Basalt Petrology, Water Chemistry, and Their Impact on the CO_(2) Mineralization Simulation at Leizhou Peninsula Sites, Southern China

Mineral carbonation, which precipitates dissolved carbon dioxide(CO_(2)) as carbonate minerals in basaltic groundwater environments, is a potential technique for negative emissions. The Leizhou Peninsula in southwest Guangdong province has extensive basalt, indicating a promising potential for CO_(2) storage through rapid mineralization. However, understanding of the basic geological setting, potential, and mechanisms of CO_(2) mineralization in the basalts of the Leizhou Peninsula is still limited. The mineralization processes associated with CO_(2)storage at two candidate sites in the area are investigated in this paper: Yongshi Farm and Tianyang Basin(of the dried maar lake). Petrography,rock geochemistry, basalt petrophysical properties, and groundwater hydrochemistry analyses are included in the study. Numerical simulation is used to examine the reaction process and its effects. The results show that basalts in the study areas mainly comprise plagioclase, pyroxene, and Fe–Ti oxides, revealing a total volume fraction exceeding 85%. Additionally, small amounts of quartz and fayalite are available, with volume fractions of 5.1% and 1.0%, respectively. The basalts are rich in divalent metal cations, which can form carbonate minerals, with an average of approximately 6.2 moles of metal cations per 1 kg of rock. The groundwater samples have a pH of 7.5–8.2 and are dominated by the Mg–Ca–HCO3 type. The basalts demonstrate a porosity range of 10.9% to 28.8%, with over 70% of interconnected pores. A 20-year geochemical simulation revealed that CO_(2) injection dissolves primary minerals, including anorthite, albite, and diopside, while CO_(2)mineralization dissolves precipitation secondary minerals, such as calcite, siderite, and dolomite. Furthermore, a substantial rise in pH from 7.6to 10.6 is observed in the vicinity of the injected well, accompanied by a slight reduction in porosity from 20% to 19.8%. Additionally, 36.8% of the injected CO_(2) underwent complete mineralization within five years, revealing an increasing percentage of 66.1% if the experimental period is extended to 20 years. The presence of abundant divalent metal cations in basalts and water-bearing permeable rocks in the Leizhou Peninsula supports the potential for mineral carbonation in basalts, as indicated by the geochemical simulation results. Additional research is necessary to identify the factors that influence the CO_(2) mineralization, storage, and sensitivity analysis of basalt in the Leizhou Peninsula.

Poly(vinylidene fluoride) Modified Commercial Paper as a Separator with Enhanced Thermal Stability and Electrolyte Affinity for Lithium-ion Battery

Commercial paper is of great potential as a ready-made substrate to make battery separator due to superior electrolyte affinity of cellulose.Nevertheless,the direct utilization of commercial paper as a separator is impracticable because of its micro-sized holes between coarse cellulose fibers,which might induce short circuits.Herein,a novel reinforced composite separator is proposed by modifying commercial paper(CP)with highdielectric polymer poly(vinylidene fluoride)(PVDF)via a vacuum filtration method.The paper substrate enables excellent electrolyte wettability and high ionic conductivity of the CP-PVDF composite separator due to the superior electrolyte affinity of cellulose molecule.Meanwhile,the strong hydrogen bonds between F atoms in PVDF and H atoms in the-OH groups of cellulose endow the separator with high thermal stability and mechanical strength.Moreover,the CP-PVDF exhibits outstanding interfacial compatibility toward Li metal anode and guarantees the prominent cycle durability of symmetric Li/Li cells up to 600 h.As a result,the LiFePO_(4)/Li cells assembled with CP-PVDF separator show dramatic rate performance with high discharge capacity of 113.7 m Ah g^(-1),and prolonged cycle life at 5 C.This work indicates that the paper-based composite membranes possess great potential for high-safety and electrochemical performance batteries.

