Interfacial design of silicon/carbon anodes for rechargeable batteries:A review

Silicon(Si)has been studied as a promising alloying type anode for lithium-ion batteries due to its high specific capacity,low operating potential and abundant resources.Nevertheless,huge volume expansion during alloying/dealloying processes and low electronic conductivity of Si anodes restrict their electrochemical performance.Thus,carbon(C)materials with special physical and chemical properties are applied in Si anodes to effectively solve these problems.This review focuses on current status in the exploration of Si/C anodes,including the lithiation mechanism and solid electrolyte interface formation,various carbon sources in Si/C anodes,such as traditional carbon sources(graphite,pitch,biomass),and novel carbon sources(MXene,graphene,MOFs-derived carbon,graphdiyne,etc.),as well as interfacial bonding modes of Si and C in the Si/C anodes.Finally,we summarize and prospect the selection of carbonaceous materials,structural design and interface control of Si/C anodes,and application of Si/C anodes in all-solid-state lithium-ion batteries and sodium-ion batteries et al.This review will help researchers in the design of novel Si/C anodes for rechargeable batteries.

Regulating solid electrolyte interphases on phosphorus/carbon anodes via localized high-concentration electrolytes for potassium-ion batteries

The resourceful and inexpensive red phosphorus has emerged as a promising anode material of potassium-ion batteries(PIBs) for its large theoretical capacities and low redox potentials in the multielectron alloying/dealloying reactions,yet chronically suffering from the huge volume expansion/shrinkage with a sluggish reaction kinetics and an unsatisfactory interfacial stability against volatile electrolytes.Herein,we systematically developed a series of localized high-concentration electrolytes(LHCE) through diluting high-concentration ether electrolytes with a non-solvating fluorinated ether to regulate the formation/evolution of solid electrolyte interphases(SEI) on phosphorus/carbon(P/C) anodes for PIBs.Benefitting from the improved mechanical strength and structural stability of a robust/uniform SEI thin layer derived from a composition-optimized LHCE featured with a unique solvation structure and a superior K+migration capability,the P/C anode with noticeable pseudocapacitive behaviors could achieve a large reversible capacity of 760 mA h g^(-1)at 100 mA g^(-1),a remarkable capacity retention rate of 92.6% over 200 cycles at 800 mA g^(-1),and an exceptional rate capability of 334 mA h g^(-1)at8000 mA g^(-1).Critically,a suppressed reduction of ether solvents with a preferential decomposition of potassium salts in anion-derived interfacial reactions on P/C anode for LHCE could enable a rational construction of an outer organic-rich and inner inorganic-dominant SEI thin film with remarkable mechanical strength/flexibility to buffer huge volume variations and abundant K+diffusion channels to accelerate reaction kinetics.Additionally,the highly reversible/durable full PIBs coupling P/C anodes with annealed organic cathodes further verified an excellent practical applicability of LHCE.This encouraging work on electrolytes regulating SEI formation/evolution would advance the development of P/C anodes for high-performance PIBs.

Production of carbon anodes by high-temperature mould pressing

Laboratory-scale carbon anodes were produced by a new method of high temperature mould pressing, and their physico-chemical properties were studied. The influence of mould pressing conditions and coal pitch addition on the bulk density, crushing strength, and oxidation resistance was analyzed. The mierostructure of carbon anodes was investigated by scanning electron microscopy （SEM）, and the mechanism of producing carbon anodes by high-temperature mould pressing was analyzed. The results show that when the anodes are produced by high-temperature mould pressing, coal pitch can expand into the coke particles and fill the pores inside the particles, which is beneficial for improving the quality of prebaked anodes. The bulk density of carbon anodes is 1.64-1.66 g/cm3, which is 0.08-0.12 g/cm3 higher than that of industrial anodes, and the oxidation resistance of carbon anodes is also significantly improved.

