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用于钠离子电池的硬碳负极：原理及应用进展

易淑宏 ,  符庆丰 ,  周卓涵 ,  孙玲玲 ,  刘奎立 ,  理记涛

化学进展 ›› 2026, Vol. 38 ›› Issue (7) :1246-1246

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化学进展 ›› 2026, Vol. 38 ›› Issue (7) :1246-1246 DOI: 10.7536/PC20251209
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用于钠离子电池的硬碳负极：原理及应用进展

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Hard Carbon Anodes for Sodium-Ion Batteries： Principles and Application Progress

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摘要

钠离子电池有望彻底改变全球能源储存格局，提供一种具有成本效益且资源丰富的锂离子电池替代方案。在这一新兴生态系统中，硬碳凭借其结构稳定性和低工作电压，确立了其作为首选负极材料的地位。然而，从学术发现到规模制造的转变仍面临巨大挑战。目前，硬碳的商业可行性受到低初始库仑效率（ICE）的制约，这会通过迫使正极增大尺寸而带来严重的经济成本，同时在前驱体可扩展性和全电池集成方面仍存在显著工程空白。本文旨在弥合钠存储机制基础理解与电池工程实践之间的关键鸿沟。首先，整合关于吸附-嵌入-孔隙填充机制的最新共识，为理性设计建立坚实的理论框架。与传统只关注容量指标的综述不同，本文批判性地评估先进合成策略的工业可行性，强调异质原子掺杂与效率之间的潜在权衡，并讨论生物质前驱体的可扩展性挑战，如灰分含量和一致性问题。其次，对ICE问题进行全面分析，将其直接与电池成本相联系，并评估包括先进电解液和预钠化在内的缓解策略。最后，本文还针对全电池特定失效模式（如气体生成和低体积密度）提出务实的开发路线，为研发坚固且具有商业可行性的硬碳负极提供指导。

Abstract

Sodium-ion batteries （SIBs） are poised to revolutionize the global energy storage landscape， offering a cost-effective and resource-abundant alternative to lithium-ion batteries. Within this emerging ecosystem， hard carbon （HC） has secured its position as the premier anode material， prized for its structural stability and low operating voltage. Yet， the transition from academic discovery to GWh-scale manufacturing faces formidable hurdles. The commercial viability of HC is currently compromised by a low initial coulombic efficiency （ICE）， which imposes a severe economic penalty by forcing cathode oversizing， and by significant engineering gaps in precursor scalability and full-cell integration. This review aims to bridge the critical gap between the fundamental understanding of sodium storage mechanisms and the practical realities of battery engineering. First， we begin by consolidating the latest consensus on the adsorption-intercalation-pore filling mechanism， establishing a solid theoretical framework for rational design. Unlike traditional reviews that focus solely on capacity metrics， we critically evaluate the industrial feasibility of advanced synthesis strategies， highlighting the hidden trade-offs between heteroatom doping and efficiency， and addressing the scalability challenges of biomass precursors， such as ash content and consistency. Second， we provide a comprehensive analysis of the ICE challenge， linking it directly to cell cost， and evaluate mitigation strategies including advanced electrolytes and pre-sodiation. Finally， the review addresses specific full-cell failure modes， such as gassing and low volumetric density， offering a pragmatic roadmap for developing robust， commercially viable hard carbon anodes.

Contents

1 Introduction

2 Understanding of Na-ion storage mechanism in HC

2.1 Fundamentals of hard carbon

2.2 Sodium ions storage mechanisms

2.3 Advanced characterization techniques

3 Advanced synthesis and structural engineering

3.1 Biomass-derived hard carbons

3.2 Heteroatom doping

3.3 Morphological and pore structure engineering

4 How to solve the low ICE

4.1 Understanding the root causes of low ICE

4.2 Electrolyte engineering （mitigation）

4.3 Surface engineering and coatings （mitigation）

4.4 Pre-sodiation （compensation）

5 Full-cell development： bridging the gap to commercialization

5.1 Sodium inventory problem

5.2 Pouch cell and cylindrical cell prototyping

5.3 Practical failure modes

6 Challenges and future perspectives

7 Conclusions

Graphical abstract

关键词

硬碳 / 生物质 / 钠离子电池 / 钠存储机制 / 结构工程

Key words

hard carbon / biomass / sodium-ion batteries / sodium storage mechanism / structural engineering

引用本文

引用格式 ▾
易淑宏, 符庆丰, 周卓涵, 孙玲玲, 刘奎立, 理记涛. 用于钠离子电池的硬碳负极：原理及应用进展[J]. 化学进展, 2026, 38(7): 1246-1246 DOI:10.7536/PC20251209
Shuhong Yi, Qingfeng Fu, Zhuohan Zhou, Lingling Sun, Kuili Liu, Jitao Li. Hard Carbon Anodes for Sodium-Ion Batteries： Principles and Application Progress[J]. Progress in Chemistry, 2026, 38(7): 1246-1246 DOI:10.7536/PC20251209

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1 Introduction

The global energy landscape of the 21st century is characterized by an urgent need for rapid decarbonization of power grids and transportation systems to address climate change. This transition is heavily reliant on the adoption of renewable energy sources， particularly solar and wind power. However， these sources’ inherent intermittency highlights the necessity for the development of efficient， scalable， and cost-effective electrochemical energy storage systems that can manage supply and demand on a terawatt-hour （TWh） scale. Over the past thirty years， lithium-ion batteries （LIBs） have been central to this energy transition， powering a wide range of devices， from consumer electronics to electric vehicles， due to their high energy density and established manufacturing processes[1-2]. Yet， as demand shifts from gigawatt-hour （GWh） to TWh levels， the limitations of the Lithium Age become apparent. The dependence on Li， Co， and Ni， resources that are limited in supply， environmentally challenging to extract， and prone to price volatility， creates a significant supply chain bottleneck that threatens the progress of the global energy transition. This situation has sparked a worldwide quest for post-lithium technologies that emphasize resource availability and cost stability rather than solely focusing on energy density.

Among various post-lithium alternatives， sodium-ion batteries （SIBs） have emerged as a leading commercially viable option to complement or even replace LIBs in certain applications[3-6]. The rationale supporting SIBs is grounded in both chemistry and economics. Sodium， the sixth most abundant element in the Earth’s crust， is widely available and primarily sourced from soda ash and seawater， making it a virtually inexhaustible resource. This abundance helps stabilize energy storage costs against the volatility of critical mineral markets. Additionally， SIBs offer a significant techno-economic advantage over LIBs： sodium’s chemistry prevents alloy formation with aluminum at low potentials， allowing SIB anodes to use lightweight and cost-effective aluminum foil as a current collector， in contrast to the heavier and pricier copper foil required for LIBs[7-13]. This substitution results in notable reductions in both cell weight and material costs. Although SIBs have a lower specific energy density due to Na’s larger ionic radius （1.02 Å （1 Å=0.1 nm） for Na+ vs. 0.76 Å for Li+） and higher atomic weight， this drawback is increasingly considered acceptable for applications in stationary energy storage and entry-level electromobility， where factors such as cost， safety， and cycle life are prioritized （Fig.1a）[14].

