrusion-driven fluids is critical to the formation of Pb-Zn ore deposits.Skarn Fe-Cu ore deposits are typically localized along a terrane boundary fault, i.e., lithospheric discontinuity, through which crust-derived felsic melt mixed with Cu-rich mantle-derived mafic magmas ascending upward. Associated granitoid rocks usually bear microgranular mafic enclaves and show a zircon Hf isotope array from negative to positive eHf values (-7.3 to +6.7), supporting mixing of juvenile mantle and evolved crustal sources.The Hf isotope maps show temporal-spatial relationships between crustal structure and the location of ore deposits, demonstrating that the structure, nature, and composition of the crust controlled the localization of ore deposits and ...
The genesis of continental collision-related porphyry Cu deposits (PCDs) remains controversial. The most common hypothesis links their genesis with magmas derived from subduction-modified arc lithosphere. However, it is unclear whether a genetic linkage exists between collision-and subduction-related PCDs. Here, we studied Jurassic subduction-related Cu-Au and Miocene collision-related Cu-Mo porphyry deposits in south Tibet. The Jurassic PCDs occur only in the western segment of the Jurassic arc, which has depleted mantle-like isotopic compositions [e.g., (87 Sr/ 86 Sr) i = 0.7041-0.7048; e Nd(t) as high as 7.5, and e Hf(t) as high as 18]. By contrast, no Jurassic PCDs have been found in the eastern arc segment, which is isotopically less juvenile [e.g., (87 Sr/ 86 Sr) i = 0.7041-0.7063, e Nd(t) < 4.5, and e Hf(t) ≤ 12]. These results imply that incorporation of crustal components during underplating of Jurassic magma induced copper accumulation as sulfides at the base of the eastern Jurassic arc, inhibiting PCD formation at this time. Miocene PCDs are spatially confined to the Jurassic arc, and the giant Miocene PCDs cluster in its eastern segment where no Jurassic PCDs occur. This suggests that the arc segment barren for subduction-related PCDs could be fertile for collision-related PCDs. Miocene ore-forming porphyries have young Hf model ages and Sr-Nd-Hf isotopic compositions overlapping with those of the Jurassic rocks in the eastern segment, whereas contemporaneous barren porphyries outside the Jurassic arc have abundant zircon inheritance and crustlike Sr-Nd-Hf isotopic compositions. These data suggest that remelting of the lower crustal sulfide-bearing Cu-rich Jurassic cumulates, triggered by Cenozoic crustal thickening and/or subsequent slab break-off, led to the formation of giant Miocene PCDs. The spatial overlap and complementary metal endowment between subduction-and collision-related magmas may be used to evaluate the mineral potential for such deposits in other orogenic belts.
Environmental friendly sodium alginate (SA) cannot be used as a binder in aqueous batteries due to its high solubility in water. A water-insoluble polyvinylidene difluoride (PVDF) binder has been widely applied for an aqueous battery, in which the toxic and expensive organic solvent of N-methy-2-pyrrolidone (NMP) is required during the coating process. Herein, we report that the water-soluble SA can be utilized as a binder in aqueous Zn batteries because SA could cross-link with the Zn2+ ion to form a water-insoluble and mechanically super strong binder for electrodes. Aqueous Zn||LiFePO4 cells are assembled to demonstrate the performance of the SA binder for LiFePO4 cathodes. Due to the high adhesion strength of cross-linked Zn-SA, LiFePO4 with the SA binder displays a high capacity retention of 93.7% with a high Coulombic efficiency of nearly 100% after 100 cycles at a 0.2 C rate, while the capacity of LiFePO4 with the PVDF binder quickly decays to 84.7% after 100 cycles at 0.2 C. In addition, the LiFePO4 cathode with the SA binder also has smaller redox polarization, faster ion diffusion rate, and more favorable electrochemical kinetics than that with the PVDF binder.
Lithium ion batteries (LIBs) are widely used storage devices, which have a wide range of applications in electrical devices, hybrid electric vehicles, and for harvesting of renewable energy. [1] However, increasing demands for high-performance energy storage are unlikely to be satisfied by the theoretical capacities of the LIBs. [2] In particular, alternative cathode materials are required. [3] Recently, lithium-sulfur (Li-S) batteries have received attention owing to their high theoretical specificCarbon materials have received considerable attention as host cathode materials for sulfur in lithium-sulfur batteries; N-doped carbon materials show particularly high electrocatalytic activity. Efforts are made to synthesize N-doped carbon materials by introducing nitrogen-rich sources followed by sintering or hydrothermal processes. In the present work, an in situ hollow cathode discharge plasma treatment method is used to prepare 3D porous frameworks based on N-doped graphene as a potential conductive matrix material. The resulting N-doped graphene is used to prepare a 3D porous framework with a S content of 90 wt% as a cathode in lithium-sulfur cells, which delivers a specific discharge capacity of 1186 mAh g −1 at 0.1 C, a coulombic efficiency of 96% after 200 cycles, and a capacity retention of 578 mAh g −1 at 1.0 C after 1000 cycles. The performance is attributed to the flexible 3D structure and clustering of pyridinic N-dopants in graphene. The N-doped graphene shows high electrochemical performance and the flexible 3D porous stable structure accommodates the considerable volume change of the active material during lithium insertion and extraction processes, improving the long-term electrochemical performance.
A unique C-S@PANI composite with a conductive polymer spherical network (PSN) has been successfully designed and synthesized by a simple processing approach. The PSN framework is formed at the surface of the oxidized carbon black by conductive polymer self-assembly and grafting, followed by pouring elemental sulfur into the pores of the polymer matrix. As the cathode material for lithium-sulfur batteries, the C-S@PANI composite delivered a high specific capacity of 1453 mA h g(-1) at a 0.1 C current rate and a stable cycling performance of 948 mA h g(-1) after 200 cycles. The composite also demonstrated high capacities of 922 and 581 mA h g(-1) at 50 °C and 0 °C, respectively, after 200 cycles. The conductive PANI coatings were connected with the C-S core-shell composites to form a three-dimensional conducting network, which improves the utilization of the active mass and dual conduction of Li(+) and electrons, while at the same time encapsulating sulfur into the PANI hollow spherical network. The structure effectively inhibits the dissolution and migration of polysulfides into the electrolyte, while improving the cycling stability and the coulombic efficiency of the electrode at high current rates, especially the low temperature electrochemical properties of Li-S batteries.
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