Graphitic Carbon Quantum Dots Modified Nickel Cobalt Sulfide as Cathode Materials for Alkaline Aqueous Batteries

Carbon quantum dots(CQDs)as a new class of emerging materials have gradually drawn researchers’concern in recent years.In this work,the graphitic CQDs are prepared through a scalable approach,achieving a high yield with more than 50%.The obtained CQDs are further used as structure-directing and conductive agents to synthesize novel N,S-CQDs/NiCo2S4 composite cathode materials,manifesting the enhanced electrochemical properties resulted from the synergistic effect of highly conductive N,S-codoped CQDs offering fast electronic transport and unique micro-/nanostructured NiCo2S4 microspheres with Faradaic redox characteristic contributing large capacity.Moreover,the nitrogen-doped reduced graphene oxide(N-rGO)/Fe2O3 composite anode materials exhibit ultrahigh specific capacity as well as significantly improved rate property and cycle performance originating from the high-capacity prism-like Fe2O3 hexahedrons tightly wrapped by highly conductive N-rGO.A novel alkaline aqueous battery assembled by these materials displays a specific energy(50.2 Wh kg^−1),ultrahigh specific power(9.7 kW kg^−1)and excellent cycling performance with 91.5%of capacity retention at 3 A g^−1 for 5000 cycles.The present research offers a valuable guidance for the exploitation of advanced energy storage devices by the rational design and selection of battery/capacitive composite materials.

In-situ growth of vertically aligned nickel cobalt sulfide nanowires on carbon nanotube fibers for high capacitance all-solid-state asymmetric fiber-supercapacitors

Fiber-supercapacitors(FSCs)are promising power sources for miniature portable and wearable electronic devices.However,the development and practical application of these FSCs have been severely hindered by their low volumetric capacitance and narrow operating voltage.In this work,vertically aligned nickel cobalt sulfide(Ni Co2S4)nanowires grown on carbon nanotube(CNT)fibers were achieved through an in-situ two-step hydrothermal reaction method.The as-prepared Ni Co2S4@CNT fiber electrode exhibits a high volumetric capacitance of 2332 F cm-3,benefiting from its superior electric conductivity,large surface area,and rich Faradic redox reaction sites.Furthermore,a Ni Co2S4@CNT//VN@CNT(vanadium nitride nanosheets grown on CNT fibers)asymmetric fiber-supercapacitor(AFSC)was successfully fabricated.The device exhibits an operating voltage up to 1.6 V and a high volumetric energy density of 30.64m Wh cm-3.The device also possesses outstanding flexibility as evidenced by no obvious performance degradation under various bending angles and maintaining high capacitance after 5000 bending cycles.This work promotes the practical application of flexible wearable energy-storage devices.

Electrocatalytic water splitting at nitrogen-doped carbon layers-encapsulated nickel cobalt selenide

Generally,the catalytic overpotentials of hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)are unavoidable because of the low charge transfer.In this work,two strategies of alloying of Co with Ni and enclosing of electrocatalysts with carbonaceous materials were both used to accelerate the catalytic efficiency of cobalt selenide for water splitting.The nitrogen-doped carbon(NC)layer improves the reaction kinetics by efficient charge transfer.The alloying of metal into composited electrocatalysts can modify the electronic properties of host materials,thereby tuning the adsorption behavior of intermediate and improving the electrocatalytic activity.As expected,Nyquist plots reveal that the charge-transfer resistance(Rct)of nickel cobalt selenide encapsulated into nitrogen-doped carbon layer(CoNiSe/NC-3,Co:Ni=1:1)are just 5 and 9 for HER and OER,respectively,which are much lower than those of CoSe/NC-1(Co:Ni=1:0)(81 and 138)and CoNiSe/NC-3 without NC(CoNiSe-3)(54 and 25).With the high charge transfer and porous structure,CoNiSe/NC-3 shows good performance for both HER and OER.When current density reaches 10 m A cm-2,only 100 and 270 mV overpotentials are required for HER and OER,respectively.With the potential of 1.65 V,full water splitting also can be catalyzed by Co Ni Se/NC-3 with current density of 20 m A cm-2,suggesting that CoNiSe/NC-3 could be used as replacement for noble metal electrocatalysts.