Despite these compelling advantages， the commercialization of SIBs has been historically delayed by a critical anode bottleneck. The graphitic anode， which is the cornerstone of the LIB industry， is electrochemically inactive in SIBs using standard carbonate electrolytes[15]. The thermodynamic barrier for inserting the larger Na+ ion into the tight interlayer spacing of graphite （0.335 nm） is insurmountable， resulting in negligible capacity. This incompatibility forced the scientific community to explore alternative anode chemistries， including alloying materials and conversion materials[16-19]. While these alternatives offer high theoretical capacities， they are plagued by massive volumetric expansion （up to 400%） during cycling， leading to particle pulverization， electrical isolation， and rapid cell failure.

Amidst this landscape of unstable alternatives， hard carbon （HC） as the definitive solution， which is a non-graphitizable form of carbon with the disordered microstructure， turbostratic nanodomains， offers a goldilocks combination of properties： a high reversible specific capacity （300~350 mAh/g）， excellent structural stability with near-zero volume expansion， and a low operating potential platform （<0.1 V vs. Na/Na+） that maximizes full-cell voltage[20-23] （Fig.1b）. However， a chasm exists between the promise of HC and its reality in GWh-scale manufacturing. While academic literature is replete with reports of HC anodes achieving high capacities， the transition to commercial viability is currently compromised by several formidable engineering hurdles. The most significant of these is the low initial coulombic efficiency （ICE）. Typically hovering between 75% and 85%， the low ICE means that a significant portion of the sodium inventory supplied by the cathode is irreversibly consumed during the first cycle to form the solid electrolyte interphase （SEI） and fill irreversible trap sites[11,24 -26]. In a commercial full cell， where the cathode is the most expensive component， this loss is economically devastating. It forces manufacturers to oversize the cathode by 15%~25% simply to compensate for the anode’s inefficiency， directly inflating the cost-per-kWh and negating the primary economic advantage of the SIB.

Furthermore， the path to scalability is obstructed by inconsistencies in precursors. While the narrative of deriving HC from sustainable biomass （e.g.， nutshells， fruit peels） is attractive， the industrial reality is that biomass is chemically heterogeneous. Variations in lignin， cellulose， and ash content leads to unpredictable electrochemical performance and batch-to-batch inconsistency， which is unacceptable for automotive-grade manufacturing. Additionally， the fundamental mechanism of sodium storage in HC remains a subject of debate. The contributions of “adsorption” in the sloping voltage region versus “pore filling” in the plateau region are often misunderstood， impeding the rational design of microstructures that balance high capacity with fast kinetics[27-30].

This review aims to bridge the critical gap between the fundamental of sodium storage and the practical realities of battery engineering. We move beyond the standard cataloging of synthesis methods to provide a critical， techno-economic analysis of the field. We begin by consolidating the latest consensus on the “adsorption-intercalation-pore filling” mechanism， establishing a theoretical framework for material design （Section 2）. We then critically evaluate advanced synthesis strategies， specifically addressing the industrial feasibility of biomass precursors and the often-overlooked trade-offs between heteroatom doping and ICE （Section 3）. A major focus of this review is the systematic analysis of ICE challenges （Section 4）， where we link efficiency directly to cell cost and evaluate mitigation strategies ranging from electrolyte engineering to scalable pre-sodiation techniques. Finally， we address the integration of these optimized anodes into full cells （Section 5）， discussing practical failure modes such as gassing and volumetric density limitations. By synthesizing recent advances （2022-present） through the lens of industrial viability， this review offers a pragmatic roadmap for overcoming the remaining barriers to the commercial applications.

2 Understanding of Na-ion storage mechanism in HC

2.1 Fundamentals of hard carbon

HC typically refers to a carbonaceous material with high mechanical hardness， defined by its resistance to graphitization even at temperatures above 2500 ℃ and commonly produced by the pyrolysis of polymers， petrochemicals， or biomass. Unlike graphite， which consists of highly ordered， long-range stacks of graphene layers （AB stacking）， HC possesses a turbostratic microstructure. This structure is composed of small， randomly oriented domains of curved graphene sheets， cross-linked by disordered carbon chains[31]. This inherent disorder is the material’s defining feature， preventing the layers from flattening and stacking into graphite （Fig.2a）. Key characterization techniques， such as X-ray diffraction （XRD）， distinguish HC from crystalline graphite. XRD patterns reveal two broad diffraction peaks around 25° （002） and 43° （100）， indicating low crystalline coherency and large interlayer d-spacing， along with minimal stacking[32]. Raman spectroscopy further elucidates the disordered nature of HC， with the intensity ratio of the ID and IG serving as an indicator of graphitization levels[33]. Small-angle X-ray scattering （SAXS） provides insights into HC’s porosity through specific intensity patterns[34] （Fig.2b）. Numerous models have attempted to correlate HC’s structural characteristics with its electrochemical performance， particularly in sodium storage， though a universal model remains elusive （Fig.2c）. Early models proposed various structural components， including curved graphene domains and micropores[35-37]. Subsequent theories introduced defect-driven concepts， suggesting that non-hexagonal rings contribute to HC’s unique structure. Despite advancements in model development， significant controversy persists regarding the terminology and conceptual frameworks used， complicating direct comparisons among studies. Consequently， a comprehensive understanding of HC structures necessitates further exploration and validation through advanced characterization techniques to address existing ambiguities.

2.2 Sodium ions storage mechanisms

A deep and accurate understanding of the sodium storage mechanism in HC is not merely an academic exercise； it is the fundamental prerequisite for rationally designing next-generation anodes with higher capacity， improved ICE， and faster kinetics[37] （Fig.3a）. For years， the HC mechanism has been a subject of intense debate， primarily because its disordered structure defies the clean， well-defined staging behavior observed in graphitic anodes[39]. The primary piece of evidence in this debate is the characteristic galvanostatic charge-discharge （GCD） profile of the HC anode. This profile is universally composed of two distinct regions： a sloping region at higher potentials （typically from ~1.2 V down to 0.1 V vs. Na/Na+） and a plateau region at a very low potential （below 0.1 V vs. Na/Na+）. The total capacity of the anode is the sum of the capacities from these two regions （CTotal = CSlope + CPlateau）. Critically， the ratio of sloping to plateau capacity is not fixed； it is highly dependent on the precursor material and， most importantly， the final pyrolysis temperature. This variability strongly suggests that the two regions correspond to different， and tunable， storage mechanisms. Based on generalizations and conclusions made by researchers over years， three different processes for Na storage in HCs include i） capacitive adsorption， ii） nanopore filling， and iii） insertion into the carbon interlayer[40]. To correspond to the voltage profile， the Na storage mechanisms of HCs can currently be categorized into four distinct models： the intercalation-pore filling model， the adsorption-intercalation model， the adsorption-pore filling model， and the three-stage adsorption-intercalation-filling model[38] （Fig.3b）. Understanding these mechanisms is the key to unlocking rational control over the material’s electrochemical properties.