The recent progress of pitch-based carbon anodes in sodium-ion batteries

Sodium-ion batteries(SIBs)have attracted significant attentions as promising alternatives to lithium-ion batteries for large-scale energy storage applications.Here carbon materials are considered as the most competitive anodes for SIBs based on their low-cost,abundant availability and excellent structural stability.Pitch,with high carbon content and low cost,is an ideal raw precursor to prepare carbon materials for large-scale applications.Nevertheless,the microstructures of pitch-based carbon are highly ordered with smaller interlayer distances,which are unfavorable for Na ion storage.Many efforts have been made to improve the sodium storage performance of pitch-based carbon materials.This review summarizes the recent progress about the application of pitch-based carbons for SIBs anodes in the context of carbon’s morphology and structure regulation strategies,including morphology adjustment,heteroatoms doping,fabricating heterostructures,and the increase of the degree of disorder.Besides,the advantages,present challenges,and possible solutions to current issues in pitch-based carbon anode are discussed,with the highlight of future research directions.This review will provide a deep insight into the development of low-cost and high-performance pitch-based carbon anode for SIBs.

Reversible Oxygen-Rich Functional Groups Grafted 3D Honeycomb-Like Carbon Anode for Super-Long Potassium Ion Batteries

Studies have found that oxygen-rich-containing functional groups in carbon-based materials can be used as active sites for the storage performance of K^(+),but the basic storage mechanism is still unclear.Herein,we construct and optimize 3D honeycomb-like carbon grafted with plentiful COOH/C=O functional groups(OFGC)as anodes for potassium ion batteries.The OFGC electrode with steady structure and rich functional groups can effectively contribute to the capacity enhancement and the formation of stable solid electrolyte interphase(SEI)film,achieving a high reversible capacity of 230 mAh g^(-1) at 3000 mA g^(-1) after 10,000 cycles(almost no capacity decay)and an ultra-long cycle time over 18 months at 100 mA g^(-1).The study results revealed the reversible storage mechanism between K^(+)and COOH/C=O functional groups by forming C-O-K compounds.Meanwhile,the in situ electrochemical impedance spectroscopy proved the highly reversible and rapid de/intercalation kinetics of K+in the OFGC electrode,and the growth process of SEI films.In particular,the full cells assembled by Prussian blue cathode exhibit a high energy density of 113 Wh kg^(-1) after 800 cycles(calculated by the total mass of anode and cathode),and get the light-emitting diodes lamp and ear thermometer running.

Electrocatalysis of carbon anode in aluminium electrolysis

The anodic over voltage of the carbon anode in aluminumelectrolysis is of the order of 0.6 V at normal current densities.However, it can be reduced somewhat by doping the anode carbon withvarious inorganic compounds. A new apparatus was designed to improvethe precision of over voltage measurements. Anodes were doped withMgAl_2O_4 and AlF_3 both by impregnation of the coke and by addingpowder, and the measured over voltage was compared with that ofUndoped samples. For prebake type anodes baked at around 1150 deg. C,the anodic overvoltage was reduced by 40-60 mV, And for Soderbergtype anodes, baked at 950 deg. C, by 60-80 mV.

Effect of coke properties and its blending recipe on performances of carbon anode for aluminium electrolysis

The properties and blending recipe of petroleum cokes used to make high quality carbon anodes for aluminium electrolysis were studied. Three kinds of green cokes were selected for bench scale study to illustrate the effects of cokes properties and its blending recipe on anode performances. The results show that impurities derived mainly fi＇om cokes remarkably affect the CO2 reactivity and air reactivity of carbon anodes. Ca, Na and V can increase CO2 reactivity of calcined cokes but S has the contrary effect, and the cokes of high V level generally present high air reactivity. The anodes with good quality can be made by properly selecting and scientifically blending of cokes, some poor quality cokes can also be used to produce high quality anodes with a reasonable blending recipe. Na contaminated anodes have high CO2 reactivity and air reactivity, so the recycled anode butts should be well cleaned to reduce Na content before being introduced into anode production, which is especially important to the low S cokes.

