Carbon Anode Research Articles

Boosting Molecular Cross-Linking in a Phenolic Resin for Spherical Hard Carbon with Enriched Closed Pores toward Enhanced Sodium Storage Ability.

Phenolic resin (PF) is considered a promising precursor of hard carbon (HC) for advanced-performance anodes in sodium-ion batteries (SIBs) because of its facile designability and high residual carbon yield. However, understanding how the structure of PF precursors influences sodium storage in their derived HC remains a significant challenge. Herein, the microstructure of HC is controlled by the degree of cross-linking of resorcinol-benzaldehyde (RB) resin. We reveal that robust molecular cross-linking in RB resin induced by hydrothermal treatment promotes closed-pore formation in the derived HC. The mechanism is devised for the decomposition of a highly cross-linked RB three-dimensional network into randomly stacked short-range graphitic microcrystals during high-temperature carbonization, contributing to the abundant closed pores in the derived HC. In addition, the high cross-linking degree of RB resin endows its derived HC with a small-sized spherical morphology and large interlayer spacing, which improves the rate performance of HC. Consequently, the optimized hydrothermal treatment HC anode shows a higher specific capacity of 372.7 mAh g-1 and better rate performance than the HC anode without hydrothermal treatment (276.0 mAh g-1). This strategy can provide feasible molecular cross-linking engineering for the development of closed pores in PF-based HC toward enhanced sodium storage.

Unveiling the Degradation Mechanism of Sodium Ion Batteries based on Na4Fe3(PO4)2P2O7 Cathode and Hard carbon Anode suggests Anode Particle Size Reduction for Cycling Stability

To improve the cycle life of sodium‐ion batteries, it is essential to understand the microscopic processes that lead to cell degradation. The mismatched response time of anode and cathode has profound but poorly understood impact on cycle life. In this research, we combine electrochemical and materials characterization combined with electrochemical modeling to investigate the root cause of degradation in sodium‐ion full cells made from Na4Fe3(PO4)2P2O7 (NFPP) cathodes and hard carbon (HC) anode. Our results pinpoint to the slow diffusion of Na in HC as the main cause of diffusional polarization that leads to cathode experiencing high local potentials and ultimately to active material loss over cycling. We demonstrate that by reducing the anode particle size, the diffusional timescales in anode can be matched with that of cathode to improve both extractable capacity as well as cycle life. These observations shed light on non‐intuitive and intricate ways in which cathode and anode can interact with each other to cause degradation in Na‐ion batteries and how microscopic understanding of these cause and effects can help design long lasting batteries.

Enhanced Nitrate Nitrogen Removal from Constructed Wetland via Fe3O4/Granular Activated Carbon Anode Microbial Electrolysis Cell under Low C/N Ratio

In this study, a constructed wetland–Fe3O4/granular activated carbon anode microbial electrolysis cell (CW-FMEC) was constructed to enhance denitrification in low COD/N ratio wastewater. The introduction of Fe3O4 boosted the expression of functional genes involved in the denitrification pathway, and the abundance of narG, nirS, and nosZ increased by 99.29%, 70.54%, and 132.18%, respectively, compared to CW. In addition, the content of c-type cytochromes (c-Cyts) and EPS were also enhanced in the CW-FMEC. The microbial communities study displayed that Thauera, Dechloromonas, and Arenimonas became the main genera for denitrification. The denitrification performance at different COD/N ratios was investigated in depth. Under optimal working circumstances, the CW-FMEC had an excellent nitrate removal rate (88.9% ± 1.12%) while accumulating nearly no NO2−-N or NH4+-N in the effluent. This study provides a new direction for the development of CW-MEC and accelerates its implementation.