Synthesis of cobalt-doped ZnO/rGO nanoparticles with visible-light photocatalytic activity through a cobalt-induced electrochemical method

ZnO is a semiconductor photocatalyst widely applied in photodegradation of organic pollutants and in photoelectric conversion. ZnO exhibits low photocatalytic activity due to poor absorption in the visible region. In this work, a novel cobalt-induced electrochemical growth method was developed to synthesize cobalt-doped ZnO/rGO nanoparticles in an aqueous solution at room temperature. Cobalt-doped ZnO/rGO nanoparticles exhibited wider visible-light absorption band ranging from 400 nm to 700 nm due to cobalt doping. The surface structure of ZnO formed by the cobalt-induced electrochemical method without other ions is suitable for photocatalytic reactions. The cobalt-doped ZnO/rGO nanoparticles were found to exhibit in photodegradation and photo-electrochemical measurements and exhibited enhanced photocatalytic activity under visible-light irradiation.

Petrology and geochemistry of the Shilu Fe-polymetallic ore deposit in Hainan Province of South China: Implications for the origin of Neoproterozoic BIFs

The Shilu Fe-polymetallic ore deposit,a famous hematite-rich Fe-ore deposit,is situated at the western Hainan Province of south China.The deposit characterizes the upper Fe ores and the lower Co-Cu ores,which are mainly hosted within a low-grade to medium-grade,dominantly submarine metamorphosed siliciclastic and carbonate sedimentary succession of the Neoproterozoic Shilu Group.Three facies types of metamorphosed BIFs,i.e.the oxide facies,the silicate-oxide facies and the sulfide-carbonate facies BIFs,are identified within the sixth sequence of the Shilu Group.The oxide facies BIF(i.e.the Fe-rich itabirites or ores)consists of alternating hematite-rich microbands with quartz-rich microbands;the silicate-oxide facies BIF(i.e.the Fe-poor itabirites or ores)comprises alternating millimeter-to a few tens meter-scale,magnetite-hematite-rich bands with calcsilicate-rich(garnet+actinolite+diopside+epidote+quartz)meso-to microbands;and the sulfide-carbonate facies BIF(i.e.the Co-Cu ores)contains alternating macro-to mesobands of Co-bearing pyrite and pyrrhotite,and chalcopyrite with mesobands of dolomite+calcite+diopside+quartz and/or chlorite+sericite+quartz.The blastooolitic,blastopelletoid blastocolloidal and blastopsammitic textures,and blasobedding structures which most likely represent primary sedimentation are often observed in these BIF facies.The interbedded host rocks with the BIFs mainly are the pyroxene-amphibole rocks and the banded or impure dolostones,and also contain banded or laminated structures,and lepido-gra-noblastic,nematoblastic and/or blastoclastic textures.Compositionally,the main host rocks,the pyroxene-amphibole rocks contain basic-intermediate SiO_2(~54.00 wt.%),CaO(~14.19 wt.%),MgO(~9.68 wt.%)and Al_2O_3(~8.49 wt.