Relationship between initial efficiency and structure parameters of carbon anode material for Li-ion battery

The initial efficiency is a very important criterion for carbon anode material of Li-ion battery.The relationship between initial efficiency and structure parameters of carbon anode material of Li-ion battery was investigated by an artificial intelligence approach called Random Forests using D10,D50,D90,BET specific surface area and TP density as inputs,initial efficiency as output.The results give good classification performance with 91%accuracy.The variable importance analysis results show the impact of 5 variables on the initial efficiency descends in the order of D90,TP density,BET specific surface area,D50 and D10;smaller D90 and larger TP density have positive impact on initial efficiency.The contribution of BET specific surface area on classification is only 18.74%,which indicates the shortcoming of BET specific surface area as a widely used parameter for initial efficiency evaluation.

Hard-carbon hybrid Li-ion/metal anode enabled by preferred mesoporous uniform lithium growth mechanism

To achieve high energy density in lithium batteries,the construction of lithium-ion/metal hybrid anodes is a promising strategy.In particular,because of the anisotropy of graphite,hybrid anode formed by graphite/Li metal has low transport kinetics and is easy to causes the growth of lithium dendrites and accumulation of dead Li,which seriously affects the cycle life of batteries and even causes safety problems.Here,by comparing graphite with two types of hard carbon,it was found that hybrid anode formed by hard carbon and lithium metal,possessing more disordered mesoporous structure and lithophilic groups,presents better performance.Results indicate that the mesoporous structure provides abundant active site and storage space for dead lithium.With the synergistic effect of this structure and lithophilic functional groups(–COOH),the reversibility of hard carbon/lithium metal hybrid anode is maintained,promoting uniform deposition of lithium metal and alleviating formation of lithium dendrites.The hybrid anode maintains a 99.5%Coulombic efficiency(CE)after 260 cycles at a specific capacity of 500 m Ah/g.This work provides new insights into the hybrid anodes formed by carbon-based materials and lithium metal with high specific energy and fast charging ability.

Pioneering the direct large-scale laser printing of flexible“graphenic silicon”self-standing thin films as ultrahigh-performance lithium-ion battery anodes

Recent technological advancements,such as portable electronics and electric vehicles,have created a pressing need for more efficient energy storage solutions.Lithium-ion batteries(LIBs)have been the preferred choice for these applications,with graphite being the standard anode material due to its stability.However,graphite falls short of meeting the growing demand for higher energy density,possessing a theoretical capacity that lags behind.To address this,researchers are actively seeking alternative materials to replace graphite in commercial batteries.One promising avenue involves lithiumalloying materials like silicon and phosphorus,which offer high theoretical capacities.Carbon-silicon composites have emerged as a viable option,showing improved capacity and performance over traditional graphite or pure silicon anodes.Yet,the existing methods for synthesizing these composites remain complex,energy-intensive,and costly,preventing widespread adoption.A groundbreaking approach is presented here:the use of a laser writing strategy to rapidly transform common organic carbon precursors and silicon blends into efficient“graphenic silicon”composite thin films.These films exhibit exceptional structural and energy storage properties.The resulting three-dimensional porous composite anodes showcase impressive attributes,including ultrahigh silicon content,remarkable cyclic stability(over 4500 cycles with∼40%retention),rapid charging rates(up to 10 A g^(-1)),substantial areal capacity(>5.1 mAh cm^(-2)),and excellent gravimetric capacity(>2400 mAh g^(-1) at 0.2 A g^(-1)).This strategy marks a significant step toward the scalable production of high-performance LIB materials.Leveraging widely available,cost-effective precursors,the laser-printed“graphenic silicon”composites demonstrate unparalleled performance,potentially streamlining anode production while maintaining exceptional capabilities.This innovation not only paves the way for advanced LIBs but also sets a precedent for transforming various materials into high-performing electrodes,promising reduced complexity and cost in battery production.

