Lignin-derived hard carbon anode with a robust solid electrolyte interphase for boosted sodium storage performance

Hard carbon is regarded as a promising anode candidate for sodium-ion batteries due to its low cost,relatively low working voltage,and satisfactory specific capacity.However,it still remains a challenge to obtain a high-performance hard carbon anode from cost-effective carbon sources.In addition,the solid electrolyte interphase(SEI)is subjected to continuous rupture during battery cycling,leading to fast capacity decay.Herein,a lignin-based hard carbon with robust SEI is developed to address these issues,effectively killing two birds with one stone.An innovative gas-phase removal-assisted aqueous washing strategy is developed to remove excessive sodium in the precursor to upcycle industrial lignin into high-value hard carbon,which demonstrated an ultrahigh sodium storage capacity of 359 mAh g^(-1).It is found that the residual sodium components from lignin on hard carbon act as active sites that controllably regulate the composition and morphology of SEI and guide homogeneous SEI growth by a near-shore aggregation mechanism to form thin,dense,and organic-rich SEI.Benefiting from these merits,the as-developed SEI shows fast Na+transfer at the interphases and enhanced structural stability,thus preventing SEI rupture and reformation,and ultimately leading to a comprehensive improvement in sodium storage performance.

Free radicals trigger the closure of open pores in lignin-derived hard carbons toward improved sodium-storage capacity

The chemical activation of various precursors is effective for creating additional closed pores in hard carbons for sodium storage.However,the formation mechanism of closed pores under the influence of pore-forming agents is not well understood.Herein,an effective chemical activation followed by a high-temperature self-healing strategy is employed to generate interconnected closed pores in lignin-derived hard carbon(HCs).By systematic experimental design combined with electron paramagnetic res-onance spectroscopy,it can be found that the content of free radicals in the carbon matrix influences the closure of open pores at high temperatures.Excessively high activation temperature(>700 C)leads to a low free radical concentration,making it difficult to achieve self-healing of open pores at high tempera-tures.By activation at 700°C,a balance between pore making and self-healing is achieved in the final hard carbon.A large number of free radicals triggers rapid growth and aggregation of carbon microcrys-tals,blocking pre-formed open micropores and creating additional interconnected closed pores in as-obtained hard carbons.As a result,the optimized carbon anode(LK-700-1300)delivers a high reversible capacity of 330.8 mA h g^(-1) at 0.03 A g^(-1),which is an increase of 86 mA h g^(-1) compared to the pristine lignin-derived carbon anode(L-700-1300),and exhibits a good rate performance(202.1 mA h g^(-1) at 1 A g^(-1)).This work provides a universal and effective guidance for tuning closed pores of hard carbons from otherprecursors.

Hybrid hard carbon framework derived from polystyrene bearing distinct molecular crosslinking for enhanced sodium storage

Exploiting high-performance yet low-cost hard carbon anodes is crucial to advancing the state-of-the-art sodium-ion batteries.However,the achievement of superior initial Coulombic efficiency(ICE)and high Na-storage capacity via low-temperature carbonization remains challenging due to the presence of tremendous defects with few closed pores.Here,a facile hybrid carbon framework design is proposed from the polystyrene precursor bearing distinct molecular bridges at a low pyrolysis temperature of 800℃ via in situ fusion and embedding strategy.This is realized by integrating triazine-and carbonylcrosslinked polystyrene nanospheres during carbonization.The triazine crosslinking allows in situ fusion of spheres into layered carbon with low defects and abundant closed pores,which serves as a matrix for embedding the well-retained carbon spheres with nanopores/defects derived from carbonyl crosslinking.Therefore,the hybrid hard carbon with intimate interface showcases synergistic Na ions storage behavior,showing an ICE of 70.2%,a high capacity of 279.3 mAh g^(-1),and long-term 500 cycles,superior to carbons from the respective precursor and other reported carbons fabricated under the low carbonization temperature.The present protocol opens new avenues toward low-cost hard carbon anode materials for high-performance sodiumion batteries.

