Generation Lithium-ion Batteries Research Articles

Unveiling the potential of lithium fluoride phosphate (Li2MPO4F, M = Fe, V, Mn) for the next generation of lithium-ion batteries: A comparative study based on first principles and molecular dynamic simulations

LiFePO4 (LFP) cathode with olivine crystal structure has been a key player in safe and affordable energy storage, owing to its low-cost iron and high electrochemical stability within a voltage range of commercial electrolytes (2.8–3.4 V). To maintain these benefits while enhancing its energy density, Li2MPO4F was developed by introducing fluorine (F) and replacing iron with other transition metals (M). However, previous studies on these materials primarily measured performance within a limited voltage window (e.g., 2.5–4.5 V), making it challenging to analyze their performance under advanced electrolytes with a broader voltage range. In this study, we took a novel approach by utilizing first principles and molecular dynamic calculations to investigate the electrochemical performance of Li2MPO4F with three types of transition metals (M = V, Fe, Mn). This unique methodology, which includes calculations on theoretical voltages, atomic structures, and diffusion coefficient after structural optimization, allowed us to predict the impact of transition metals on cathode performance. By closely comparing the expected results, this study discusses the pros and cons of each cation substitution and suggests suitable cathode materials for batteries with high energy density and superior rate capability.

Constructing Targeted Strong Nb4d-O2p-Li2s Configurations to Obtain Excellent Energy Density and Long Life for Li-Rich Cathodes.

The Li-rich Mn-based cathode materials (LMRs) deliver excellent energy density and exhibit low cost, which are considered as the most promising cathode materials for the next generation lithium-ion batteries. However, the irreversible redox reaction of the oxygen atoms directly leads to release oxygen and intensifies phase transformation. Besides, the local stress and strain will be generated due to the unit-cell volume difference between R-3m and C2/m phases, which continuously aggravates the collapse of secondary particles. Herein, the strong Nb4d-O2p-Li2s configurations at the Li1 sites of the TM-layer in the C2/m phase and secondary particles with the radial arrangement of refined primary particles are designed to inhibit oxygen release and relieve lattice stress by Nb2O5 treatment. Meanwhile, the preferential growth of the active {010} planes is presented to obtain an excellent transmission rate of Li+. As a result, the designed LMR delivers remarkable electrochemical properties with high discharge capacity and initial coulomb efficiency of 276 mAh g-1 and 85 % at 0.1 C, outstanding cycling retention rate of 81 % after 300 cycles. This novel crystal structure combining oxygen coordination regulation and micro-nano scale design provides inspiration for the design of high-performance LMRs.

Structural design and investigation of Ti3C2 MXene as a conductive interlayer for improving the lithium-storage performance of PSi@C anode material

Silicon stands out as an ideal anode material for the next generation of lithium-ion batteries (LIBs) due to its abundant sources, low lithiation/delithiation potential, and high specific capacity. However, its practical application is impeded by significant volume expansion, leading to electrode structure damage. In this study, the Porous silicon(PSi)@C/Ti3C2 MXene composite was developed by dispersing porous micro-silicon@carbon (PSi@C) particles into layered stackable Ti3C2 MXene sheets using ultrasonic and freeze drying. The Ti3C2 MXene interlayer played a crucial role in enhancing the conductive crosslinking network between PSi@C particles, and providing efficient channels for electron transport/ion diffusion. Additionally, the Ti3C2 MXene interlayer served as a buffer to accommodate the substantial volume changes in silicon during electrochemical cycling. Consequently, the PSi@C/Ti3C2 MXene composite electrode demonstrated rapid electron/ion conduction and maintained structural stability. Remarkably, the electrode exhibited outstanding long cycle stability with 952 mAh g-1 at 0.5 A g-1 after 200 cycles and excellent rate performance with 542 mAh g-1 at 2 A g-1.

Controllable Synthesis of Hollow Dodecahedral Si@C Core-Shell Structures for Ultrastable Lithium-Ion Batteries.