Homogenous metallic deposition regulated by abundant lithiophilic sites in nickel/cobalt oxides nanoneedle arrays for lithium metal batteries

Although lithium(Li)metal delivers the highest theoretical capacity as a battery anode,its high reactivity can generate Li dendrites and"dead"Li during cycling,resulting in poor reversibility and low Li utilization.Inducing uniform Li plating/stripping is the core of solving these problems.Herein,we design a highly lithiophilic carbon film with an outer sheath of the nanoneedle arrays to induce homogeneous Li plating/stripping.The excellent conductivity and 3D framework of the carbon film not only offer fast charge transport across the entire electrode but also mitigate the volume change of Li metal during cycling.The abundant lithiophilic sites ensure stable Li plating/stripping,thereby inhibiting the Li dendritic growth and"dead"Li formation.The resulting composite anode allows for stable Li stripping/plating under 0.5 mA cm^(-2) with a capacity of 0.5 mA h cm^(-2) for 4000 h and 3 mA cm^(-2) with a capacity of3 mA h cm^(-2) for 1000 h.The Ex-SEM analysis reveals that lithiophilic property is different at the bottom,top,or channel in the structu re,which can regulate a bottom-up uniform Li deposition behavior.Full cells paired with LFP show a stable capacity of 155 mA h g^(-1) under a current density of 0.5C.The pouch cell can keep powering light-emitting diode even under 180°bending,suggesting its good flexibility and great practical applications.

Bimetallic nickel cobalt sulfides with hierarchical coralliform architecture for ultrafast and stable Na-ion storage

A series of bimetallic nickel cobalt sulfides with hierarchical micro/nano architectures were fabricated via a facile synthesis strategy of bimetallic micro/nano structure precursor construction-anion exchange via solvothermal method. Among the nickel cobalt sulfides with different Ni/Co contents, the coral-like Ni1.01Co1.99S4 (Ni/Co, 1/2) delivers ultrafast and stable Na-ion storage performance (350 mAh·g−1 after 1,000 cycles at 1 A·g−1 and 355 mAh·g−1 at 5 A·g−1). The remarkable electrochemical properties can be attributed to the enhanced conductivity by co-existence of bimetallic components, the unique coral-like micro/nanostructure, which could prevent structural collapse and self-aggregation of nanoparticles, and the easily accessibility of electrolyte, and fast Na+ diffusion upon cycling. Detailed kinetics studies by a galvanostatic intermittent titration technique (GITT) reveal the dynamic change of Na+ diffusion upon cycling, and quantitative kinetic analysis indicates the high contribution of pseudocapacitive behavior during charge-discharge processes. Moreover, the ex-situ characterization analysis results further verify the Na-ion storage mechanism based on conversion reaction. This study is expected to provide a feasible design strategy for the bimetallic sulfides materials toward high performance sodium-ion batteries.

Enriching redox active sites by interconnected nanowalls-like nickel cobalt phospho-sulfide nanosheets for high performance supercapacitors

Although transition metal phospho-sulfides deliver outstanding electrochemical performance,complex preparation methods hindered their further development.Herein,we report a facile one-step electrodeposition approach to deposit interconnected nanowalls-like nickel cobalt phospho-sulfide(Ni-Co-P-S)nanosheets onto the surface of carbon cloth.The thin Ni-Co-P-S nanosheets with multi-components and synergetic effects delivered rich active sites,further enhancing reversible capacitance.Therefore,the as-prepared Ni-Co-P-S electrode materials exhibit excellent electrochemical performance in a three-electrode system,showcasing a high specific capacitance of 2744 F/g at 4 A/g.The full supercapacitors based on Ni-Co-P-S as positive electrode and active carbon as negative electrode showcase a high specific capacitance of 110.9 F/g at 1 A/g,impressive energy density of 39.4 Wh/kg at a power density of 797.5 W/kg in terms of excellent cycling stability(91.87%retention after 10,000 cycles).This simple electrode position strategy for synthesizing Ni-Co-P-S can be extended to prepare electrode materials for various sustainable electrochemical energy storage/conversion technologies.