A review of hard carbon anodes for rechargeable sodium-ion batteries

Hard carbons(HCs)are recognized as potential anode materials for sodium-ion batteries(SIBs)because of their low cost,environmental friendliness,and the abundance of their precursors.The presence of graphitic domains,numerous pores,and disordered carbon layers in HCs plays a significant role in determining their sodium storage ability,but these structural features depend on the precursor used.The influence of functional groups,including heteroatoms and oxygen-containing groups,and the microstructure of the precursor on the physical and electrochemical properties of the HC produced are evaluated,and the effects of carbonization conditions(carbonization temperature,heating rate and atmosphere)are also discussed.

Rational manipulation of electrolyte to induce homogeneous SEI on hard carbon anode for sodium-ion battery

Sodium-ion batteries (SIBs) have great potential to be the next major energy storage devices due to their obvious advantages and developing advanced electrodes and electrolytes is urgently necessary to promote its future industrialization.However,hard carbon as a state-of-the-art anode of SIBs still suffers from the low initial Coulomb efficiency and unsatisfactory rate capability,which could be improved by forming desirable solid electrolyte interphases (SEI) to some extent.Indeed,the chemistry and morphology of these interfacial layers are fundamental parameters affecting the overall battery operation,and optimizing the electrolyte to dictate the quality of SEI on hard carbon is a key strategy.Hence,this review summarizes the recent research on SEI design by electrolyte manipulation from solvents,salts,and additives.It also presents some potential mechanisms of SEI formation in various electrolyte systems.Besides,the current advanced characterization techniques for electrolyte and SEI structure analyses have been comprehensively discussed.Lastly,current challenges and future perspectives of SEI formation on hard carbon anode for SIBs are provided from the viewpoints of its compositions,evolution processes,structures,and characterization techniques,which will promote SEI efficient manipulation and improve the performance of hard carbon,and further contribute to the development of SIBs.

High-efficiently doping nitrogen in kapok fiber-derived hard carbon used as anode materials for boosting rate performance of sodium-ion batteries

The engineering of plant-based precursor for nitrogen doping has become one of the most promising strategies to enhance rate capability of hard carbon materials for sodium-ion batteries;however,the poor rate performance is mainly caused by lack of pyridine nitrogen,which often tends to escape because of high temperature in preparation process of hard carbon.In this paper,a high-rate kapok fiber-derived hard carbon is fabricated by cross-linking carboxyl group in 2,6-pyridinedicarboxylic acid with the exposed hydroxyl group on alkalized kapok with assistance of zinc chloride.Specially,a high nitrogen doping content of 4.24%is achieved,most of which are pyridine nitrogen;this is crucial for improving the defect sites and electronic conductivity of hard carbon.The optimized carbon with feature of high nitrogen content,abundant functional groups,degree of disorder,and large layer spacing exhibits high capacity of 401.7 mAh g^(−1)at a current density of 0.05 A g^(−1),and more importantly,good rate performance,for example,even at the current density of 2 A g^(−1),a specific capacity of 159.5 mAh g^(−1)can be obtained.These findings make plant-based hard carbon a promising candidate for commercial application of sodium-ion batteries,achieving high-rate performance with the enhanced pre-cross-linking interaction between plant precursors and dopants to optimize aromatization process by auxiliary pyrolysis.

Regulating solid electrolyte interphase film on fluorinedoped hard carbon anode for sodium-ion battery

For the performance optimization strategies of hard carbon,heteroatom doping is an effective way to enhance the intrinsic transfer properties of sodium ions and electrons for accelerating the reaction kinetics.However,the previous work focuses mainly on the intrinsic physicochemical property changes of the material,but little attention has been paid to the resulting interfacial regulation of the electrode surface,namely the formation of solid electrolyte interphase(SEI)film.In this work,element F,which has the highest electronegativity,was chosen as the doping source to,more effectively,tune the electronic structure of the hard carbon.The effect of F-doping on the physicochemical properties of hard carbon was not only systematically analyzed but also investigated with spectroscopy,optics,and in situ characterization techniques to further verify that appropriate F-doping plays a positive role in constructing a homogenous and inorganic-rich SEI film.The experimentally demonstrated link between the electronic structure of the electrode and the SEI film properties can reframe the doping optimization strategy as well as provide a new idea for the design of electrode materials with low reduction kinetics to the electrolyte.As a result,the optimized sample with the appropriate F-doping content exhibits the best electrochemical performance with high capacity(434.53 mA h g^(-1)at 20mA g^(-1))and excellent rate capability(141 mAh g^(-1)at 400 mA g^(-1)).