Deciphering the storage mechanism of biochar anchored with different morphology Mn3O4 as advanced anode material for lithium-ion batteries

Biochar is regarded as a promising lithium-ion batteries anode material, owing to its high cost-effectiveness. However, the poor specific capacity and cycling stability have limited its practical applications. A straightforward and cost-efficient solvothermal method is presented for synthesizing Mn3O4/biochar composites in this study. By adjusting solvothermal temperatures, Mn3O4 with different morphology is prepared and anchored on the biochar surface (MKAC-T) to improve the electrochemical performance. Due to the morphological effect of nanospherical Mn3O4 on the biochar surface, the MKAC-180 anode material demonstrates outstanding reversible capacity (992.5 mAh/g at 0.2 A/g), significant initial coulombic efficiency (61.1 %), stable cycling life (605.3 mAh/g at 1.0 A/g after 1000 cycles), and excellent rate performance (385.8 mAh/g at 1.6 A/g). Moreover, electro-kinetic analysis and ex-situ physicochemical characterizations are employed to illustrate the charge storage mechanisms of MKAC-180 anode. This study provides valuable insights into the “structure–activity relationship” between Mn3O4 microstructure and electrochemical performance for the Mn3O4/biochar composites, illuminating the industrial utilization of biomass carbon anode materials.

Characteristics and properties of anode materials for lithium-ion batteries

Lithium-ion secondary batteries (LIBs) are battery systems with high energy densities. They are essential components of todays information-rich, mobile societys portable, entertainment, computing, and telecommunications technology. After 1981, most of the research on anode materials mainly focused on the anode containing Li, such as LiAl alloy, LiC alloy, etc. These materials have high prices, unstable cycling performance, and are difficult to be commercialized. The successful commercialization of LIBs began in 1991 with SONYs manufacturing of petroleum coke-based anode materials. Among them, anode plays a crucial role in LIBs. Anode materials that have been commercialized include carbon, alloys, and lithium titanate. Lithium-ion batteries using carbon anode materials and lithium titanate anode materials can meet the needs of electric vehicles (EVs) and large-scale energy storage applications to a certain extent, and alloy anode materials can promote the energy density of LIBs. The properties of the commercialized anode materials are covered in this paper. Next generation anode materials such as silicon anode materials are also introduced.

Phenolic Resin Derived Hard Carbon Anode for Sodium-Ion Batteries: A Review

Phenolic Resin Derived Hard Carbon Anode for Sodium-Ion Batteries: A Review

Magnetron Sputtered SnO₂ Layer Combined with NiCo−LDH Nanosheets for High‐Performance All‐Solid‐State Supercapacitors

AbstractNickel‐cobalt layered double hydroxide (NiCo−LDH) has attracted much attention because of its excellent electrochemical properties and regulability. And it is a potential pseudocapacitive electrode material, which is commonly used in supercapacitors and lithium‐ion batteries. Its application in the field of supercapacitors can improve the energy density, power density and cycle life of devices. However, NiCo−LDH still faces some challenges, such as poor electrical conductivity and the capacity attenuation caused by agglomeration of layered structures, which require further research and optimization. In this paper, SnO2 films were prepared on carbon cloth (CC) by magnetron sputtering method, and Ni−Co LDH nanosheets were grown by hydrothermal reaction to obtain NiCo−LDH@SnO2 composites. Due to the synergistic effect between NiCo−LDH and SnO2, NiCo−LDH@SnO2 composites exhibit high Cs and good cyclic stability. In addition, an all‐solid‐state flexible asymmetric supercapacitor (ASC) was assembled with activated carbon (AC) anodes, showing good specific capacitance(Cs) and energy density. And a high initial capacitance can still be retained after 10,000 cycles. This paper shows that NiCo−LDH@SnO2 shows excellent application potential in supercapacitors.

Investigating the effects of silicon and carbon components on the thickness evolution and performance degradation of silicon–carbon electrodes through electrochemical dilatometry

The severe volumetric changes occur during the lithiation/de-lithiation of silicon materials, which are the main cause of battery capacity failure. In this study, the expansion behavior of a cell composed of a silicon-carbon anode and Li(Ni0.5Co0.2Mn0.3)O2 (NCM523) was measured using the electrochemical dilatometry, and the contributions of different silicon and carbon components to the expansion were analyzed, along with factors affecting the cyclic stability of the silicon carbon anode. The results indicate that amorphous carbon can inhibit the volume expansion of monocrystalline silicon in the late stage of lithiation, thereby ensuring the cyclic stability of silicon. The cyclic stability of silicon-carbon composites is affected by irreversible expansion and expansion variation, and these two factors are negatively correlated. This research provides insights and guidance for the design of silicon carbon electrodes with superior electrochemical performance.