2.2.1 The sloping region

The high-voltage sloping region， spanning potentials greater than 0.1 V， is a critical component of the HC voltage profile， typically contributing between 30% and 50% of the total sodium storage capacity[41]. However， this adsorption-only model fails to account for the total observed capacity， which is often far too large to be explained by the material’s specific surface area （BET） alone. This discrepancy has led to a widely accepted consensus that the sloping region hosts a second， simultaneous mechanism： the intercalation of Na+ ions into the expanded graphitic interlayers of the HC’s “house-of-cards” structure[42]. Unlike pristine graphite， these disordered nanodomains have an interlayer spacing （d002） expanded to >0.37 nm， which is sufficient to accommodate sodium. Because these domains are disordered and have a wide range of local environments， the intercalation occurs over a continuous range of potentials rather than at a flat plateau， thus contributing to the slope. Therefore， the sloping capacity is now understood to be a combination of both Na+ adsorption and Na+ intercalation[43]. From an engineering perspective， this dichotomy presents a double-edged sword： while maximizing the sloping region can significantly boost total capacity， it often signals a highly defective structure that is prone to parasitic reactions， thereby compromising the cell’s first-cycle efficiency and demanding a careful balance between capacity maximization and surface passivation.

2.2.2 The plateau region

The low-voltage plateau region， situated near 0 V vs. Na/Na+， stands as the most commercially valuable attribute of HC anodes， fundamentally determining the material’s ability to support high-energy-density SIB[44]. After decades of conflicting theories oscillating between intercalation and pore-filling models， the field has reached a robust consensus supporting the pore-filling mechanism[45]. This model posits that sodium ions diffuse into the intrinsic closed pores， internal nanovoids within the turbostratic carbon matrix that remain inaccessible to the electrolyte， where they subsequently nucleate into quasi-metallic sodium clusters[46]. This mechanism offers a unique safety advantage： unlike the hazardous surface plating observed in graphite or sodium metal anodes which can lead to dendrite growth and short circuits， HC facilitates internal-plating within the protective carbon framework， ensuring safe and reversible high-capacity storage. This mechanistic clarity provides a definitive directive for material engineering： to maximize this critical plateau capacity， synthesis strategies must strictly focus on optimizing the volume of closed micropores while suppressing open porosity. This requirement has catalyzed the industry-wide adoption of high-temperature pyrolysis （>1400 ℃） utilizing cross-linked precursors， a process essential for sealing the carbon microstructure to induce the dense network of closed pores required for superior energy density.

2.2.3 The adsorption-intercalation-pore filling consensus model

In recent years， the complex sodium storage behavior of HC has been unified under a three-step consensus model known as the adsorption-intercalation-pore filling mechanism[47]. This model accurately describes the full sodiation process as a sequence： first， in the high-voltage sloping region， Na+ ions are reversibly adsorbed onto external surfaces， defect sites， and open pore walls； second， in the mid-voltage sloping region， Na+ ions reversibly intercalate between the expanded， disordered graphitic interlayers； and finally， in the low-voltage plateau region， quasi-metallic sodium clusters are reversibly formed inside the closed micropores. The power of this consensus model lies in its ability to provide a direct， causal link between the precursor/synthesis process and the final electrochemical performance[48]. Specifically， the pyrolysis temperature acts as the primary knob for tuning the HC’s microstructure and consequently， the ratio of sloping to plateau capacity （CSlope/CPlateau）. At low pyrolysis temperatures （e.g.， 1000~1300 ℃）， the structure is highly disordered， retains more heteroatoms， and has a larger interlayer spacing， but lacks fully formed closed micropores； this results in a large sloping capacity （from adsorption/intercalation） but a very small plateau. Conversely， at high temperatures （e.g.， 1400~1700 ℃）， the material reorganizes and shrinks to form an extensive network of closed micropores， leading to a massive plateau capacity （from pore-filling） but a reduced sloping capacity， demonstrating a fundamental， temperature-driven trade-off that is a cornerstone of modern HC design.

Specifically， it reveals a fundamental trade-off governed by pyrolysis temperature： low-temperature synthesis yields defect-rich structures that maximize adsorption-driven sloping capacity but suffer from low ICE， whereas high-temperature synthesis promotes the formation of closed pores， thereby maximizing the high-value plateau capacity and improving ICE at the expense of sloping capacity. This model transforms the black box of pyrolysis into a predictable engineering challenge， guiding the optimization of the slope-to-plateau ratio for specific energy or power applications.

2.2.4 Comparative analysis of storage models

To bridge the gap between theoretical modeling and practical application， it is critical to understand that these four mechanisms function as descriptors for distinct material classes rather than competing universal truths. The adsorption-intercalation and adsorption-pore filling models are primarily applicable to low-temperature （<1000 ℃）， defect-rich chars or highly porous activated carbons， respectively. While these models accurately describe materials with high power capabilities （dominated by sloping capacity）， they fundamentally fail to account for the high volumetric energy density required by commercial cells. Conversely， the intercalation-pore filling model best describes denser， graphite-like carbons but often underestimates the kinetic limitations imposed by surface chemistry. Consequently， the three-stage adsorption-intercalation-pore filling model stands as the only comprehensive framework suitable for designing commercial battery-grade HCs. It uniquely enables engineers to map synthesis temperature to performance， tuning the adsorption/intercalation stages for power-critical applications while maximizing the pore-filling stage for energy-critical applications， thereby providing a rational blueprint for targeted material development.

2.3 Advanced characterization techniques

The critical validity of the adsorption-intercalation-pore filling consensus model， and specifically the pivotal role of the closed pore engineering strategy， has been rigorously established not through conjecture， but through a convergence of powerful advanced characterization techniques that allow researchers to effectively “see” and track Na+ ions within the complex carbon architecture[49]. These sophisticated tools have been instrumental in resolving historical debates by providing direct， empirical evidence that decouples the distinct electrochemical stages. In-situ XRD serves as the primary structural probe， offering real-time visualization of crystallographic evolution during battery operation. It unequivocally demonstrates that the （002） graphitic peak shifts to lower angles only during the high-voltage sloping region， confirming that lattice expansion via intercalation is confined to this stage[32]. Crucially， this peak shift arrests completely upon reaching the low-voltage plateau， providing definitive proof that the plateau capacity arises from a mechanism that does not involve further lattice distortion. Complementing this， small-angle X-ray scattering （SAXS） acts as the definitive morphological tool， capable of detecting and quantifying the internal closed micropores that are inaccessible to electrolytes and invisible to standard gas adsorption techniques. SAXS studies have firmly established a linear quantitative correlation between the volume of these hidden voids and the magnitude of the capacity plateau， validating the closed pores as the primary storage reservoirs. The final piece of the mechanistic puzzle is provided by 23Na solid-state nuclear magnetic resonance （ssNMR）， which acts as a spectroscopic“smoking gun”. By monitoring the chemical environment of the stored sodium， ssNMR detects a distinct knight shift， the unique resonance signature of metallic sodium， exclusively during the plateau region. This observation incontrovertibly proves that sodium ions are reduced to form quasi-metallic clusters within the shielded environment of the closed pores， rather than plating on the surface. Together， this triad of crystallographic， morphological， and spectroscopic evidence forms an unassailable foundation for the pore-filling model， guiding the rational design of next-generation high-capacity anodes[50].