Synthesis strategies of hard carbon anodes for sodium-ion batteries

Sodium-ion battery(SIB)is an ideal candidate for large-scale energy storage due to high abundant sodium sources,relatively high energy density,and potentially low costs.Hard carbons,as one of the most promising anodes,could deliver high plateau capacities at low potentials,which boosts the energy densities of SIBs.Their slope capacities have been demonstrated from the defect adsorption of sodium ions,while the plateau capacity depends highly on intercalation and pore filling.Nevertheless,the specific structures of sodium ions stored in hard carbons have not been clarified,namely active sites of adsorption,intercalation,and pore-filling mechanisms.Therefore,delicate synthesis methods are required to prepare hard carbons with controllable specific structures,along with elucidating the precise active sites for enhancing the Na-ion storage performance.To offer databases for future designs,we summarized the synthesis strategies of hard carbon anodes for constructing active sites of plateau capacities.Synthesis methods were highlighted with corresponding influences on the meticulous structures of hard carbons and Na-ion storage behaviors.Last but not least,perspectives were proposed for developing hard carbon anodes from the points of research and practical applications.

Sulfur doped iron-nitrogen-hard carbon nanosheets as efficient and robust noble metal-free catalysts for oxygen reduction reaction in PEMFC

Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination reaction.The as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon structures.These unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 cycles.Meanwhile,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical operation.Additionally,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)C.These results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.

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.

Low-Temperature Carbonized Nitrogen-Doped Hard Carbon Nanofiber Toward High-Performance Sodium-Ion Capacitors

Carbon nanofiber(CNF)was widely utilized in the field of electrochemical energy storage due to its superiority of conductivity and mechanics.However,CNF was generally prepared at relatively high temperature.Herein,nitrogen-doped hard carbon nanofibers(NHCNFs)were prepared by a lowtemperature carbonization treatment assisted with electrospinning technology.Density functional theory analysis elucidates the incorporation of nitrogen heteroatoms with various chemical states into carbon matrix would significantly alter the total electronic configurations,leading to the robust adsorption and efficient diffusion of Na atoms on electrode interface.The obtained material carbonized at 600°C(NHCNF-600)presented a reversible specific capacity of 191.0 mAh g^(−1)and no capacity decay after 200 cycles at 1 A g^(−1).It was found that the sodium-intercalated degree had a correlation with the electrochemical impedance.A sodium-intercalated potential of 0.2 V was adopted to lower the electrochemical impedance.The constructed sodium-ion capacitor with activated carbon cathode and presodiated NHCNF-600 anode can present an energy power density of 82.1 Wh kg^(−1)and a power density of 7.0 kW kg^(−1).

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.

Vanadium-modified hard carbon spheres with sufficient pseudographitic domains as high-performance anode for sodium-ion batteries

Hard carbons are promising anode materials for sodium-ion batteries.To meet practical requirements,searching for durable and conductive carbon with a stable interface is of great importance.Here,we prepare a series of vanadiummodified hard carbon submicrospheres by using hydrothermal carbonization followed by high-temperature pyrolysis.Significantly,the introduction of vanadium can facilitate the nucleation and uniform growth of carbon spheres and generate abundant V-O-C interface bonds,thus optimizing the reaction kinetic.Meanwhile,the optimized hard carbon spheres modified by vanadium carbide,with sufficient pseudographitic domains,provide more active sites for Na ion migration and storage.As a result,the HC/VC-1300 electrode exhibits excellent Na storage performance,including a high capacity of 420 mAh g^(-1) at 50mA g^(-1) and good rate capability at 1 A g^(-1).This study proposes a new strategy for the synthesis of hard carbon spheres with high tap density and emphasizes the key role of pseudographitic structure for Na storage and interface stabilization.