Locally Curved Surface with CoN4 Sites Enables Hard Carbon with Superior Sodium‐Ion Storage Performances at −40 °C

AbstractThe impressive electrochemical performance of sodium‐ion batteries at low temperatures has long been recognized as a promising technical advantage. However, the inadequate transport kinetics of Na+ ions and complex interfacial reactions at the hard carbon anode surface hinder the practical implementation of commercial sodium‐ion batteries. Herein, a novel approach to address this issue by introducing a homogenized functional carbon coating layer with a locally curved configuration is proposed. This coating layer is designed to accommodate single CoN4 sites on the surface of commercial hard carbon particles, resulting in enhanced sodium storage performance at low temperatures. The surface‐modified hard carbon anode material (HC‐Z1) demonstrates a commendable rate performance of 220.6 mAh g−1 at 3 A g−1@25 °C and a substantial reversible capacity of 288.7 mAh g−1 with an 89% capacity retention at 0.06 A g−1@‐20 °C. Furthermore, even at a temperature as low as −40 °C, the reversible capacity remains at 270 mAh g−1 at 0.06 A g−1. Extensive characterizations and theoretical calculations provide evidence that the optimized interface between the electrode and electrolyte effectively enhances the desolvation and migration of Na+ ions, particularly at low temperatures.

Carbon dots promoting surface defect and interphase high anion concentration for sodium-ion battery carbon anodes

The interphase chemistry of electrode/electrolyte significantly affects the electrochemical performance. This investigation explores the solid-liquid interphase alteration of an economical asphalt-derived carbon by incorporating multifunctional carbon dots, aiming to clarify the impact of interfacial properties on sodium-ion storage mechanisms. Enhanced by high density defects and carbonyl groups, the capacity, primarily within the sloping discharge, rise from 247 to 361 mA h g−1 in non-aqueous sodium ion batteries. Integrating experimental and computational methods reveals a marked improvement in PF6- anions absorption at the interface, refining the solvation structure and concentrating these anions. Consequently, a NaF/Na2CO3-dominated, inorganic-rich solid-electrolyte interphase (SEI) forms, attributed to the swift PF6- anion dissociation facilitated by the electrode's rapid electron mobility. This effect promotes sodium ion diffusion and accelerates the kinetics of sodium (de)intercalation. Beyond elucidating interfacial property contributions to the sodium storage in disordered carbon, this study highlights the genesis of irreversible capacity and draws connections between SEI's inorganic components and Coulombic efficiency. The insights offered furnish a pioneering perspective for engineering high-performance carbon anodes.

Fluorinated sodium aluminate main conducting salt boosting sodium storage of hard carbon

Tuning electrolyte components plays a very important role in improving the sodium storage of hard carbon (HC) anode. Herein, we unprecedentedly synthesize a fluorinated moisture resistant aluminum-centered sodium salt of sodium bis(perfluoropinacolato)aluminate (NaAl[OC(CF3)2]4, NaBPPA), which enhances the sodium storage and specific capacity of HC anode when serving as main conducting salt in electrolyte. It is revealed that NaBPPA induces the formation of a mechanically robust and fast Na+ conducting SEI layer on HC anode. In specific, the NaBPPA-based electrolyte facilitates the enrichment of unique inorganic species (such as NaAlF4, NaF, AlF3 and Al2O3), which endow the SEI layer with high Young's modulus and fast Na+ transportation. Thus, the problem of SEI layer dissolution is alleviated and the formation of quasi-metallic Na clusters at low potential plateau region is promoted by using NaBPPA as a main salt in electrolytes. This work reveals the great importance of novel sodium salt anions beyond conventional ones in boosting sodium storage of HC anode.