3 Advanced synthesis and structural design

The establishment of the adsorption-intercalation-pore filling consensus model has transformed HC research from an empirical cook-and-look exercise into a sophisticated field of structural engineering. The modern objective is clear： to rationally synthesize microstructures that maximize the high-value plateau capacity （via closed pores） and minimize irreversible losses （via surface passivation）， all while utilizing cost-effective， scalable precursors. This shift requires precise control over precursor chemistry， cross-linking density， and pyrolysis thermodynamics. The following sections critically analyze the state-of-the-art strategies in biomass conversion， heteroatom doping， and pore architecture design， evaluating them not just by their laboratory performance， but by their potential for industrial adoption.

3.1 Biomass-derived hard carbons

The utilization of biomass as a precursor for HC represents the most commercially attractive synthesis route， aligning perfectly with the ethos of SIBs： low cost， sustainability， and resource abundance[51]. Unlike synthetic polymers （e.g.， phenolic resins） which are petro-chemically derived and relatively expensive， biomass precursors such as coconut shells， wood， fruit peels， and agricultural waste are effectively carbon-negative feedstocks. However， biomass is not a monolith； it is a complex composite primarily consisting of cellulose， hemicellulose， and lignin， and the ratio of these components dictates the final electrochemical performance[52] （Fig.4a）.

The electrochemical performance of biomass-derived HC is fundamentally dictated by the precursor’s intrinsic chemical composition and the thermal dynamics of its conversion[53] （Fig.4b）. The primary constituents， cellulose and lignin， direct the microstructural evolution along divergent paths： crystalline cellulose favors the formation of ordered， graphitic-like domains that facilitate sodium intercalation， thereby enhancing the high-voltage sloping capacity[54-55]. Conversely， the complex， cross-linked aromatic structure of lignin acts as a steric anchor， preventing graphitization even at high temperatures and preserving a disordered house-of-cards architecture rich in closed micropores[56]. This disordered structure is critical for maximizing the low-voltage plateau capacity via the pore-filling mechanism， making lignin-rich precursors structurally predisposed for high-energy-density applications. The transformation from raw biomass to functional anode occurs through three distinct thermal stages. Initial low-temperature heating （<600 ℃） releases volatiles to form a porous char， while intermediate temperatures （800~1200 ℃） drive aromatization， resulting in a defect-rich material with high sloping capacity but low ICE[57-58]. Crucially， the final high-temperature stage （>1400 ℃） is the engineering sweet spot； it induces the coalescence of graphene sheets to seal off micropores， creating the closed pores necessary for high plateau capacity and annealing surface defects to improve ICE， albeit at the cost of increased manufacturing energy consumption （Table 1）.

While the academic narrative of “turning banana peels into batteries” is compelling， its industrial application faces a critical scalability bottleneck centered on consistency. Battery manufacturing demands feedstocks with purity exceeding 99.9% and rigorous reproducibility， criteria that heterogeneous biomass， varying in lignin and cellulose composition due to seasonal and geographical factors， struggles to meet. A more severe impediment is the intrinsic ash content， where bio-accumulated inorganic minerals like Si， K， and Ca wreak havoc in electrochemical systems. These impurities catalyze continuous electrolyte decomposition， thickening the SEI and permanently degrading ICE， while also inducing uncontrolled self-activation during pyrolysis that creates undesirable open porosity. Consequently， the industrial viability of biomass-derived HC depends less on discovering exotic precursors and more on engineering scalable purification processes[59]. Although acid leaching can effectively reduce ash to acceptable levels （<0.5%，mass fraction）， it introduces substantial chemical waste and processing costs that erode the material's economic advantage. To bridge the gap between low raw material costs and high processing expenses， future efforts must focus on developing standardized pre-purification protocols or selecting naturally low-ash precursors， ensuring biomass serves as a reliable， consistent feedstock for GWh-scale production.

3.2 Heteroatom doping

Intrinsic HC， defined by its disordered and turbostratic microstructure， inherently suffers from a scarcity of reversible active storage sites and sluggish sodium-ion kinetics， factors that significantly constrain its rate capability and practical implementation in high-performance SIBs. To surmount these intrinsic limitations， heteroatom doping has established itself as a powerful and versatile strategy for engineering the carbonaceous framework at the atomic scale. By chemically substituting carbon atoms with foreign elements such as N， S， P， or B， material scientists can effectively modulate the local electronic structure and geometric architecture of the anode[66-72]. Nitrogen stands out as the most extensively studied element， exhibiting three primary bonding configurations： pyridinic-N， pyrrolic-N， and quaternary-N （graphitic N）. The first two configurations， pyridinic-N and pyrrolic-N， are known to induce carbon vacancy defects， which facilitate the creation of electron acceptor states capable of attracting electrons from sodium atoms， thereby improving sodium ion storage capacity， while graphitic nitrogen substitution injects free electrons into the conduction band， fundamentally improving bulk electrical conductivity and high-rate performance. To illustrate the efficacy of targeted nitrogen configuration， recent studies have utilized naturally nitrogen-rich biomass， such as mushroom cultivation waste， to elucidate the role of pyridinic-N defects. By introducing extrinsic nitrogen sources （e.g.， hexamethylenetetramine） during carbonization， the electronic structure of the carbon matrix can be fundamentally altered. Liu et al. demonstrated that maximizing the ratio of pyridinic-N defects， rather than simply increasing total nitrogen content， is the key driver for enhanced sodium storage[73]. This configuration effectively lowers the adsorption energy barrier for sodium ions， doubling the reversible capacity compared to undoped counterparts （218 vs. 111 mAh/g）. However， this substantial capacity gain serves as a critical case study for the Doping Dilemma： while the defect-rich structure significantly boosts sodium uptake in the sloping region， it underscores the necessity of balancing defect density with initial coulombic efficiency for practical applications.

In parallel， doping with larger atoms like phosphorus and sulfur leverages steric effects to act as structural props. These dopants physically force the graphene layers apart， expanding the interlayer spacing （d002） to reduce the thermodynamic energy barrier for intercalation， effectively creating ion-highways that facilitate rapid sodium diffusion. Furthermore， boron doping utilizes its electron-deficient character to shift the material’s Fermi level， creating specific sites with strong binding affinity for sodium that significantly augment capacitive storage. Thus， heteroatom doping transforms the passive carbon matrix into a tunable， electrochemically active landscape， optimizing the critical balance between capacity， conductivity， and kinetics.

