Preparation of lithium-ion battery anode materials from graphitized spent carbon cathode derived from aluminum electrolysis

Graphitized spent carbon cathode(SCC)is a hazardous solid waste generated in the aluminum electrolysis process.In this study,a flotation-acid leaching process is proposed for the purification of graphitized SCC,and the use of the purified SCC as an anode material for lithium-ion batteries is explored.The flotation and acid leaching processes were separately optimized through one-way experiments.The maximum SCC carbon content(93wt%)was achieved at a 90%proportion of−200-mesh flotation particle size,a slurry concentration of 10wt%,a rotation speed of 1600 r/min,and an inflatable capacity of 0.2 m^(3)/h(referred to as FSCC).In the subsequent acid leaching process,the SCC carbon content reached 99.58wt%at a leaching concentration of 5 mol/L,a leaching time of 100 min,a leaching temperature of 85°C,and an HCl/FSCC volume ratio of 5:1.The purified graphitized SCC(referred to as FSCC-CL)was utilized as an anode material,and it exhibited an initial capacity of 348.2 mAh/g at 0.1 C and a reversible capacity of 347.8 mAh/g after 100 cycles.Moreover,compared with commercial graphite,FSCC-CL exhibited better reversibility and cycle stability.Thus,purified SCC is an important candidate for anode material,and the flotation-acid leaching purification method is suitable for the resourceful recycling of SCC.

Oxidative exfoliation of spent cathode carbon:A two-in-one strategy for its decontamination and high-valued application

Spent cathode carbon(SCC)from aluminum electrolysis is a potential graphite resource.However,full use of the SCC remains a challenge,since it contains many hazardous substances(e.g.,fluoride salts,cyanides),encapsulated within the thick carbon layers and thus posing serious environmental concerns.This work presents a chemical oxidative exfoliation route to achieve the recycling of SCC and the decontaminated SCC with high-valued graphene oxide(GO)-like carbon structures(SCC-GO)is applied as an excellent adsorbent for organic pollutants.Specifically,after the oxidative exfoliation,the embedded hazardous constituents are fully exposed,facilitating their subsequent removal by aqueous leaching.Moreover,benefiting from the enhanced specific surface areas along with abundant O-containing functional groups,the as-produced SCC-GO,shows an adsorption capacity as high as 347 mg·g^(-1)when considering methylene blue as a pollutant model,which exceeds most of the recently reported carbon-based adsorbents.Our study provides a feasible solution for the efficient recycling of hazardous carbonaceous wastes.

Ambient electrical conductivity of carbon cathode materials for aluminum reduction cells

The ambient electrical conductivity (AEC) of carbon cathode materials was investigated in respect to their open porosity, crystal structure and graphite content using hydrostatic method, four-probe technique and X-ray diffraction (XRD), respectively. The AEC is proportional to the specific conductivity (σ0) and the exponential of (1?ε) (ε is porosity) by a quasi-uniform formula based on the percolation theory. Theσ0 can reflect the intrinsic conductivity of the carbon cathodes free of pores, and it depends on the mean crystallite size parallel to the layer (002). The exponentn is dependent on the materials nature of the cathode aggregates, while an averaged value, 4.65, can practically work well with 5 types of cathode materials. The calculation ofσ0 can be extended to the graphitic cathodes containing different aggregates using the simple rule of mixture.

Iron and copper recovery from copper slags through smelting with waste cathode carbon from aluminium electrolysis

To recover metal from copper slags,a new process involving two steps of oxidative desulfurization followed by smelting reduction was proposed in which one hazardous waste(waste cathode carbon)was used to treat another(copper slags).The waste cathode carbon is used not only as a reducing agent but also as a fluxing agent to decrease slag melting point.Upon holding for 60 min in air atmosphere first and then smelting with 14.4 wt%waste cathode carbon and 25 wt%CaO for 180 min in high purity Ar atmosphere at 1450℃,the recovery rates of Cu and Fe reach 95.89%and 94.64%,respectively,and meanwhile greater than 90%of the fluoride from waste cathode carbon is transferred into the final slag as CaF_(2) and Ca_(2)Si_(2)F_(2)O_(7),which makes the content of soluble F in the slag meet the national emission standard.Besides,the sulphur content in the obtained Fe-Cu alloy is low to 0.03 wt%.