Sandwich-like high-performance Ti3C2Tx MXene/NiCo2O4 nanosphere composites for asymmetric supercapacitor application

NiCo2O4 is a promising electrode material for supercapacitors due to its low cost, high theoretical specific capacitance and good cycling stability. However, NiCo2O4 has the disadvantages of poor electronic and ionic conductivities and easy agglomeration. Moreover, the irreversible structural damage caused by the NiCo2O4 volume expansions during charging and discharging limits its use in supercapacitors. Herein, we fabricated sandwich Ti3C2Tx MXene/NiCo2O4 composites via an electrostatic self-assembly method. The problem of easy agglomeration of the NiCo2O4 nanospheres was solved by intercalating Ti3C2Tx MXene layers with the NiCo2O4 nanospheres. Furthermore, the Ti3C2Tx MXene layer was also utilized as a protective layer to limit serious volume expansion and protect the structure of NiCo2O4 nanospheres from destruction. The results showed that the prepared Ti3C2Tx MXene/NiCo2O4 composite exhibited a high specific capacitance of 1025 F g−1 at a current density of 1 A g−1 and had an initial capacity of 81 % when the current density was increased to 10 A g−1. The Ti3C2Tx MXene/NiCo2O4 composite cathode and activated carbon anode were assembled in an asymmetric supercapacitor, which showed an energy density of 36.67 Wh kg−1 at 800 W kg−1 and a capacity retention of 88.2 % after 5000 cycles.

Long‐Life High‐Voltage Sodium‐Ion Batteries Enabled by Electrolytes with Cooperative Na+‐Solvation

AbstractStabilizing the electrode interphases is urgently required to enhance the lifetime of high‐voltage sodium‐ion batteries (SIBs). However, the continuous anode solid–electrolyte interphase (SEI) growth associated with electron leakage and the fragile cathode–electrolyte interphase (CEI) lead to capacity fade at high voltage; and yet the solvation‐interphase‐performance relationship is inadequately addressed. Herein, a cooperative Na+‐solvation strategy is reported to stabilize the interphases by a holistic design of electrolytes combining soft and moderate co‐solvents. The rationally regulated Na+‐solvation leads to CEI/SEI with the desired thickness and component stability. As such, remarkable cycling stability is achieved for 4.3‐V Na3V2O2(PO4)2F (NVOPF) cathodes with 83.3% capacity retention over 3000 cycles at 1 C, significantly outperforming the carbonate counterpart (41.6% capacity retention). Meanwhile, the restrained SEI growth via reducing the formation of electron‐leaking Na2CO3 stabilizes the long‐term cycling of the hard carbon (HC) anode. The assembled NVOPF||HC full cells achieve superior rate capability (up to 15 C) and stable cycling stability over 500 cycles. The demonstrated engineering of electrolyte chemistry, Na+‐solvation, and interphase structure/component contributes toward the rational establishment of design rules for high‐voltage SIBs and possibly other similar chemistries.

Doping effect and oxygen vacancy engineering in nickel-manganese layered double hydroxides for high-performance supercapacitors

Design of electrode materials with high electrochemical capacitance and long lifetime remains a challenging issue for high-performance supercapacitors. Herein, we successfully synthesized a binder-free composite electrode comprising oxygen vacancy-abundant NiMnMg-layered double hydroxides grown on 3D graphene foam (Vo-NiMnMg-LDH@3DG) by Mg doping during hydrothermal process and subsequently Ar plasma etching. Thanks to the incorporation of electrochemically inert Mg element, the enhanced charge transfer capability, and enriched active sites that induced by plentiful oxygen vacancies, Vo-NiMnMg-LDH@3DG manifests a high specific capacity of 374.8 mAh g−1 at a current density of 1 A g−1 and satisfactory rate performance (74.26% at 20 A g−1). Furthermore, the asymmetric supercapacitor (ASC) assembled with Vo-NiMnMg-LDH@3DG cathode and activated carbon anode exhibits a specific capacitance up to 171 F g−1 at 1 A g−1, achieving a maximum energy density of 53.62 Wh kg−1 and the highest power density of 7500 W kg−1. This work not only provides innovative approaches for preparing oxygen vacancy-rich LDH materials, but also offers insights for the design and improvement of energy storage devices based on transition metal-based LDH.

Mechanical Activation of Graphite for Na-Ion Battery Anodes: Unexpected Reversible Reaction on Solid Electrolyte Interphase via X-Ray Analysis.