Calculation model of edge carbon atoms in graphite particles for anode of lithium-ion batteries

Based on the hexagonal crystallite model of graphite,the electrochemical characteristics of carbon atoms on the edge and basal plane were proposed by analyzing graphite crystal structure and bonds of carbon atoms in different sites.A spherical close-packed model for graphite particle was developed.The fractions of surface carbon atoms（SCA） and edge carbon atoms（ECA） were derived in the expression of crystallographic parameters and particle size,and the effects of ECA on the initial irreversible capacity and the mechanisms of action were analyzed and verified.The results show that the atoms on the edge are more active for electrochemical reactions,such as electrolyte decomposition and tendency to form stable bond with other atoms and groups.For the practical graphite particle,corresponding modifying factors were introduced to revise the difference in calculating results.The revised expression is suitable for the calculation of the fractions of SCA and ECA for carbon materials such as graphite,disordered carbon and modified graphite.

Interconnected carbon nanocapsules with high N/S co-doping as stable and high-capacity potassium-ion battery anode

Carbonaceous materials have drawn much attention in potassium-ion batteries (PIBs) due to their low price and superior physicochemical properties. However, the application of carbonaceous materials in PIB anodes is hindered by sluggish kinetics and large volume expansion. Herein, N/S co-doped carbon nanocapsule (NSCN) is constructed for superior K+ storage. The NSCN possesses 3D nanocapsule framework with abundant meso/macropores, which guarantees structural robustness and accelerates ions/electrons transportation. The high-level N/S co-doping in carbon matrix not only generates ample defects and active sites for K+ adsorption, but also expands interlayer distance for facile K+ intercalation/deintercalation. As a result, the NSCN electrode delivers a high reversible capacity (408 mAh g^(−1) at 0.05 A g^(−1)), outstanding rate capability (149 mAh g^(−1) at 5 A g^(−1)) and favorable cycle stability (150m Ah g^(−1) at 2 A g^(−1) after 2000 cycles). Ex situ TEM, Raman and XPS measurements demonstrate the excellent stability and reversibility of NSCN electrode during potassiation/depotassiation process. This work provides inspiration for the optimization of energy storage materials by structure and doping engineering.

Hollow carbon microbox from acetylacetone as anode material for sodium-ion batteries

Carbon-based materials have attracted much interest as one of the promising anodes for sodium-ion batteries. However, low utilization of electrolyte and slow ion-transfer rate during electrochemical process hinder the further application of traditional bulk carbon. In order to enhance the diffusion kinetics and maintain the reversibility, hierarchical hollow carbon microbox was successfully prepared through a tunable bottom-up self-template routine for sodium-ion batteries. During annealing process, the morphology construction and activation happened synchronously. Based on that, a range of cross-linked porous nanosheet and hollow microbox were attained by manipulating reactant condition. The generation of texture and physical property are analyzed and are established linkages related to the electrochemical behavior. As results depicted in kinetic exploration and simulation based on cyclic voltammetry, the surfacecontrolled electrochemical behavior gradually turns to be the diffusion-controlled behavior as the hollow microbox evolves to porous nanosheet. The probable reason is that the rational microstructure/texture design leads to the accelerated diffusion kinetic procedure and the reduced concentration difference polarization. Sodium storage mechanism was deduced as reversible binding of Na-ions with local defects,including vacancies on sp2 graphitic layers, at the edges of flakes and other structural defects instead of intercalation. Bestowed by the morphology design, the broad pore width distribution, abundant defects/active sites and surface functionality, hollow microbox electrode delivers great electrochemical performances. This work is expected to propose a novel and effective strategy to prepare tunable hierarchical hollow carbon microbox and induce the fast kinetic of carbon anode material.

Engineering homotype heterojunctions in hard carbon to induce stable solid electrolyte interfaces for sodium-ion batteries