Recovery of nickel,cobalt,copper and zinc in sulphate and chloride solutions using synergistic solvent extraction

A number of synergistic solvent extraction(SSX) systems have been developed to recover nickel,cobalt,zinc and copper from sulphuric and chloride leach solutions by the solvent extraction team of CSIRO,Australia.These include(1) Versatic 10/CLX50 system for the separation of Ni from Ca in sulphate solutions,(2) Versatic 10/4PC system for the separation of Ni and Co from Mn/Mg/Ca in sulphate solutions,(3) Cyanex 471X/HRJ-4277 system for the separation of Zn from Cd in sulphate solutions,(4) Versatic 10/LIX63 system for the separation of Co from Mn/Mg/Ca in sulphate solutions,(5) Versatic 10/LIX63/TBP system for separation of Ni and Co from Mn/Mg/Ca in sulphate solutions,(6) Versatic 10/LIX63 system for the separation of cobalt from nickel in sulphate solutions by difference in kinetics,(7) Cyanex 272/LIX84 system for the separation of Cu/Fe/Zn from Ni/Co in sulphate solutions,(8) Versatic 10/LIX63/TBP system to recover Cu/Ni from strong chloride solutions,and(9) Versatic10/LIX63 system to separate Cu from Fe in strong chloride solutions.The synergistic effect on metal separation and efficiency is presented and possible industrial applications are demonstrated.The chemical stability of selected SSX systems is also reported.

Extraction studies of cobalt (Ⅱ) and nickel (Ⅱ) from chloride solution using PC88A

Solvent extraction study of cobalt and nickel were carried out from a chloride solution with a high ratio of Co to Ni using the sodium salt of PC88A as extractant diluted in kerosene. The solution was generated in batches by leaching a tungsten super alloy scraps. The results show that extraction rate of metal ions increases with increase of aqueous phase pH value. The pH0.5 value difference of 1.40 with PC88A indicates the possible separation of cobalt and nickel. Increase of the concentration of the solvent can enhance the percentage extraction of both metal ions. Improvement of temperature is beneficial to extraction separation of cobalt and nickel. Extraction and stripping processes were also studied in a cross-current solvent extraction unit and the results were also given.

Separation of nickel, cobalt and copper by solvent extraction with P204

Nickel, cobalt and copper were separated by solvent extraction with P204. The experimental results show that [Co(NH 3) 6] 3+ is an inert complex in extraction kinetics, therefore cobalt can be separated from nickel and copper by non equilibrium solvent extraction. Under the conditions of temperature 25?℃, contact time of two phases 10?min, phase ratio 1∶1, aqueous pH 10.10 and concentration of P204 20%, [Co(NH 3) 6] 3+ is hardly extracted by P204, while the percentage extractions of nickel and copper are 79.3% and 93.9% respectively. Nickel and copper are separated by equilibrium solvent extraction with P204. Under the conditions of temperature 25?℃, contact time of two phases 1?min, phase ratio 1∶1, equilibrium pH 4.01 and concentration of P204 20%, the separation factor of copper and nickel is 216.

Simultaneous spectrophotometric determination of cobalt,copper and nickel using 1-(2-thiazolylazo)-2-naphthol by chemometrics methods

The simultaneous determination of cobalt, copper and nickel using 1-（2-thiazolylazo）-2-naphthol （first figure of this article） by spectrophotometric method is a difficult problem in analytical chemistry, due to spectral interferences. By multivariate calibration methods, such as partial least squares （PLS） regression, it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration range. Orthogonal signal correction （OSC） is a preprocessing technique used for removing the information unrelated to the target variables based on constrained principal component analysis. OSC is a suitable preprocessing method for PLS calibration of mixtures without loss of prediction capacity using spectrophotometric method. In this study, the calibration model is based on absorption spectra in the 550-750-nm range for 21 different mixtures of cobalt, copper and nickel. Calibration matrices were formed from samples containing 0.05-1.05, 0.05-1.30 and 0.05-0.80 μg·mL^-1 for cobalt, copper and nickel, respectively. The root mean square error of prediction （RMSEP） for cobalt, copper and nickel with OSC and without OSC were 0.007, 0.008, 0.011 and 0.031,0.037, 0.032 μg· mL^-1, respectively. This procedure allows the simultaneous determination of cobalt, copper and nickel in synthetic and real samples and good reliability of the determination was proved.