An environmentally benign and sustainable process for carbon recovery and efficient defluorination of spent carbon cathode

A systematic and green low-temperature sulfation roasting−water leaching strategy was put forward to achieve a very high fluorine removal rate of 97.82%for spent carbon cathode(SCC),which was believed as a hazardous solid waste.And the carbon could be recycled with a purity of 90.29 wt.%in the flaky microstructure.Thermodynamic analysis and the results of SEM,XRD and EDS indicate that most of the fluoride could convert into water-soluble sulfate at low temperature.And the highest fluorine removal rate could be obtained when<0.15 mm SCC particles were mixed with sulfuric acid at a liquid-to-solid ratio of 1:1,and then roasted at 300℃ for 0.5 h.The sulfate was removed to purify the carbon via water-leaching process.Avrami exponents and corresponding activation energy for the roasting and leaching process demonstrated that both processes are controlled by diffusion.

Revealing dual capacitive mechanism of carbon cathode toward ultrafast quasi-solid-state lithium ion capacitors

High-performance lithium ion capacitors(LICs) have been seriously hindered by the very low capacity and unclear capacitive mechanism of carbon cathode.Herein,after the combination of experimental results and theoretical calculations,it is found that the critical pore size of 0.8 nm for PF_6~-ion adsorption decreases strong interactive repulsion of electrons and largely reduces adsorption energy barrier,which greatly improves the charge accommodation capacity in electrical double-layer behavior.Most importantly,the chemical-bond evolution process of C=O group has been firstly revealed by X-ray photoelectron spectroscopy(XPS),indicating that the introduction of C=O group can provide abundant redox active sites for PF_6~-ion adsorption accompanied with enhanced pseudocapacitive capacity.Attributed to the synergistic effect of dual capacitive mechanism,porous carbon sheet(PCS) cathode shows a reversible specific capacity of 53.6 mAh g^(-1) even at a high current density of 50 A g^(-1).Significantly,the quasisolid-state LIC manifests state-of-the-art electrochemical performances with an integrated maximum energy density of 163 Wh kg^(-1) and an outstanding power density of 15,000 W kg^(-1).This elaborate work promotes better fundamental understanding about capacitive mechanism of PF_6~-ion and offers a rational dual-capacitive strategy for the design of advanced carbon cathodes.

Comparative Study of Two Carbon Fiber Cathodes and Theoretical Analysis in Microbial Fuel Cells on Ocean Floor

Cathode activity plays an important role in the improvement of the microbial fuel cells on ocean floor （BMFCs）. A comparison study between Rayon-based （CF-R） and PAN-based carbon fiber （CF-P） cathodes is conducted in the paper. The two carbon fibers were heat treated to improve cell performance （CF-R-H ＆ CF-P-H）, and were used to build a new BMFCs structure with a foamy carbon anode. The maximum power density was 112.4mWm-2 for CF-R-H, followed by 66.6mWm-2 for CF-R, 49.7 mWm-2 for CF-P-H and 21.6mWm-2 for CF-P respectively. The higher specific area and deep groove make CF-R have a better power output than with CF-P. Meanwhile, heat treatment of carbon fiber can improve cell power, nearly two-fold higher than heat treatment of plain fiber. This improvement may be due to the quinones group formation to accelerate the reduction of oxygen and electron transfer on the fiber surface in the three phase boundary after heat treatment. Compared to PAN-based carbon fiber, Rayon-based carbon fiber would be preferentially selected as cathode in novel BMFCs design due to its high surface area, low cost and higher power. The comparison research is significant for cathode material selection and cell design.