%)with a positive correlation between Al_2O_3 and TiO_2.The UCC-like Zr and Hf abundances,high Ba content andεNd(t)value(^-5.99)as well as the ratios of La/YbPAAS(0.17~1.00),δEuPAAS(0.88~1.12)andδCePAAS(0.93~1.13)commonly reveal that the protoliths to this type rocks are hydrogenic with a large contribution of terrigenous sediments and minor hydrothermal input.The high CaO+MgO+LOI contents and the extremely low trace element and REEconcentrations as well as the ratios of Y/Ho(44~45),δEuPAAS(1.13~1.57)andδCePAAS(0.69~0.98)reflect a marine origin with minor terrigenous materials for the banded or impure dolostones.Moreover,this type rocks also account for a negativeεNd(t)value(^-7.49).The oxide facies BIF is dominated by Fe_2O_3+FeO(~75.59wt.%)and SiO_2(~20.47 wt.%)with aεNd(t)value of^-6.10.The variable contents in Al_2O_3,TiO 2,K2O,Na2O,Zr,Hf and∑REE,and variable ratios of Y/Ho(24~39)andδEuPAAS(0.86~11.07)suggest the precursor sediments to this facies BIF are admixtures of sea-floor hydrothermal fluids and seawaters with minor involvement of detrital components.Compared to the oxide facies BIF,the silicate-oxide facies BIF is lower in Fe_2O_3+Fe O(~39.81wt.%)and Ba but higher in SiO_2(~42.54 wt.%),Al2O3(~3.60 wt.%),TiO_2(~0.19 wt.%),MgO(~1.12 wt.%),CaO(~9.06 wt.%),K_2O(~0.98 wt.%),Mn and Zr.The ratios of Y/Ho(25~34),La/YbPAAS(0.14-0.74)andδEuPAAS(0.91~1.12)most likely are linked to higher degree of detrital contamintants.While the sulfide-caronate facies BIF is main but variable in Fe_2O_3+Fe O(15.79~57.91 wt.%),SiO 2(0.54~61.52 wt.%),MgO(0.12~16.09wt.%),CaO(0.17~23.41 wt.%)and LOI(8.28-30.06 wt.%).The generally low contents in trace elements(including REE)except for an obvious enrichment in Pb,and the positive Ce anomalies(δCePAAS=1.04~1.95)and negative Pr anomalies(δPrPAAS=0.67~0.93),as well as the variable ratios ofδEuPAAS(0.72~1.71),La/YbPAAS(0.26~1.60)and Y/Ho(26~57)suggest that the precursors to the sulfide-carbonate facies BIF mainly are metalliferious sediments from deep-marine hydrotheral source with minor detrital components.The T2DM ages(ca.2.0 Ga)imply that the Shilu BIFs and interbedded host rocks contain a component with Paleoproterozoic crustal residence age due to a significant crustal accretion event at ca.2.0 Ga in Hainan Island.In connection with the petrographical and mineralogical relationship,we conclude that the precursor precipitates to the Shilu BIFs are variable degree of admixtures of the Fe-Co-Cu-(Si)-rich hydrothermal fluids and detrital components from seawater and fresh water carring continental landmass;whereas the protolith to the main interbedded host rocks,i.e.the pyroxene-amphibole rocks,most likely was terrigenous,fine-grained clastic-sediments but with significant input of hydrothermal fluids in a seawater environment.As a result,a continent marginal marine basin is proposed for deposition of the Shilu BIFs and interbedded host rocks.Sea-level fluctuations caused by marine transgression–regressions possibly contributed to changes in the composition and varied input of the terrigenous sediments.