Despite the widespread academic enthusiasm for doping， a critical engineering trade-off is frequently glossed over： the inverse relationship between doping-induced capacity and ICE. This is the Doping Dilemma. Therefore， from an industrial perspective， the pursuit of “high capacity via high doping” often proves to be a false economy， requiring a strategic pivot toward efficiency-neutral doping methodologies that decouple capacity gains from efficiency losses. To overcome the inherent trade-off between increased active sites and degraded ICE， future research must prioritize three distinct engineering approaches[74]. First， low-concentration doping should be employed to enhance bulk electronic conductivity using only trace amounts of heteroatoms， thereby avoiding the generation of excessive surface defects that consume sodium. Second， sophisticated surface-bulk differentiation architectures must be developed， where dopants are concentrated within the bulk to expand interlayer spacing and facilitate ion transport， while the surface remains pristine and undoped to minimize parasitic SEI formation. Finally， the industry must acknowledge a strict pre-sodiation dependence， accepting that highly doped， high-capacity anodes are only commercially viable when paired with scalable pre-sodiation technologies capable of compensating for their inevitable efficiency penalties.

3.3 Morphological and pore structure engineering

The ultimate objective of HC engineering is to design an ideal architecture that effectively balances the conflicting requirements of sodium storage mechanisms； a challenge fundamentally rooted in the closed vs. open pore dichotomy. This structural dilemma dictates the trade-off between kinetic performance and electrochemical efficiency. Open pores， which are accessible to the electrolyte， offer the advantage of rapid ion infiltration and provide the necessary surface area for adsorption-driven sloping capacity， thereby enhancing rate capability. However， this accessibility is also their fatal flaw； the large exposed surface area acts as the primary site for extensive SEI formation， leading to significant irreversible sodium loss and a critically low ICE[75]. Conversely， closed pores， internal voids sealed within the carbon matrix， serve as shielded reservoirs for metallic sodium clusters， generating the high-value plateau capacity essential for energy density while protecting the sodium from parasitic side reactions， thus ensuring high ICE[76]. Yet， accessing these sequestered voids requires Na+ ions to diffuse through the bulk carbon lattice， which can impede reaction kinetics. Consequently， the central imperative for designing commercially viable HC anodes is to synthesize materials that simultaneously minimize open porosity to secure an ICE exceeding 85%， while maximizing the volume of closed micropores to guarantee superior energy density， thereby resolving this inherent structural paradox[77-78].

The transition from kinetic-favorable open pores to capacity-dense closed pores represents a critical engineering frontier. A sophisticated pore-closure strategy was effectively demonstrated by Pan et al.， who utilized a sequential etching-and-deposition approach[79]. By first creating a generic open-pore framework via KOH etching and subsequently sealing these voids using CVD of acetylene， they successfully engineered a pseudo-graphitic architecture rich in closed voids （Fig.5）. This study is particularly valuable not just for its high capacity （398.6 mAh/g）， but for its mechanistic validation using in-situ Raman spectroscopy. The spectroscopic data provided direct evidence of the storage sequence： sodium ions first saturate the defect sites （adsorption）， followed by a massive insertion into the newly formed closed pores （plateau）， confirming that precisely engineered pore closure is the primary driver for maximizing the low-voltage plateau capacity without sacrificing reversibility.

While closed pores are essential for energy density， they often suffer from sluggish ion transport. To resolve this kinetic bottleneck， the design of bicontinuous mesoporous architectures offers a compelling solution. The concept of a single primitive （SP） microstructure， as introduced by Mai et al.， utilizes ordered meso-channels to act as high-speed ion highways that permeate the bulk material[80] （Fig.6）. This structure effectively decouples electron transport from ion diffusion， allowing for rapid sodium access to deep storage sites even at high current densities. The industrial relevance of this morphology is highlighted by its exceptional durability； the ability to sustain 100000 cycles at 10 A/g suggests that maintaining a continuous， stress-dissipating carbon framework is crucial for preventing the mechanical degradation typically seen in isolated pore structures.

Moving from qualitative descriptions to quantitative engineering， the ability to precisely tune and measure closed pore volume is a prerequisite for commercial adoption. Yu et al. established a direct， linear correlation between the volume of roughly 2 nm closed pores and the magnitude of the voltage plateau， utilizing Rosin-derived gases as an internal spacing agent[81] （Fig.7a）. By validating these findings with SAXS， this work shifts the field toward measurable structural metrics rather than trial-and-error synthesis. Critically， when benchmarked in full pouch cells against commercial hard carbon standards， the optimized pine HC demonstrated superior volumetric and gravimetric energy density （315.8 Wh/kg） （Fig.7b）. This comparison serves as a vital proof-of-concept， illustrating that rational pore size regulation， specifically targeting the 2 nm regime， is the most effective pathway to exceed the performance limits of currently available commercial anodes （Fig.7c）.

To realize the holy grail of a closed-pore-dominant microstructure， researchers have developed advanced synthesis strategies that transcend simple pyrolysis. While traditional template synthesis using hard templates like silica can precisely engineer pore dimensions， the requirement for corrosive etching processes renders it costly and environmentally problematic for mass production. A more sustainable and scalable alternative has emerged in molten salt synthesis， where precursors are carbonized within a molten salt medium （e.g.， NaCl/KCl）； the salt acts as a liquid template and solvent that facilitates the formation of graphitic domains while preventing pore collapse， and crucially， it can be easily washed away with water and recycled. For precursors prone to melting， such as pitch， cross-linking stabilization via oxidative heating is essential to freeze the polymeric structure prior to carbonization， ensuring the retention of a high volume of closed pores. It is imperative to distinguish these modern techniques from traditional chemical activation， which aggressively etches carbon to create massive open surface areas （>2000 m2/g）； while beneficial for supercapacitors， this is disastrous for SIB anodes due to excessive SEI formation. Finally， state-of-the-art engineering increasingly employs composite and coating strategies， such as chemical vapor deposition， to deposit a thin， disordered carbon shell over a porous core. This hierarchical core-shell architecture effectively seals reactive surface defects， mitigating SEI losses， while preserving the high-capacity closed pores within， representing the current pinnacle of anode design for balancing performance with commercial viability.

4 How to solve the low iCE

If the structural engineering described in Section 3 represents the scientific foundation of HC， then the ICE is its single greatest commercial and engineering hurdle. The ICE quantifies the irreversibility of the first charge-discharge cycle， defined as the ratio of discharge capacity to charge capacity[82]. For standard HC anodes， this value typically stagnates between 75% and 85%. This metric is not merely a number； it implies that 15%~25% of the active sodium ions， supplied by the expensive cathode， are permanently consumed and locked away during the very first cycle[83]. Therefore， solving the low ICE problem， pushing it from ~80% to >95%， is arguably the most critical and intensely researched challenge bridge the gap to commercial viability.