A systematic correlation between morphology of porous carbon cathode and electrolyte in lithium-sulfur battery

Porous carbon has been applied for lithium-sulfur battery cathodes,and carbonized metal-organic framework(MOF)is advantageous in tuning the morphology.Herein,we have systematically synthesized water-distorted MOF(WDM)derived porous carbon via controlling the proportion of both water in a mixed solvent(dimethylformamide and water)and ligand in MOF-5 precursors(metal and ligand),which is categorized by its morphology(i.e.Cracked stone(closed),Tassel(open)and Intermediate(semi-open)).For example,decrease in water and increase in ligand content induce Cracked stone WDMs which showed the highest specific surface area(2742-2990 m^(2)/g)and pore volume(2.81-3.28 cm^(3)/g)after carbonization.Morphological effect of carbonized WDMs(CWDMs)on battery performance was examined by introducing electrolytes with different sulfur reduction mechanisms(i.e.DOL/DME and ACN_(2) LiTFSITTE):Closed framework effectively confines polysulfide,whereas open framework enhances electrolyte accessibility.The initial capacities of the batteries were in the following order:Cracked stone>Intermediate>Tassel for DOL/DME and Intermediate>Tassel>Cracked stone for ACN_(2) LiTFSI-TTE.To note,Intermediate CWDM exhibited the highest initial capacity and retained capacity after 100 cycles(1398 and 747 mAh/g)in ACN_(2) LiTFSI-TTE electrolyte having advantages from both open and closed frameworks.In sum,we could correlate cathode morphology(openness and pore structure)and electrolyte type(i.e.polysulfide solubility)with lithium-sulfur battery performance.

In-situ fabrication of dual porous titanium dioxide films as anode for carbon cathode based perovskite solar cell

We develop a dual porous （DP） TiO2 film for the electron transporting layer （ETL） in carbon cathode based perovskite solar cells （C-PSCs）. The DP TiO2 film was synthesized via a facile PS-templated method with the thickness being controlled by the spin-coating speed. It was found that there is an optimum DP TiO2 film thickness for achieving an effective ETL, a suitable perovskite]TiO2 interface, an efficient light harvester and thus a high performance C-PSC. In particular, such a DP TiO2 film can act as a scaffold for complete-filling of the pores with perovskite and for forming high-quality perovskite crystals that are seamlessly interfaced with Ti02 to enhance interracial charge injection. Leveraging the unique advantages of DP TiO2 ETL, together with a dense-packed and pinhole-free TiO2 compact layer, PCE of the C-PSCs has reached 9.81% with good stability.

Vacuum Outgassing Behavior of Carbon Nanotube Cathode with High-Intensity Pulsed Electron Emission

Experimental investigations on the vacuum outgassing of a carbon nanotube （CNT） cathode with high-intensity pulsed electron emission on a 2 MeV linear induction accelerator injector are presented. Under the 1.60 MV diode voltage, the CNT cathode could provide 1.67 kA electron beam with the amount of outgassing of about 0.51 Pa.L. It is found that the amount of outgassing, which determines the cathode emission current, depends on the diode voltage and the vacuum.

Synthesis and Properties of Li_2MnSiO_4/C Cathode Materials for Li-ion Batteries

Carbon was coated on the surface of LiMnSiOto improve the electrochemical performance as cathode materials, which were synthesized by the solution method followed by heat treatment at 700 ℃ and the solid-state method followed by heat treatment at 950 ℃. It is shown that the cycling performance is greatly enhanced by carbon coating, compared with the pristine LiMnSiOcathode obtained by the solution method. The initial discharge capacity of LiMnSiO/C nanocomposite is 280.9 m Ah/g at 0.05 C with the carbon content of 33.3 wt%. The reasons for the improved electrochemical performance are smaller grain size and higher electronic conductivity due to the carbon coating. The LiMnSiO/C cathode material obtained by the solid-state method exhibits poor cycling performance, the initial discharge capacity is less than 25 m Ah/g.