Developing effective strategies to improve the initial Coulombic efficiency(ICE)and cycling stability of hard carbon(HC)anodes for sodium-ion batteries is the key to promoting the commercial application of HC.In this paper,homotype heterojunctions are designed on HC to induce the generation of stable solid electrolyte interfaces,which can effectively increase the ICE of HC from 64.7%to 81.1%.The results show that using a simple surface engineering strategy to construct a homotypic amorphous Al_(2)O_(3) layer on the HC could shield the active sites,and further inhibit electrolyte decomposition and side effects occurrence.Particularly,due to the suppression of continuous decomposition of NaPF 6 in ester-based electrolytes,the accumulation of NaF could be reduced,leading to the formation of thinner and denser solid electrolyte interface films and a decrease in the interface resistance.The HC anode can not only improve the ICE but elevate its sodium storage performance based on this homotype heterojunction composed of HC and Al_(2)O_(3).The optimized HC anode exhibits an outstanding reversible capacity of 321.5mAhg^(−1) at 50mAg^(−1).The cycling stability is also improved effectively,and the capacity retention rate is 86.9%after 2000 cycles at 1Ag^(−1) while that of the untreated HC is only 52.6%.More importantly,the improved sodium storage behaviors are explained by electrochemical kinetic analysis.

Carbon materials toward efficient potassium storage:Rational design,performance evaluation and potassium storage mechanism

Potassium-ion batteries(PIBs)are potential“Beyond Li-ion Batteries”candidates for their resource advantage and low standard electrode potential.To date,the research on PIBs is in its early stages,the most urgent task is to develop high-performance electrode materials and reveal their potassium storage mechanism.For PIBs anode materials,carbon with tunable microstructure,excellent electrochemical activity,nontoxicity and low price is considered as one of the most promising anode materials for commercialization.Although some breakthrough works have emerged,the overall electrochemical performance of the reported carbon anode is still far away from practical application.Herein,we carry out a comprehensive overview of PIBs carbon anode in terms of three aspects of rational design of structure,performance evaluation criteria and characterization of potassium storage mechanism.First,the regulation mechanism of key structural features of carbon anode on its potassium storage performance and the representative structural regulation strategies are introduced.Then,in view of the undefined performance evaluation criteria of PIBs carbon anode,a reference principle for evaluating the potassium storage performance of carbon anode is proposed.Finally,the advanced characterization techniques for the potassium storage mechanism of carbon anode are summarize.This review aims to provide guidance for the development of practical PIBs anode.

Electro-Oxidation of Concentrated Ce(Ⅲ) at Carbon Felt Anode in Nitric Acid Media

Electro-oxidation of Ce （ Ⅲ ） to Ce （ Ⅳ ） in parallel plate flow type electrolyzer divided with cation exchange membrane was carried out in nitric acid media at carbon felt anode under galvanostatic conditions. Carbon felt was used as an anode for its high specific surface area and high oxygen evolution overpotential. Pt coated Ti plates were used as cathode and anode current feeder. The oxidation of 1 mol· L^-1 Ce（ Ⅲ ） solution in 2 mol· L^- 1 HNO3 was proceeding with a high current efficiency （92%） until about 80% of Ce（ Ⅲ ） was oxidized. Then, oxygen evolution, accompanied by terminal voltage jump, took place, lowering current efficiency. Ce（ Ⅲ ） was oxidized up to 90% with current efficiency of 62%. In this mode, strong carbon felt anode oxidation was observed. The wear out of carbon felt was 46% in six consequent runs （6 h of operation）. After each run, carbon felt surface had to be renewed with slightly alkaline solution to remove carbon oxidation products and ensure regular operational conditions. When anode surface was blocked, oxygen evolution took place from the beginning of electrolysis due to higher actual current density. The wear out of carbon felt anode could be minimized by means of oxygen evolution prevention. In the case when electrolysis had been stopped before oxygen evolution started （at Ce（ Ⅳ ） conversion of about 80% ）, the wear out of anode was less than 2% during 6 consequent runs （4 h of operation）.