4.1 Understanding the root causes of low ICE

To rationally engineer a solution for the low ICE， the 15%~30% irreversible sodium loss must be deconstructed into three distinct， fundamental failure mechanisms that operate concurrently during the first cycle. The primary and most debilitating source of loss is the formation of the SEI. Unlike the robust， self-limiting passivation layer observed on graphite in LIBs， the SEI formed on HC in SIBs is inherently more soluble and mechanically distinct. The larger ionic radius of the sodium ion facilitates the formation of a fragile mosaic structure that is prone to partial dissolution and continuous fracturing， necessitating a perpetual repair process that parasitically consumes the finite sodium inventory. This instability is compounded by irreversible trapping within the bulk microstructure， where Na+ ions are chemically sequestered at high-energy defect sites， edges， and heteroatom interfaces. These sites， often introduced via doping strategies to enhance capacity， exhibit binding energies that exceed the extraction capabilities of the anode’s operating potential， effectively locking away active lithium. Finally， the surface chemistry of the anode， particularly in sustainable biomass-derived carbons， contributes a third layer of loss through the reactivity of residual functional groups. Oxygenated moieties such as carboxyl （—COOH） and hydroxyl （—OH） groups react irreversibly with electrolyte salts to precipitate stable， insulating byproducts like Na2CO3 and NaOH[84]. Critically， these side reactions are not merely electrochemical sinks； they actively generate gaseous byproducts （H2， CO2） that lead to dangerous cell swelling and delamination， presenting a severe safety hurdle for pouch cell integration.

4.2 Electrolyte engineering （mitigation）

Since the instability of the SEI constitutes the primary root cause for the low ICE in HC anodes， engineering the electrolyte formulation represents the most immediate and impactful first line of defense. The ultimate objective is to design a liquid environment that spontaneously forms a robust， nanometrically thin， and electronically insulating passivation layer upon the very first charge， thereby arresting further solvent decomposition[85].

Traditional carbonate-based ester electrolytes （e.g.， EC/DEC） often fail this mandate， as they are prone to solvent co-intercalation into the disordered carbon structure and form thick， organic-rich SEI layers that are mechanically fragile and soluble， leading to continuous efficiency losses over cycling[86]. To overcome this， ether-based electrolytes （e.g.， diglyme） have emerged as a powerful alternative； their ability to form stable coordination complexes with sodium ions effectively suppresses co-intercalation and facilitates the formation of a highly uniform， thin SEI， frequently enabling ICE values exceeding 90% and superior kinetic performance， although their poor oxidation stability remains a challenge for full-cell voltage pairing. Simultaneously， the industry has widely adopted functional additives like fluoroethylene carbonate （FEC） as a standard mitigation strategy. Possessing a higher reduction potential than bulk solvents， FEC decomposes preferentially to generate a compact， inorganic-rich SEI dominated by NaF. This fluorinated layer acts as a robust physical shield， though the sacrificial nature of FEC means its eventual depletion can lead to sudden cell failure， known as the“FEC cliff”. Moving beyond additives， High-concentration electrolytes （HCEs） represent a radical shift in solvation chemistry. By increasing salt concentrations above 3 mol/L， HCEs force anions （such as FSI-） into the primary solvation sheath， driving them to decompose before the solvent. This anion-derived decomposition creates a ceramic-like， inorganic SEI that yields exceptional stability and ICE values >95%. While currently hindered by the high cost of salts and prohibitive viscosity， emerging“localized high-concentration electrolytes” （LHCEs） that utilize non-solvating diluents offer a promising pathway to harness these benefits at a commercially viable price point.

Beyond chemical stability， a frequently overlooked bridging the gap challenge in commercial cell assembly is the physical wettability of the electrode. High-performance hard carbons， particularly those annealed at ultra-high temperatures （>1400 ℃） to maximize plateau capacity， undergo a near-complete removal of surface oxygen functional groups. This renders the material surface highly non-polar and hydrophobic. Conversely， standard SIB electrolytes are polar solvents. This mismatch creates a high contact angle that severely impedes electrolyte infiltration， particularly in the tightly wound or stacked environment of large-format pouch and cylindrical cells.

In addition， step-by-step desolvation： Lu et al.[87] recent studied using 3A zeolite molecular sieve films to regulate the solvation structure at the interface. The zeolite nanopores （approx. 3.2 Å） induce a pre-desolvation effect， stripping solvent molecules and creating a localized beyond concentrated electrolyte environment near the anode surface （Fig.8）. This lowers the activation energy for desolvation and promotes the formation of a thin， inorganic-dominated （NaF-rich） SEI. Unlike traditional methods， this approach significantly improves rate capability and cycle life by ensuring the SEI is mechanically robust and highly conductive to Na+ ions.

4.3 Surface engineering and coatings （mitigation）

To effectively mitigate surface-driven irreversible losses， surface engineering strategies have evolved to modify the reaction surface itself， creating a stable interface that minimizes electrolyte decomposition without impeding Na+ ion transport. The most fundamental approach involves defect healing via high-temperature annealing （>1400 ℃）， which thermally eliminates residual functional groups and anneals surface defects， thereby reducing the specific surface area available for parasitic reactions. For more precise control， atomic layer deposition （ALD） offers a route to engineer an artificial SEI by depositing ultrathin， conformal coatings of metal oxides （e.g.， Al2O3） or phosphates[88]. These nanometric layers are physically robust and ionically conductive， effectively blocking electron tunneling to the electrolyte while permitting Na+ ions intercalation； however， the scalability of ALD is currently limited by its slow， vacuum-based batch processing. Consequently， industry is increasingly adopting soft carbon coatings as a pragmatic， scalable alternative. This technique involves encapsulating porous HC particles within a precursor （such as pitch） which is subsequently carbonized to form a dense， low-defect soft carbon shell. This core-shell architecture effectively seals the reactive open pores of the HC core， preventing excessive SEI formation， while maintaining a permeable pathway for Na+ ions to access the high-capacity closed pores within， representing the current state-of-the-art for balancing high capacity with high ICE[26].

Recent studies have deepened the understanding of defect healing by focusing on oxygen regulation. Oxygen atoms in the HC precursor induce wrinkling in the graphitic layers， expanding interlayer spacing. Precisely regulating the release of oxygen （e.g.， via treatment at 1500 ℃） eliminates these kinks， resulting in flatter， longer graphitic layers with narrower spacing[89] （Fig.9a~c）. This structural evolution facilitates the formation of abundant closed pores， which significantly boosts plateau capacity and raises ICE values to ~85% by reducing the surface active sites responsible for electrolyte decomposition （Fig.9d）. This work reveals the structural regulation mechanism of HC by adjusting the oxygen content and introduces a strategy to develop HC for high-performance SIBs （Fig.9e）.