A low-outgassing-rate carbon fiber array cathode

In this paper, a new carbon fiber based cathode — a low-outgassing-rate carbon fiber array cathode — is investigated experimentally, and the experimental results are compared with those of a polymer velvet cathode. The carbon fiber array cathode is constructed by inserting bunches of carbon fibers into the cylindrical surface of the cathode. In experiment, the diode base pressure is maintained at 1×10^（-2） Pa–2×10^（-2） Pa, and the diode is driven by a compact pulsed power system which can provide a diode voltage of about 100 kV and pulse duration of about 30 ns at a repetition rate of tens of Hz.Real-time pressure data are measured by a magnetron gauge. Under the similar conditions, the experimental results show that the outgassing rate of the carbon fiber array cathode is an order smaller than that of the velvet cathode and that this carbon fiber array cathode has better shot-to-shot stability than the velvet cathode. Hence, this carbon fiber array cathode is demonstrated to be a promising cathode for the radial diode, which can be used in magnetically insulated transmission line oscillator（MILO） and relativistic magnetron（RM）.

Status and Opportunities of Zinc Ion Hybrid Capacitors: Focus on Carbon Materials, Current Collectors, and Separators

Zinc ion hybrid capacitors(ZIHCs), which integrate the features of the high power of supercapacitors and the high energy of zinc ion batteries, are promising competitors in future electrochemical energy storage applications. Carbon-based materials are deemed the competitive candidates for cathodes of ZIHC due to their cost-effectiveness, high electronic conductivity, chemical inertness, controllable surface states, and tunable pore architectures. In recent years, great research efforts have been devoted to further improving the energy density and cycling stability of ZIHCs. Reasonable modification and optimization of carbon-based materials offer a remedy for these challenges. In this review, the structural design, and electrochemical properties of carbon-based cathode materials with different dimensions, as well as the selection of compatible, robust current collectors and separators for ZIHCs are discussed. The challenges and prospects of ZIHCs are showcased to guide the innovative development of carbon-based cathode materials and the development of novel ZIHCs.

A Sustainable Strategy for Spent Cathode Carbon Blocks Hazardous Waste Recycling Using Binary Molten Salt Thermal Treatment

Waste-to-Energy treatment is a promising path to environment and energy management in the future.This work detailed a binary molten salt thermal treatment methodology for the detoxification of spent cathode carbon block(SCCB)waste and the recycling of carbonaceous materials.The thermal behavior of SCCB and SCCB blended with molten salts was investigated.It was found that the NaCl-Na_(2)CO_(3)binary molten salts significantly contributed to reducing pyrolysis onset temperature by 334.3 K compared to that of SCCB itself(i.e.,activation energy of pyrolysis reaction was reduced from 4.24×10^(5)to 2.30×10^(5)J/mol),thus helping to lower thermal treatment energy consumption.With the addition of binary molten salts,the residue after thermal treatment in a horizontal tube furnace experiment was separated into two layers.The bottom-layer residue was mainly composed of molten salts.The fluorine content in the form of NaF and CaF_(2)of top-layer residue was reduced significantly while the carbon content remained unchanged.Specifically,the leaching concentration of fluoride ion was decreased from 4620 mg/L to 856 mg/L.It is noted that the NaF and CaF_(2)can be removed through water-leaching and hydrothermal acid-leaching methods and thus the carbonaceous materials with a calorific value of 17.5 MJ/kg were obtained.