Extraction and separation of nickel and cobalt from saprolite laterite ore by microwave-assisted hydrothermal leaching and chemical deposition

Extraction and separation of nickel and cobalt from saprolite laterite ore were studied by using a method of microwave-assisted hydrothermal leaching and chemical deposition. The effects of leaching temperature and time on the extraction efficiencies of Ni2＋ and Co2＋ were investigated in detail under microwave conditions. It is shown that the extraction efficiencies of Ni2＋ and Co2＋ from the ore pre-roasted at 300℃ for 5 h were 89.19% and 61.89% when the leaching temperature and time were about 70℃ and 60 min, respectively. For the separation process of Ni and Co, the separation of main chemical components was performed by adjusting the pH values of sulfuric leaching solutions using a NaOH solution based on the different pH values of precipitation for metal hydroxides. The final separation efficiencies of Ni and Co were 77.29% and 65.87%, respectively. Furthermore, the separation efficiencies of Fe of 95.36% and Mg of 92.2% were also achieved at the same time.

Process development for the direct solvent extraction of nickel and cobalt from nitrate solution:aluminum,cobalt,and nickel separation using Cyanex 272

A direct solvent extraction（DSX） process for purifying nickel and cobalt from the nitric acid leach solution of nickel laterite ores was conceived and experimentally probed. The proposed process consists of two solvent extraction（SX） steps but with only one extractant - bis（2,4,4-trimethylpentyl）phosphinic acid（Cyanex？ 272） - used in both steps. The first extraction step involved the removal of aluminum and zinc, whereas the second extraction step involved the separation of cobalt along with manganese from nickel. The experimental results showed essentially quantitative removal of aluminum（〉97%） and zinc（〉99%） in a single extraction stage using 20vol% Cyanex 272 at pH 2.1. Some cobalt（32%） and manganese（55%） were co-extracted but were easily scrubbed out completely from the loaded organic phase using dilute sulfuric acid at pH ≤ 1.38. Cobalt and manganese in the first extraction raffinate were extracted completely in four extraction stages at staggered pH values of 4.0, 4.4, 4.5, and 4.0 in the first, second, third, and fourth stages, respectively, using also 20vol% Cyanex 272. A small amount of nickel（up to 6.6%） was co-extracted but was easily scrubbed out completely with dilute sulfuric acid at pH 2.0. A flow diagram showing the input and output conditions and the metals separated under the deduced optimum conditions is presented.

Dialkyl phosphinic acids:Synthesis and applications as extractant for nickel and cobalt separation

Three kinds of dialkylphosphinic acids(DAPAs),i.e.dihexylphophinic acid(DHPA),di-(2,4,4-trimethylpentyl) phosphinic acid(DTMPPA)and didecylphophinic acid(DDPA),were synthesized through free radical addition reaction.The influence of the types of initiator,reation time and reaction temperature on the yield of DAPAs were investigated.The products were characterized by NMR and MS.By using DHPA,DTMPPA and DDPA(10%in kerosene)as extractants,the extraction of Co2 +and Ni2 +in sulphate medium at different equilibrium pH values were measured.The results show that the maximum yield of DHPA, DTMPPA and DDPA can all be achieved at about 130℃under the initiation of di-tert-butyl peroxide(DTBP).All the extraction of cobalt with respect to DHPA,DDPA and DTMPPA precedes that of nickel.The difference in pH1/2 value(defined as the pH at which 50%metal extraction occurs)between cobalt and nickel increases in the following sequence from large to small:DHPA,DDPA and DTMPPA,which indicates that the separation ability for cobalt and nickel ascends from DHPA,DDPA to DTMPPA.