4.4 Pre-sodiation （compensation）

Even with optimized electrolytes and surface coatings， thermodynamically eliminating all irreversible losses remains an elusive goal， compelling the industry to adopt pre-sodiation not merely as an optional enhancement， but as an economic necessity for high-energy SIBs[90]. This strategy fundamentally shifts the engineering paradigm from mitigating loss to actively compensating for it by introducing a sacrificial sodium reservoir to satisfy the anode’s irreversible capacity， thereby eliminating the need for expensive cathode oversizing[91]. While direct anode pre-sodiation methods， such as physical lamination of sodium foil or chemical soaking in reactive solutions like sodium biphenyl， offer high efficacy in laboratory settings， they are fraught with severe scalability issues[92]. The handling of highly reactive metallic sodium presents extreme fire hazards and compatibility challenges with high-speed roll-to-roll manufacturing， rendering them largely impractical for gigafactory deployment. Consequently， the industry is converging on cathode-side strategies as the most viable path forward. This approach utilizes sacrificial additives， such as sodium-rich salts （e.g.， Na2C2O4， Na2CO3， Na3N）， which are blended directly into the cathode slurry. These additives decompose during the initial charge to release a surplus of Na+ ions that fill the anode's traps， leaving behind a harmless residue or gas. This method integrates seamlessly into existing production lines without requiring specialized equipment or hazardous materials handling. However， it is not without its own techno-economic hurdles； the decomposition process often generates significant gas volumes， necessitating rigorous degassing protocols that complicate cell assembly， particularly for pouch cells. Furthermore， any residual solid byproducts act as dead mass， marginally reducing the specific energy. Thus， the ultimate “holy grail” for pre-sodiation lies in the development of air-stable， residue-free additives that decompose cleanly at specific potentials， balancing manufacturing simplicity with electrochemical performance.

Ultimately， the most elegant solution to the sodium inventory problem is to render pre-sodiation obsolete through intrinsic material design. A notable advance in this direction was achieved by Yu et al.， who demonstrated that catalytic graphitization can push HC ICE values beyond the critical 90% threshold （achieving 91.6%）[93]. By employing cobalt ions as catalytic centers during the pyrolysis of xylose， they induced the formation of expanded graphitic nanodomains within the disordered matrix （Fig.10a）. This work provides a crucial mechanistic insight into the self-healing of porosity： utilizing 3D electron tomography， the study revealed that initially isolated nanopores dynamically collapse into interconnected pancake-like voids during cycling （Fig.10b~e）. This stress-adaptive restructuring allows for rapid sodium transport while maintaining a low surface area for parasitic reactions （Fig.10f~h）. By achieving such high intrinsic efficiency （396.4 mAh/g reversible capacity）， this catalytic approach validates that precise microstructural control can effectively eliminate the economic and safety burdens associated with external pre-sodiation steps， representing a zero-compensation ideal for next-generation anodes.

5 Full-cell development： bridging the gap to commercialization

The true validation of any battery innovation lies not in the controlled environment of a half-cell， but in the rigorous， interconnected reality of a full-cell device. While Section 2 through Section 4 have established the scientific foundations of HC， its storage mechanism， rational synthesis， and efficiency mitigation， this section addresses the complex engineering required to integrate these advanced anodes into commercially viable SIBs. The transition from lab coin cells to industrial pouch or cylindrical formats is non-trivial； it introduces a new set of system-level challenges， including precise sodium inventory management， cathode matching， and the mitigation of catastrophic failure modes like gassing and swelling[94]. In addition to academic full-cell studies， commercial SIBs， although not always employing biomass-derived HC， offer valuable benchmarks that illustrate the practical viability of this technology. Moreover， several companies have initiated the commercialization of SIBs using HC as the anode material， as summarized in Table 2. This phase of development represents the “Valley of Death” for battery materials， where promising chemistry often fails due to practical engineering constraints.

5.1 Sodium inventory problem

In a full SIB， the system operates as a closed loop where the total available sodium inventory is finite and strictly determined by the cathode mass （Fig.11）. This creates a critical design constraint known as the sodium inventory problem， which is directly exacerbated by the low ICE of HC anodes. Since typical HC anodes exhibit an ICE of approximately 80%， roughly 20% of the active sodium extracted from the cathode during the first charge is irreversibly consumed by SEI formation and deep trapping within the anode microstructure. Because this Na+ ions cannot return to the cathode， the cell’s reversible capacity is permanently capped， necessitating a strategy of cathode oversizing. Manufacturers must load the cell with 20%~30% excess cathode material merely to act as a sacrificial sodium donor， a practice that incurs severe economic and gravimetric penalties given that the cathode is the heaviest and most expensive component. Consequently， the selection of a cathode partner becomes a strategic exercise in balancing these trade-offs against specific application requirements. Layered oxides （NaxTMO2） are often favored for maximizing energy density due to their high capacity and voltage compatibility with the low-potential plateau of HC， despite their moisture sensitivity. Conversely， prussian blue analogs （PBAs） offer a cost-effective solution with fast kinetics suitable for grid storage， though they struggle with low tap density and residual water issues that can trigger gassing[96]. Finally， polyanionic compounds （Na3V2（PO4）3） provide an ultra-safe， long-life alternative thanks to their robust 3D frameworks， making them ideal for stationary applications where thermal stability outweighs the need for maximum energy density， provided the initial inventory loss is effectively managed[97].

5.2 Pouch cell and cylindrical cell prototyping

The transition from lab-scale coin cells to commercial formats， such as 18650 cylindrical or multi-layer pouch cells， introduces profound engineering challenges that fundamentally alter the electrochemical environment. While academic research often relies on coin cells operating under flooded electrolyte conditions and high stack pressures to mask kinetic limitations， commercial applications demand lean electrolyte volumes to maximize volumetric energy density. This constraint exposes a critical vulnerability in HC anodes： the continuous consumption of electrolyte for SEI repair. In a flooded system， this loss is buffered， but in a commercial cell， it leads to rapid electrolyte dry-out， resulting in a catastrophic rise in internal resistance and premature capacity fade. Therefore， developing HC materials with exceptionally stable surfaces that minimize parasitic consumption is a non-negotiable requirement for industrial adoption. Additionally， the integration of aluminum current collectors， a key cost advantage of SIBs， presents unique processing hurdles. Unlike the Cu foils used in LIBs， Al requires tailored slurry engineering to ensure adequate adhesion[98]. Overcoming these mechanical interfaces necessitates the development of optimized binder formulations， particularly aqueous systems like CMC/SBR， to maintain robust electrical contact and structural integrity against the mechanical stresses of volume expansion during long-term cycling[99-100].