Recent advances in hard carbon anodes with high initial Coulombic efficiency for sodium-ion batteries

Initial Coulombic efficiency(ICE)has been widely adopted in battery research as a quantifiable indicator for the lifespan,energy density and rate performance of batteries.Hard carbon materials have been accepted as a promising anode family for sodium-ion batteries(SIBs)owing to their outstanding performance.However,the booming application of hard carbon anodes has been significantly slowed by the low ICE,leading to a reduced energy density at the cell level.This offers a challenge to develop high ICE hard carbon anodes to meet the applications of high-performance SIBs.Here,we discuss the definition and factors of ICE and describe several typical strategies to improve the ICE of hard carbon anodes.The strategies for boosting the ICE of such anodes are also systematically categorized into several aspects including structure design,surface engineering,electrolyte optimization and pre-sodiation.The key challenges and perspectives in the development of high ICE hard carbon anodes are also outlined.

Innovative discontinuous-SEI constructed in ether-based electrolyte to maximize the capacity of hard carbon anode

Compared with graphite,the lower sodiation potential and larger discharge capacity of hard carbon(HC)makes it the most promising anode material for sodium-ion battery.Utilizing ether-based electrolyte rather than conventional carbonate-based electrolyte,HC achieves superior electrochemical performance.Nevertheless,the mechanism by which ether-based electrolyte improves the properties of HC is still controversial,primarily focusing on whether it forms solid electrolyte interphase(SEI)film.In this work,according to the sodium storage mechanisms in HC at low voltage(<0.1 V),including Na^(+)-diglyme co-interaction into the carbon layer(SEI forbidden)and desolvated Na^(+)insertion in the irregular carbon holes(SEI required),the NaPF6concentration in ether-based electrolyte was regulated,so as to construct a discontinuous-SEI on the surface of the HC anode,which significantly enhances the electrochemical performances of HC.Specifically,with 0.2 M NaPF6ether-based electrolyte,HC deliverers a discharge capacity of 459.7 mA h g^(-1)at 0.1 C and stays at 357.2 mA h g^(-1)after 500 cycles at 1 C,which is substantially higher than that of higher/lower salt concentration electrolytes.

Boosting high initial coulombic efficiency of hard carbon by in-situ electrochemical presodiation

Hard carbon(HC)is a promising anode material for sodium ion batteries(SIBs),whereas inferior initial coulombic efficiency(ICE)severely limits its practical application.In the present work,we propose an in situ electrochemical presodiation approach to improve ICE by mixing sodium biphenyl(Na-Bp)dimethoxyethane(DME)solution with DME-based ether electrolyte.A solid electrolyte interface(SEI)could be formed beforehand on the HC electrode and Na^(+)was absorbed to nanopores and graphene stacks,compensating for the sodium loss and preventing electrolyte decomposition during the initial charge and discharge cycle.By this way,the ICE of half-cells was increased to nearly 100%and that of full-cells from 45%to 96%with energy density from 132.9 to 230.5 W h kg^(-1).Our work provides an efficient and facile method for improving ICE,which can potentially promote the practical application of HCbased materials.

Sulfur-doped hard carbon hybrid anodes with dual lithium-ion/metal storage bifunctionality for high-energy-density lithium-ion batteries

Bifunctional hybrid anodes(BHAs),which are both a high-performance active host material for lithium-ion storage as well as a guiding agent for homogeneous lithium metal nucleation and growth,exhibit significant potential as anodes for next-generation high-energy-density lithium-ion batteries(LIBs).In this study,sulfur-doped hard carbon nanosphere assemblies(S-HCNAs)were prepared through a hydrothermal treatment of a liquid organic precursor,followed by high-temperature thermal annealing with elemental sulfur for application as BHAs for LIBs.In a carbonate-based electrolyte containing fluoroethylene carbonate additive,the S-HCNAs showed high lithium-ion storage capacities in sloping as well as plateau voltage sections,good rate capabilities,and stable cyclabilities.In addition,high average Coulombic efficiencies(CEs)of~96.9%were achieved for dual lithium-ion and lithium metal storage cycles.In the LIB full-cell tests with typical NCM811 cathodes,the S-HCNA-based BHAs containing~400 mA h g^(−1) of excess lithium led to high energy and power densities of~500Wh kg^(−1) and~1695Wkg^(−1),respectively,and a stable cycling performance with~100%CEs was achieved.