Carbon Foam Anode Modified by Urea and Its Higher Electrochemical Performance in Marine Benthic Microbial Fuel Cell

Electrode materials have an important effect on the property of microbial fuel cell(MFC). Carbon foam is utilized as an anode and further modified by urea to improve its performance in marine benthic microbial fuel cell(BMFC) with higher voltage and output power. The electrochemical properties of plain carbon foam(PC) and urea-modified carbon foam(UC) are measured respectively. Results show that the UC obtains better wettability after its modification and higher anti-polarization ability than the PC. A novel phenomenon has been found that the electrical potential of the modified UC anode is nearly 100 m V lower than that of the PC, reaching-570 ±10 m V(vs. SCE), and that it also has a much higher electron transfer kinetic activity, reaching 9399.4 m W m-2, which is 566.2-fold higher than that from plain graphite anode(PG). The fuel cell containing the UC anode has the maximum power density(256.0 m W m-2) among the three different BMFCs. Urea would enhance the bacteria biofilm formation with a more diverse microbial community and maintain more electrons, leading to a lower anodic redox potential and higher power output. The paper primarily analyzes why the electrical potential of the modified anode becomes much lower than that of others after urea modification. These results can be utilized to construct a novel BMFC with higher output power and to design the conditioner of voltage booster with a higher conversion ratio. Finally, the carbon foam with a bigger pore size would be a potential anodic material in conventional MFC.

Prebaked Anode Carbon Project with 400 Thousand Tons Annual Capacity to Be Built in Guangxi

On January 19, 2008, the ground breaking ceremony of prebaked anode carbon project with 400 thousand tons annual capacity of Pingguo Haohai Carbon Co. , Ltd was held in Pingguo Industry Zone of Guangxi province. After being put into production, the project with an investment of CNY 0.8 billion, will reach CNY 1.6 billion annual production value.

From Micropores to Ultra-micropores inside Hard Carbon: Toward Enhanced Capacity in Room-/ Low-Temperature Sodium-Ion Storage

Pore structure of hard carbon has a fundamental influence on the electrochemical properties in sodium-ion batteries(SIBs).Ultra-micropores(<0.5 nm)of hard carbon can function as ionic sieves to reduce the diffusion of slovated Na+but allow the entrance of naked Na^(+) into the pores,which can reduce the interficial contact between the electrolyte and the inner pores without sacrificing the fast diffusion kinetics.Herein,a molten diffusion-carbonization method is proposed to transform the micropores(>1 nm)inside carbon into ultra-micropores(<0.5 nm).Consequently,the designed carbon anode displays an enhanced capacity of 346 mAh g^(−1) at 30 mA g^(−1) with a high ICE value of~80.6%and most of the capacity(~90%)is below 1 V.Moreover,the high-loading electrode(~19 mg cm^(−2))exhibits a good temperature endurance with a high areal capacity of 6.14 mAh cm^(−2) at 25℃ and 5.32 mAh cm^(−2) at −20℃.Based on the in situ X-ray diffraction and ex situ solid-state nuclear magnetic resonance results,the designed ultra-micropores provide the extra Na+storage sites,which mainly contributes to the enhanced capacity.This proposed strategy shows a good potential for the development of high-performance SIBs.

High Capacity and Fast Kinetics of Potassium‑Ion Batteries Boosted by Nitrogen‑Doped Mesoporous Carbon Spheres

In view of rich potassium resources and their working potential,potassium-ion batteries(PIBs)are deemed as next generation rechargeable batteries.Owing to carbon materials with the preponderance of durability and economic price,they are widely employed in PIBs anode materials.Currently,porosity design and heteroatom doping as efficacious improvement strategies have been applied to the structural design of carbon materials to improve their electrochemical performances.Herein,nitrogen-doped mesoporous carbon spheres(MCS)are synthesized by a facile hard template method.The MCS demonstrate larger interlayer spacing in a short range,high specific surface area,abundant mesoporous structures and active sites,enhancing K-ion migration and diffusion.Furthermore,we screen out the pyrolysis temperature of 900°C and the pore diameter of 7 nm as optimized conditions for MCS to improve performances.In detail,the optimized MCS-7-900 electrode achieves high rate capacity(107.9 mAh g^(−1) at 5000 mA g^(−1))and stably brings about 3600 cycles at 1000 mA g^(−1).According to electrochemical kinetic analysis,the capacitive-controlled effects play dominant roles in total storage mechanism.Additionally,the full-cell equipped MCS-7-900 as anode is successfully constructed to evaluate the practicality of MCS.