Carbon cathode with heteroatom doping and ultrahigh surface area enabling enhanced capacitive behavior for potassium-ion hybrid capacitors

Potassium-ion hybrid capacitors(PIHCs)are widely regarded as highly promising energy storage devices,due to their exceptional energy density,impressive power density,and abundant potassium resources.Unfortunately,restricted by the inherent capacitive storage mechanism,the carbon cathodes possess a much lower specific capacity than battery-type anodes.Therefore,designing high-performance carbon cathodes is extremely urgent for the development of PIHCs.Herein,N,O codoped porous carbon(NOPC)was fabricated through the NaCl hard template method and combined KOH/melamine chemical activation technique,displaying the characteristics of abundant N/O content(4.7 at%/16.9 at%),ultrahigh specific surface area(3092 m^(2)g^(-1))and hierarchical pore network.The designed NOPC cathode delivers a high specific capacity(164.4 mAh.g^(-1)at 0.05 A.g^(-1))and superior cyclability(95.1%retention ratio at 2 A·g^(-1)over 2500 cycles).Notably,the adjustable ratio of micropores to mesopores facilitates the achievement of the optimal bal-ance between capacity and rate capability.Moreover,the pseudocapacitance can be further augmented through the incorporation of N/O functional groups.As expected,the graphite//NOPC based PIHC possesses a high energy density of 113 Wh·kg-at 747 W·kg^(-1)and excellent capacity retention of 84.4% fter 400 cycles at 1.0 A·g^(-1).This work introduces a novel strategy for designing carbon cathodes that enhances the electrochemical performance of PIHCs.

Status and perspectives of hierarchical porous carbon materials in terms of high-performance lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries,although a promising candidate of next-generation energy storage devices,are hindered by some bottlenecks in their roadmap toward commercialization.The key challenges include solving the issues such as low utilization of active materials,poor cyclic stability,poor rate performance,and unsatisfactory Coulombic efficiency due to the inherent poor electrical and ionic conductivity of sulfur and its discharged products(e.g.,Li2S2 and Li_(2)S),dissolution and migration of polysulfide ions in the electrolyte,unstable solid electrolyte interphase and dendritic growth on an odes,and volume change in both cathodes and anodes.Owing to the high specific surface area,pore volume,low density,good chemical stability,and particularly multimodal pore sizes,hierarchical porous carbon(HPC)mate rials have received considerable attention for circumventing the above pro blems in Li-S batteries.Herein,recent progress made in the synthetic methods and deployment of HPC materials for various components including sulfur cathodes,separators and interlayers,and lithium anodes in Li-S batteries is presented and summarized.More importantly,the correlation between the structures(pore volume,specific surface area,degree of pores,and heteroatom-doping)of HPC and the electrochemical performances of Li-S batteries is elaborated.Finally,a discussion on the challenges and future perspectives associated with HPCs for Li-S batteries is provided.

Surface engineering towards high-energy carbon cathode for advanced aqueous zinc-ion hybrid capacitors

Opportunities coexist with challenges for the development of carbon-based cathodes with a high energy density applied for zinc ion hybrid capacitors(ZIHCs).In the present study,a facile and effective surface engineering approach is demonstrated to greatly improve the energy storage ability of commercial carbon paper(CP)in ZIHC.Benefiting from the introduced oxygen functional groups,larger surface area and improved surface wettability upon air calcination,the assembled aqueous ZIHC with the functionalized carbon paper(FCP)exhibits a much higher areal capacity of 0.22 mAh/cm^(2)at 1 mA/cm^(2),outperforming the counterpart with blank CP by over 5000 times.More importantly,a superior energy density and power density of 130.8μWh/cm^(2)and 7460.5μW/cm^(2),are respectively delivered.Furthermore,more than 90%of the initial capacity is retained over 10000 cycles.This surface engineering strategy to improve the energy storage capability is potentially applicable to developing a wide range of high-energy carbon electrode materials.