Factors Research on the Influence of Leaching Rate of Nickel and Cobalt from Waste Superalloys with Sulfuric Acid

Unlike the reported leaching technologies of waste superalloys, the process of the “atomized spray-sulfuric acid leaching nickel and cobalt” technology was put forward in the present work according to the compositions of waste superalloys. The effects of sulfuric acid temperature, concentration, leaching time, stirring speed and size of superalloys on leaching of Ni and Co from waste superalloys have been mainly investigated, and the optimum leaching conditions were determined and reported. The leaching rates for nickel and cobalt were 96.68% and 96.63%, respectively, and the contents of nickel and cobalt in leaching slag were 6.77% and 0.96%, respectively. The obtained leaching solution containing Ni and Co could be used for production of Ni and Co products after removal.

Synthesis and Catalytic Activity of Nickel(Ⅱ)and Cobalt(Ⅱ) Complexes Involving Chiral Leucinol

The title nickel complex I and cobalt complex II were obtained separately from the direct reaction of D-（＋）-leucinol with Ni（II） chloride and L-（-）-leucinol with Co（II） acetate tetra- hydrate in anhydrous methanol. The crystal structures of I and II were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I： [Ni（C18H45N3O3）]Cl2, orthorhombic, P212121, a = 11.2807（9）, b = 14.7115（11）, c = 16.3580（13） A, V = 2714.7（4） A3, Z = 4, Pcalcd = 1.177 Mg/m3, the final R = 0.0407, and 16539 reflections observed with I 〉 2σ（/）; For II： [Co（C45HI08N6015）], trigonal, R3：H, a = 23.981（3）, b =23.981（3）, c = 10.8925（15） A, γ = 120°, V = 5425.1（14） A3, Z = 3, Pcalcd = 1.002 Mg/m3, the final R = 0.0625 for 16556 observed reflections with I 〉 2σ（I）. The complexes were then used to catalyze the Henry reaction and obtained good catalytic results. The catalytic activity of the complexes was determined by IH NMR. And research is going towards the application to other organic reactions such as cyanosilylation reaction.

Simple, Selective, and Sensitive Spectrophotometric Method for Determination of Trace Amounts of Nickel(Ⅱ), Copper (Ⅱ), Cobalt (Ⅱ), and Iron (Ⅲ) with a Novel Reagent 2-Pyridine Carboxaldehyde Isonicotinyl Hydrazone

A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone（2-PYAINH） was synthesized and studied for the spectrophotometric determination of nickel, copper, cobalt, and iron in detail. At a pH value of 7.0, 9,0, 9.0, and 8.0, respectively, which greatly increased the selectivity; nickel, copper, cobalt, and iron reacted with 2-PYAINH to form a 1：2 yellow-orange, 1：2 yellow-green, 1：2 yellow and 1：1 yellow complexes, with absorption peaks at 363, 352, 346, and 359 nm, respectively. Under the optimal conditions, Beer＇s law was obeyed over the ranges of 0.01-1.4, 0.01-1.5, 0.01-2.7, and 0.01-5.4 mg/L respectively. The apparent molar absorptivity and Sandell＇s sensitivities were 8.4×10^4, 5.2×10^4, 7.1×10^4, and 3.9×10^4 L·mol^-l·cm^-1, respectively, and 0.00069, 0.0012, 0.00078, and 0.0014 μg·cm2, respectively. The detection limits were found to be 0.001, 0.002, 0.003, and 0.01 mg/L, respectively. The detailed study of various interfering ions to make the method more sensitive was carried out and selective and several real samples were analyzed with satisfactory results.

Stable overall water splitting in an asymmetric acid/ alkaline electrolyzer comprising a bipolar membrane sandwiched by bifunctional cobalt-nickel phosphide nanowire electrodes

Water splitting has been proposed to be a promising approach to producing clean hydrogen fuel.The two half-reactions of water splitting,that is,the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),take place kinetically fast in solutions with completely different pH values.Enabling HER and OER to simultaneously occur under kinetically favorable conditions while using exclusively low-cost,earth-abundant electrocatalysts is highly desirable but remains a challenge.Herein,we demonstrate that using a bipolar membrane(BPM)we can accomplish HER in a strongly acidic solution and OER in a strongly basic solution,with bifunctional self-supported cobaltnickel phosphide nanowire electrodes to catalyze both reactions.Such asymmetric acid/alkaline water electrolysis can be achieved at 1.567 V to deliver a current density of 10 mA/cm2 with ca.100%Faradaic efficiency.Moreover,using an“irregular”BPM with unintentional crossover the voltage needed to afford 10 mA/cm2 can be reduced to 0.847 V,due to the assistance of electrochemical neutralization between acid and alkaline.Furthermore,we show that BPM-based asymmetric water electrolysis can be accomplished in a circulated single-cell electrolyzer delivering 10 mA/cm2 at 1.550 V and splitting water very stably for at least 25 hours,and that water electrolysis is enabled by a solar panel operating at 0.908 V(@13 mA/cm2),using an“irregular”BPM.BPMbased asymmetric water electrolysis is a promising alternative to conventional proton and anion exchange membrane water electrolysis.