5.3 Practical failure modes

Beyond basic electrochemical matching， two critical physical failure modes， catastrophic gassing and low volumetric energy density， pose severe threats to the commercial viability of HC anodes， particularly in pouch cell formats[101] （Fig.12）. Gassing represents the foremost safety hazard， especially for biomass-derived HC， where residual oxygen-containing functional groups （—OH， —COOH） and adsorbed moisture within micropores react with the electrolyte during the initial charge and subsequent cycling[102]. This reaction generates significant volumes of H2， CO2， and gaseous hydrocarbons， causing sealed pouch cells to swell or pillow， which physically delaminates electrode layers， severs electrical contact， and drastically increases impedance[103]. Mitigation requires a multi-tiered strategy： ultra-high temperature firing （>1500 ℃） to fully carbonize functional groups， the implementation of rigorous industrial degassing protocols during formation cycles， and the use of electrolyte additives that passivate the surface prior to gas evolution[104]. Simultaneously， engineers face the calendaring dilemma driven by HC’s fluffy， disordered microstructure， which naturally yields a low tap density （0.8~1.0 g/mL） compared to graphite. While compressing electrodes is necessary to increase volumetric energy density （Wh/L）， the brittle “house-of-cards” structure of HC is prone to collapse under pressure， crushing the internal closed pores essential for plateau capacity. Achieving a commercially competitive electrode density （>1.1 g/mL） without sacrificing electrochemical performance thus demands the precise engineering of a goldilocks density zone， potentially through the development of spherical particles or advanced composite architectures that withstand calendaring forces while maintaining pore integrity[105]. Despite these hurdles， recent breakthroughs have proven the commercial viability of HC-based SIBs. The most notable is CATL’s 2021 announcement of their first-generation SIB， which achieved a gravimetric energy density of 175 Wh/kg in a commercial-sized cell[106]. This benchmark， which rivals entry-level LFP batteries， was achieved by pairing a high-performance HC anode （likely with a pre-sodiation strategy） with a high-capacity PBA cathode[107]. In the academic realm， high-performance pouch cells with optimized HC anodes are now routinely demonstrating energy densities of 120~140 Wh/kg with stable， long-term cycling[108]. These prototypes provide the definitive proof-of-concept that the fundamental science of HC can be successfully translated into a practical， high-performance energy storage device.

6 Challenges and future perspectives

The journey of HC from a laboratory curiosity to the foundational anode material of SIBs has been one of remarkable progress， yet the last mile to widespread GWh-scale adoption remains the most arduous. As this review has detailed， the field has successfully transitioned from fundamental mechanistic debates to pragmatic engineering solutions. However， a significant chasm still separates current prototype performance from the stringent reliability and cost requirements of the automotive and grid-storage sectors. The future of HC research must therefore pivot away from the pursuit of hero capacities in coin cells and focus intensely on solving the systemic barriers to manufacturing scalability， economic viability， and safety （Fig.13）. The era of fundamental discovery for HC is largely complete； the era of rigorous industrial engineering has begun. The successful resolution of these final challenges， ICE， scalability， and density， will determine whether HC remains a promising alternative or ascends to become the backbone of a sustainable， post-lithium energy economy.

1）Pre-sodiation paradox： perhaps the most urgent challenge is the pre-sodiation paradox. While pre-sodiation is scientifically recognized as the most effective solution to neutralize the ICE penalty and eliminate the need for costly cathode oversizing， a commercially viable method remains elusive. Current approaches face a dichotomy： methods that offer high performance （e.g.， metallic sodium lamination） are inherently unsafe and incompatible with high-speed manufacturing， while scalable methods （e.g.， cathode additives） often introduce dead mass， gas generation， and processing complexity. The industry desperately requires a breakthrough in air-stable， residue-free sacrificial additives or innovative anode-free architectures that can circumvent the sodium inventory problem entirely. Until a safe， low-cost pre-sodiation technique is standardized， the cost-per-kWh advantage of SIBs will remain partially theoretical.

2）Biomass scalability gap： the narrative of green batteries derived from food waste is compelling but belies a significant industrial risk： supply chain consistency. Unlike synthetic polymers， biomass is subject to seasonal variation， geographical heterogeneity， and trace impurity profiles （ash content） that wreak havoc on electrochemical reproducibility. For HC to become a commodity， the industry must bridge this scalability gap. Future efforts should focus not on discovering novel exotic precursors， but on developing standardized， low-cost purification and carbonization protocols that can homogenize diverse feedstocks into a battery-grade product with 99.9% consistency. Alternatively， a strategic pivot toward low-cost synthetic precursors， such as recycled plastics or pitch， may offer a more reliable path to scale， even if it sacrifices some degree of green marketing appeal.

3）Volumetric & kinetic ceiling： HC’s intrinsic low density and fluffy microstructure impose a volumetric energy density ceiling that limits its penetration into space-constrained applications like passenger EVs. Overcoming this requires a fundamental redesign of the particle morphology. Future research must prioritize the engineering of dense， spherical HC particles capable of achieving tap densities >1.1 g/mL without pore collapse during calendaring. Simultaneously， the sluggish solid-state diffusion in the plateau region limits fast-charging capabilities. Developing ion-highway architectures， hierarchically porous structures that align diffusion channels， will be critical to unlocking the high-power performance required for modern applications.

4）Data-driven design and solid-state compatibility： looking beyond immediate engineering fixes， two transformative opportunities lie on the horizon. First， the quantitative gap in synthesis， the black box of pyrolysis， must be illuminated by Materials Informatics. By leveraging machine learning to correlate precursor chemistry and pyrolysis conditions with pore evolution， the field can move from Edisonian trial-and-error to rational， predictive design-on-demand. Second， as the industry looks toward all-solid-state SIBs for ultimate safety， HC must be re-engineered for solid-solid interfaces. Understanding the mechanochemical compatibility of HC with sulfide or halide solid electrolytes will be the next great frontier in SIBs.

7 Conclusions

Hard carbon has undeniably cemented its position as the definitive anode material for the inaugural generation of commercial SIBs， serving as the critical enabler for a new era of cost-effective， sustainable energy storage. The scientific trajectory of this material has been transformative： beginning with foundational debates over storage mechanisms， the field has coalesced around the adsorption-intercalation-pore filling consensus， which now serves as a robust blueprint for rational material design. This mechanistic clarity has empowered researchers to move beyond trial-and-error synthesis， enabling the targeted engineering of closed-pore architectures that maximize energy density. However， the path from successful prototype to ubiquitous GWh-scale adoption is no longer a question of fundamental science， but one of intense， pragmatic engineering. As highlighted in this review， the commercial viability of HC and by extension， the SIB hinges on overcoming a triad of interconnected hurdles： the economic penalty of low ICE， the manufacturing risks of biomass precursor inconsistency， and the safety challenges of cell gassing. Addressing these issues requires a holistic approach that integrates scalable pre-sodiation technologies， standardized precursor purification protocols， and advanced electrolyte formulations. If the research community can successfully navigate these final engineering barriers， HC will not merely serve as a low-cost alternative to graphite， but will ascend as the foundational pillar of a sustainable， post-lithium energy grid， unlocking the full potential of sodium-ion technology for a decarbonized future.

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基金资助

河南省自然科学基金项目(252300423022)

河南省自然科学基金项目(252300423540)

河南省高等学校重点科研项目(26A140018)

河南省大学生创新创业训练计划项目(S202510478047)

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