Uniform lithium deposition induced by copper phthalocyanine additive for durable lithium anode in lithium-sulfur batteries

Copper phthalocyanine(CuPc)is adopted as an electrolyte additive to stabilize lithium anode for lithiumsulfur(Li-S)batteries.CuPc with a planar molecular structure and lithiophilic N-containing group,is likely to be adsorbed on the surface of Li anode to form a coating layer,which can restrict the direct contact between Li anode and solvents,and guide the uniform deposition of Li^(+)ions.The Li||Li symmetric cells demonstrate a stable cycle performance,and Li||Cu cells show high Coulombic efficiencies.In Li-S batteries,the formed stable solid-electrolyte interface(SEI)film containing copper sulfides can protect Li anode from the polysulfide corrosion and side reactions with the electrolyte,leading to the compact and smooth surface morphology of Li anode.Therefore,the Li-S batteries with CuPc additive deliver much higher capacity,better cycle performance and rate capability as compared to the one without CuPc additive.

An organometallic salt as the electrolyte additive to regulate lithium polysulfide redox and stabilize lithium anodes for robust lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries with high theoretical specific energy are considered to be one of the highly promising next-generation energy storage systems.However,the shuttle effect of lithium polysulfides(LiPSs)and the interfacial instability of Li anodes have seriously hindered the practical application of Li-S batteries.Optimizing the electrolyte composition with additives can significantly improve the battery performance and has attracted great attention.Herein,we propose an organometallic salt,i.e.,nickel bromide dimethoxyethane(NiBr_(2)DME),as an electrolyte additive,which serves as the dual function of regulating LiPSs redox and synchronously stabilizing Li anodes.We reveal that NiBr_(2)DME can interact with LiPSs via Ni-S and Li-Br bonds,and accelerate the mutual transformation of LiPSs,thus reducing the accumulation of LiPSs in the electrolyte.In addition,NiBr_(2)DME can form a stable LiBr-containing interfacial layer on the Li metal surface,and promote the uniform electrodeposition of Li^(+)ions,and inhibit the formation of Li dendrites.Thus,Li-S batteries with a concentration of 0.5 mmol L^(-1)NiBr_(2)DME show an initial capacity of 919.8 mAh g^(-1)at 0.2 C,and a high capacity retention of 89.3%after 100 cycles.Even at the 4 C rate,a high discharge capacity of 602.9 mAh g^(-1)is achieved.Surprisingly,the good cycling performance is maintained under poor electrolyte conditions with sulfur loading of 4.8 mg cm^(-2)and electrlyte/sulfur ratio of 5µL mg^(-1).This work provides a positive solution to achieve the suppression of shuttle effect,the regulation of LiPSs redox and the stabilization of Li anodes.

Improving sulfur transformation of lean electrolyte lithium-sulfur battery using nickel nanoparticles encapsulated in N-doped carbon nanotubes

Efficient redox reactions of lean electrolyte lithium-sulfur(Li-S)batteries highly rely on rational catalyst design.Herein,we report an electrocatalyst based on N-doped carbon nanotubes(CNT)-encapsulated Ni nanoparticles(Ni@NCNT)as kinetics regulators for Li-S batteries to propel the polysulfide-involving multiphase transformation.Moreover,such a CNT-encapsulation strategy greatly prevents the aggregation of Ni nanoparticles and enables the extraordinary structural stability of the hybrid electrocatalyst,which guarantees its persistent catalytic activity on sulfur redox reactions.When used as a modified layer on a commercial separator,the Ni@NCNT interlayer contributes to stabilizing S cathode and Li anode by significantly retarding the shuttle effect.The corresponding batteries with a 3.5 mg cm^(−2)sulfur loading achieve the promising cycle stability with~85%capacity retention at the electrolyte/sulfur ratios of 5 and 3μL mg^(−1).Even at a high loading of 12.2 mg cm^(−2),the battery affords an areal capacity of 7.5 mA h cm^(−2).

Needle-like cobalt phosphide arrays grown on carbon fiber cloth as a binder-free electrode with enhanced lithium storage performance

Cobalt phosphide(CoP) is a promising anode candidate for lithium-ion batteries(LIBs) due to its high specific capacity and low working potential.However,the poor cycling stability and rate performance,caused by low electrical conductivity and huge volume variation,impede the further practical application of CoP anode materials.Herein,we report an integrated binder-free electrode featuring needle-like CoP arrays grown on carbon fiber cloth(CC) for efficient lithium storage.The as-prepared CoP/CC electrode integrates the advantages of 1 D needle-like CoP arrays for efficient electrolyte wettability and fast cha rge transpo rtation,and 3 D CC substrate for superior mechanical stability,flexibility and high conductivity.As a result,the CoP/CC electrode delivers an initial specific capacity of 1283 mAh/g and initial Coulombic effeciencies of 85.4%,which are much higher than that of conventional CoP electrode.Notably,the Co P/CC electrode shows outstanding cycling performance up to 400 cycles at 0.5 A/cm^(2) and excellent rate performance with a discharge capacity of 549 mAh/g even at 5 A/cm^(2).This work demonstrates the great potential of integrated CoP/CC hybrid as efficient bind-free and freestanding electrode for LIBs and future flexible electronic devices.