Separation of cobalt and nickel by non-equilibrium solvent extraction

The separation of cobalt and nickel in the ammoniacal sulfate solution by non equilibrium solvent extraction with a phosphate (P303) as extractant was studied. In the experiment, the effects of equilibrium pH value in aqueous phase, contact time of the two phases, the air blowing time for feed liquor in the open beaker on percentage extraction of cobalt and nickel and percentage reextraction of nickel from the loaded organic phase with dilute H 2SO 4. etc were studied. The results showed that: Co(Ⅱ) can be oxidized to Co(Ⅲ) ammino complex by adding (NH 4) 2S 2O 8 or blowing air to the aqueous phase, and Co(Ⅲ) ammino complex is a kind of kinetically inert complex. Its extractive speed is very slow, while the nickel′s is much faster than that of cobalt. By controlling the contact time of the two phases, nickel can be separated from cobalt by non equilibrium solvent extraction. Then nickel was reextracted from the loaded organic phase with dilute H 2SO 4.

Syntheses and Crystal Structures of Cobalt(II) and Nickel(II) Coordination Polymers with 3-Aminobenzoic Acid Ligand

Two coordination polymers, [ML2]n （M = Co （1）, Ni （2）, L = 3-aminobenzoic acid anion）, were synthesized by hydrothermal reaction, and their crystal structures were determined by X-ray diffraction analysis. Both compounds crystallize in monoclinic, space group P21/n with a = 8.8029（8）, b = 4.5297（4）, c = 15.2002（14）A°, β= 105.6280（10）°, C14H12CoN2O4, Mr= 331.19, Z= 2, V = 583.69（9）A°^3 Dc= 1.884 g/cm^3,μ=1.490 mm^-1, F（000） = 338, R = 0.0234 and wR = 0.0679 for 1337 observed reflections （I 〉 2σ（I）） for 1, and a = 8.7501（7）, b = 4.5191（4）, c = 15.1448（12） A°,β = 105.7730（10）° C14H12 NiN2O4, Mr = 330.97, Z = 2, V = 576.31（8）A°3, Dc = 1.907 g/cm^3,μ = 1.703 mm^-1, F（000） = 340, R = 0.0206 and wR = 0.0572 for 1209 observed reflections （I 〉 2σ（I）） for 2. In the title complexes, the M （Ⅱ） ion presents an octahedral geometry with four oxygen donors in the equatorial positions and two nitrogen donors in the axial positions. Each of the complexes has a two-dimensional network structure that is formed by the bridging of the ligand in a μ3-bridging mode via its amino and carboxyl groups.

Chemical forms of cobalt and nickel extracted by M1,M3 and CaCl_(2)-DTPA

Mehlich 1(M1), mehlich 3(M3) and CaCl 2 DTPA have been used to predict the available micronutrient in soil. However, the forms of micronutrient extractable by these extractants are not known. In the present study, ten soils, collected from five provinces and the capital of China, representing a wide range of chemical and physical properties, were analyzed by sequential extraction to isolate five forms of cobalt and nickel, they are exchangeable, carbonate bound, Fe Mn oxide bound, organically bound and residual forms. The chemical forms extracted by M1, M3 and CaCl 2 DTPA were also investigated. The results show strong correlation between the carbonate bound or organically bound forms of Co or Ni and the amounts of extractable by any of the above three extractants. The main forms extracted by these extractants are carbonate and organically bound forms. The ranking of these three extractants for extraction of Co and Ni are M1>M3=CaCl 2 DTPA and M1=M3>CaCl 2 DTPA, respectively.