Enhanced photoelectrocatalytic decomplexation of Ni-EDTA and simultaneous recovery of metallic nickel via TiO_(2)/Ni-Sb-SnO_(2) bifunctional photoanode and activated carbon fiber cathode

In order to enhance Ni-EDTA decomplexation and Ni recovery via photoelectrocatalytic (PEC)process,TiO_(2)/Ni-Sb-SnO_(2)bifunctional electrode was fabricated as the photoanode and activated carbon fiber (ACF) was introduced as the cathode.At a cell voltage of 3.5 V and initial solution pH of 6.3,the TiO_(2)/Ni-Sb-SnO_(2)bifunctional photoanode exhibited a synergetic effect on the decomplexation of Ni-EDTA with the pseudo-first-order rate constant of 0.01068 min^(-1)with 180 min by using stainless steel (SS) cathode,which was 1.5 and 2.4times higher than that of TiO_(2)photoanode and Ni-Sb-SnO_(2)anode,respectively.Moreover,both the efficiencies of Ni-EDTA decomplexation and Ni recovery were improved to 98%from 86%and 73%from 41%after replacing SS cathode with ACF cathode,respectively.Influencing factors on Ni-EDTA decomplexation and Ni recovery were investigated and the efficiencies were favored at acidic condition,higher cell voltage and lower initial Ni-EDTA concentration.Ni-EDTA was mainly decomposed via·OH radicals which generated via the interaction of O_(3),H_(2)O_(2),and UV irradiation in the contrasted PEC system.Then,the liberated Ni^(2+)ions which liberated from Ni-EDTA decomplexation were eventually reduced to metallic Ni on the ACF cathode surface.Finally,the stability of the constructed PEC system on Ni-EDTA decomplexation and Ni recovery was exhibited.

High-performance, stable and low-cost mesoscopic perovskite （CH3NH3PbI3） solar cells based on poly（3-hexylthiophene）- modified carbon nanotube cathodes

This work explores the use of poly（3- hexylthiophene） （P3HT） modified carbon nanotubes （CNTs@P3HT） for the cathodes of hole transporter free, mesoscopic perovskite （CH3NH3PbI3） solar cells （PSCs）, simultaneously achieving high-performance, high stability and low-cost PSCs. Here the thin P3HT modifier acts as an electron blocker to inhibit electron transfer into CNTs and a hydrophobic polymer binder to tightly cross-link the CNTs together to compact the carbon electrode film and greatly stabilize the solar cell. On the other hand, the presence of CNTs greatly improve the conductivity of P3HT. By optimizing the concentration of the P3HT modifier （2 mg/mL）, we have improved the power conversion efficiencies （PCEs） of CNTs@P3HT based PSCs up to 13.43% with an average efficiency of 12.54%, which is much higher than the pure CNTs based PSCs （best PCE 10.59%） and the sandwich-type P3HT/CNTs based PSCs （best PCE 9.50%）. In addition, the hysteresis of the CNTs@P3HT based PSCs is remarkably reduced due to the intimate interface between the perovskite and CNTs@P3HT electrodes. Degradation of the CNTs@ P3HT based PSCs is also strongly retarded as compared to cells employing the pure CNTs electrode when exposed to the ambient condition of 20%- 40% humidity.

Improved performance of Li-Se battery based on a novel dual functional CNTs@graphene/CNTs cathode construction

A dual functional CNTs@graphene/CNTs cathode for Li–Se battery was constructed by a CNTs@graphene network and a CNTs interlayer. CNTs were first integrated with graphene to form a three-dimensional（3D） framework and work together as a conductive matrix for Se confinement. The optimized composite cathode delivers a high initial capacity of 575 mAh·g^-1 at 0.5 A·g^-1 and good rate capacity with a retained capacity of 479 mAh·g^-1 at 2.0 A·g^-1（73% of the capacity at 0.2 A·g^-1）. CNTs were further served as an interlayer to confine the diffusion of polyselenides by constructing a thin CNTs layer outside the CNTs@graphene network. An improved initial capacity of 616 mAh·g^-1 at 0.5 A·g^-1 is achieved with a retained capacity of 538 mAh·g^-1 after 80 cycles, indicating the effective dual function of CNTs in this novel cathode construction and great application potential for Li–Se battery.