Although sodium-ion batteries (SIBs) offer promising low-cost alternatives to lithium-ion batteries (LIBs), several challenges need to be overcome for their widespread adoption. A primary concern is the optimization of carbon anodes. Graphite, vital to the commercial viability of LIBs, has a limited capacity for sodium ions. Numerous alternatives to graphite are explored, particularly focusing on disordered carbons, including hard carbon. However, compared with graphite, most of these materials underperform in LIBs. Furthermore, the reaction mechanism between carbon and sodium ions remains ambiguous owing to the structural diversity of disordered carbon. A straightforward mechanical approach is introduced to enhance the sodium ion storage capacity of graphite, supported by comprehensive analytical techniques. Mechanically activated graphite delivers a notable reversible capacity of 290.5 mAh·g-1 at a current density of 10 mA·g-1. Moreover, it maintains a capacity of 157.7 mAh·g-1 even at a current density of 1 A·g-1, benefiting from the defect-rich structure achieved by mechanical activation. Soft X-ray analysis revealed that this defect-rich carbon employs a sodium-ion storage mechanism distinct from that of hard carbon. This leads to an unexpected reversible reaction on the solid electrolyte surface. These insights pave the way for innovative design approaches for carbon electrodes in SIB anodes.

Algal biomass-based zero-waste biorefinery for producing optically pure (R)-γ-valerolactone and carbonaceous electrodes applicable for energy storage devices

Mankind is facing a severe climate crisis caused by fossil fuel-derived CO2 emissions. Although biorefineries utilizing biomass have been considered the best option for carbon-neutrality, most biorefinery-derived products have not yet been promising for economic feasibility; various strategies have been developed to increase economic competitiveness, and zero-waste biorefineries are challenging options. Herein, we aim to develop an algal biomass-based zero-waste biorefinery for producing enantioselective (R)-γ-valerolactone ((R)-GVL) and carbonaceous electrodes applicable for Li-ion batteries (LiBs). Various algal biomasses were hydrothermally oxidized to produce levulinic acid (LA) as an intermediate for producing (R)-GVL, resulting that Gracilaria verrucosa was selected as feedstock. For the hydroxylation of G. verrucosa-derived LA to 4-hydroxyvaleric acid (4-HV), 3-hydroxybutyrate dehydrogenase (HBDH) was explored through genome mining and further engineered. The engineered HBDH successfully converted G. verrucosa-derived LA to 4-HV, which was subsequently lactonized under acidic conditions, resulting in optically pure (R)-GVL. To our knowledge, this is the first report of the production of an algal biomass-derived enantioselective (R)-GVL with a perfect enantiomeric excess (>99.99 %) that can be used as a precursor for more valuable biopharmaceuticals and bioplastics than biofuels. Furthermore, residual G. verrucosa after hydrothermal oxidation was used as a carbonaceous anode material for LIBs for the first time; hard carbon anodes, which were prepared through simple heat treatment (800 ℃, 3 h, argon atmosphere), exhibit good capacities of 231, 191, 133, 108, 97 and 86 mAh/g at 0.05, 0.1, 0.5, 1, 1.5, and 2 A/g, respectively. The results discussed herein can provide insights into zero-waste biorefineries applicable for diverse industrial fields (e.g., biopolymer, biopharmaceutical and energy storage) and contribute to the construction of closed-carbon-loops for coping with climate change.

Unleashing the impact of Nb-doped, single crystal, cobalt-free P2-type Na0.67Ni0.33Mn0.67O2 on elevating the cycle life of sodium-ion batteries