Revealing sodium storage mechanism of hard carbon anodes through in-situ investigation of mechano-electrochemical coupling behavior

Hard carbon(HC)is considered a promising anode material for sodium-ion batteries due to its relatively low price and high specific capacity.However,HC still suffers from unclear reaction mechanisms and unsatisfactory cycling stability.The study of mechano-electrochemical coupling behavior by in-situ measurement techniques is expected to understand the sodium storage and degradation mechanisms.In this paper,the strain and stress evolution of HC anodes at different sodiation/desodiation depths and cycles are investigated by combining electrochemical methods,digital image correlation,and theoretical equations.The observation by monitoring the in-situ strain evolution during the redox process supports the“adsorption-intercalation/filling”mechanism in reduction and the“de-filling/de-intercalation-deso rption”mechanism in oxidation.Further studies have demonstrated that the strain and stress of the electrode show periodic changes accompanied by a continuous accumulation of residual stress during cycles,explaining the capacity degradation mechanism of HC from a mechanical perspective.In addition,when the higher current density is applied,the electrodes experience greater strain and stress associated with the Na+insertion rate.This work clarifies the Na-storage mechanism and the mechano-electrochemical coupling mechanism of HC anodes by in-situ strain measurement,which helps optimize and design the anode materials of sodium-ion batteries from the perspective of interface microstructure and multi-field coupling,such as in situ integrated interface structure design.

Furfural residues derived nitrogen-sulfur co-doped sheet-like carbon: An excellent electrode for dual carbon lithium-ion capacitors

The state-of-the-art lithium-ion capacitors (LICs),consisting of high-capacity battery-type anode and high-rate capacitor-type cathode,can deliver high energy density and large power density when comparing with traditional supercapacitors and lithium-ion batteries,respectively.However,the ion kinetics mismatch between cathode and anode leads to unsatisfied cycling lifetime and anode degradation.Tremendous efforts have been devoted to solving the abovementioned issue.One promising strategy is altering high conductive hard carbon anode with excellent structural stability to match with activated carbon cathode,assembling dual-carbon LIC.In this contribution,one-pot in-situ expansion and heteroatom doping strategy was adopted to prepare sheet-like hard carbon,while activated carbon was obtained involving activation.Ammonium persulfate was used as expanding and doping agent simultaneously.While furfural residues (FR) were served as carbon precursor.The resulting hard carbon (FRNS-HC) and activated carbon (FRNS-AC)show excellent electrochemical performance as negative and positive electrodes in a lithium-ion battery (LIB).To be specific,374.2 m Ah g^(-1)and 123.1 m Ah g^(-1)can be achieved at 0.1 A g^(-1)and 5 A g^(-1)when FRNS-HC was tested as anode.When combined with a highly porous carbon cathode (S_(BET)=2961 m^(2)g^(-1)) synthesized from the same precursor,the LIC showed high specific energy of147.67 Wh kg^(-1)at approximately 199.93 W kg^(-1),and outstanding cycling life with negligible capacitance fading over 1000 cycles.This study could lead the way for the development of heteroatom-doped porous carbon nanomaterials applied to Li-based energy storage applications.

Recent Progress in Improving Rate Performance of Cellulose-Derived Carbon Materials for Sodium-Ion Batteries

Cellulose-derived carbon is regarded as one of the most promising candidates for high-performance anode materials in sodium-ion batteries;however,its poor rate performance at higher current density remains a challenge to achieve high power density sodium-ion batteries.The present review comprehensively elucidates the structural characteristics of cellulose-based materials and cellulose-derived carbon materials,explores the limitations in enhancing rate performance arising from ion diffusion and electronic transfer at the level of cellulose-derived carbon materials,and proposes corresponding strategies to improve rate performance targeted at various precursors of cellulose-based materials.This review also presents an update on recent progress in cellulose-based materials and cellulose-derived carbon materials,with particular focuses on their molecular,crystalline,and aggregation structures.Furthermore,the relationship between storage sodium and rate performance the carbon materials is elucidated through theoretical calculations and characterization analyses.Finally,future perspectives regarding challenges and opportunities in the research field of cellulose-derived carbon anodes are briefly highlighted.