A synergistic stabilization effect in a Nb-doped P2-type single crystal cobalt-free layered oxide cathode material, offering remarkable cycling stability and high-power performance for Na-ion batteries have unveiled in this study. The introduction of Nb in the transition metal layer not only reduces the electronic band gap but also enhances electronic conductivity and mitigates ionic diffusion energy barriers. The induction of a robust Nb-O bond expedites electron and Na+ transfer, contributing to the stabilization of the host structure is further confirmed through the density functional theory calculations, including electron localization function (ELF) and crystal orbital Hamiltonian population (COHP). To the best of our knowledge, this study is the first to demonstrate a homogeneous distribution of niobium throughout the single crystal, specifically doped at the nickel site within the bulk, without inducing atomic-scale surface reorganization. The presence of single crystals improves various kinetic factors, demonstrating the profound correlation between structural defects and chemical proliferation, thereby reducing the evolution of oxygen gas. The P2-type Nb-doped single crystal cathode (Na0.67Ni0.31Mn0.67Nb0.02O2) exhibits remarkable capacity retention, >95 % after 100 cycles at 0.1 C and >90 % after an extended cycling of 2000 cycles at 1 C. Practical assessments in complete cell setups with a pre-sodiated hard carbon anode further validate the material's viability, showcasing capacity retention of over 93 % after 100 cycles in a coin cell and approximately 89 % in a pouch cell format. This comprehensive study establishes the transformative potential of Nb-doped single crystal cobalt-free P2-type layered oxide cathode materials, marking a significant advancement in sodium-ion battery technology.

Consummating ion desolvation in hard carbon anodes for reversible sodium storage

Hard carbons are emerging as the most viable anodes to support the commercialization of sodium-ion (Na-ion) batteries due to their competitive performance. However, the hard carbon anode suffers from low initial Coulombic efficiency (ICE), and the ambiguous Na-ion (Na+) storage mechanism and interfacial chemistry fail to give a reasonable interpretation. Here, we have identified the time-dependent ion pre-desolvation on the nanopore of hard carbons, which significantly affects the Na+ storage efficiency by altering the solvation structure of electrolytes. Consummating the pre-desolvation by extending the aging time, generates a highly aggregated electrolyte configuration inside the nanopore, resulting in negligible reductive decomposition of electrolytes. When applying the above insights, the hard carbon anodes achieve a high average ICE of 98.21% in the absence of any Na supplementation techniques. Therefore, the negative-to-positive capacity ratio can be reduced to 1.02 for full cells, which enables an improved energy density. The insight into hard carbons and related interphases may be extended to other battery systems and support the continued development of battery technology.

Coal-based hard carbon anode for high-performance sodium ion batteries via coal-based graphene oxide as a multi-functional binder

Coal-based hard carbon for sodium ion batteries (SIBs) was successfully prepared using Shenfu bituminous coal (SFC) by one-step pyrolysis method. In the present work, we reported a novel method to fabricate carbon electrodes for SIBs from coal-based hard carbon with coal-based graphene oxide (CGO) as a multi-functional conductive binder to realize dual functional utilization of coal. As compared to traditional binder (CMC), electrodes with the CGO binder exhibits significantly increased reversible capacity and rate capability. This work provides a facile method for coal-based carbon materials used in SIBs.

A generic F-doped strategy for biomass hard carbon to achieve fast and stable kinetics in sodium/potassium-ion batteries

N/F-doped nanospheres hard carbon (CDC-F-900) was prepared via simple annealing followed by HF solvothermal reaction. F-doping is achieved by replacing –OH and –COOH groups with F− to form C-F and C-F2. Abundant micropores and defect structures exist in CDC-F-900, providing a rapid diffusion pathway for Na+/K+. Therefore, it provides the capacity of 372.2 mAh/g after 1000 cycles at 0.1 A/g in sodium-ion batteries (SIBs). Especially in potassium-ion batteries (PIBs), it can still provide an ultra-high capacity of 214.2 mAh/g at 10 A/g after 5000 cycles. This is due to the inorganics-rich SEI which possesses higher ionic conductivity and stability, resulting in excellent long-cycle stability. Density functional theory (DFT) calculations indicate that the conjugate effect of N/F leads to an appropriate adsorption energy for K+ at defects. Not only does it increase the reversible capacity by reducing irreversible K+ adsorption, but it also accelerates ion transport rate, resulting in better rate capability. The potassium storage mechanism of CDC-F-900 is elaborated in detail through in-situ Raman spectroscopy and XRD pattern. This work provides a new insight for the design and development of low-cost, source-rich, and long-life hard carbon anodes for SIBs/PIBs.