Silicon (Si) has attracted considerable attention as a promising alternative to graphite in lithium-ion batteries (LIBs) because of its high theoretical capacity and voltage. However, the durability and cycling stability of Si-based composites have emerged as major obstacles to their widespread adoption as LIBs anode materials. To tackle these challenges, a hollow core-shell dodecahedra structure of a Si-based composite (HD-Si@C) is developed through a novel double-layer in situ growth approach. This innovative design ensures that the nano-sized Si particles are evenly distributed within a hollow carbon shell, effectively addressing issues like Si fragmentation, volume expansion, and detachment from the carbon layer during cycles. The HD-Si@C composite demonstrates remarkable structural integrity as a LIBs anode, resulting in exceptional electrochemical performance and promising practical applications, as evidenced by tests in pouch-type full cells. Notably, the composite shows outstanding cycling stability, retaining 85% of its initial capacity (713 mAh g-1) even after 3000 cycles at a high current rate of 5000mA g-1. Additionally, the material achieves a gravimetric energy density of 369Wh kg-1, showcasing its potential for efficient energy storage solutions. This research signifies a significant step toward realizing the practical utilization of Si-based materials in the next generation of LIBs.

Pyrrolidinium-Based Ionic Liquids as Advanced Non-Aqueous Electrolytes for Safer Next Generation Lithium Batteries

In the current context of increasing energy demand, ionic liquids (ILs) are presented as possible candidates to replace conventional electrolytes and to develop more efficient energy storage devices. The IL 1-Methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide has been selected for this work, due to the good thermal and chemical stabilities and good electrochemical performance of the pyrrolidinium cation based ILs. Binary mixtures of this IL and lithium salt with the same anion, [TFSI], have been prepared with the aim of assessing them, as possible electrolytes for lithium batteries. These mixtures were thermally and electrochemically characterised through DSC and dielectric spectroscopy studies. The ionic conductivity decreases as the salt concentration increases, finding values ranging between 0.4 S/m and 0.1 S/m at room temperature. Additionally, a wide liquid range was found for the mixtures, which would reduce or even eliminate some of the most common problems of current electrolytes, such as their crystallisation at low temperatures and flammability. Finally, the toxicity of pure IL and the intermediate salt concentration was also evaluated in terms of the bioluminescence inhibition of the Alivibrio Fischeri bacteria, observing that, although the toxicity increases with the salt addition, both samples can be classified as practically harmless.

Phase compatible surface engineering to boost the cycling stability of single-crystalline Ni-rich cathode for high energy density lithium-ion batteries

Nickel-rich layered oxide is a promising cathode material for the next generation lithium-ion batteries (LIBs) because of its high energy density and cost efficiency. Unfortunately, it suffers from unsatisfying electrochemical performance owing to intrinsic interfacial and structural instability, which limits its application at scale. In this work, a phase compatible TiBO3 coating layer on single crystalline LiNi0.83Co0.11Mn0.06O2 (TBO-SC-NCM) is constructed via modified solid-state chemical reaction. The coating layer serves as a protective screen to mitigate the erosion of organic electrolyte towards TBO-SC-NCM. Furthermore, both titanium ions and boron ions successfully diffuse into the TBO-SC-NCM bulk phase during the annealing process, with titanium ions being uniformly distributed while boron ions accumulating close to the surface. The formation of strong Ti-O bond effectively inhibits the bulk phase structure degradation of TBO-SC-NCM. The near-surface enriched B-O bond greatly stabilizes the surface lattice oxygen at the deeply delithiated state. Additionally, the spread of layer spacing due to the doping of heterogeneous ions ensures the rapid diffusion of Li+, thus improving the rate performance of TBO-SC-NCM. As a h cathode materials.

High-Performance p-type organic electrode materials with oxygen atoms as active centers enabled by molecular design and in situ electropolymerization

Redox-active organic molecules are considered to be one type of promising electrode materials for next generation lithium-ion batteries (LIBs), among which p-type electrode materials with higher voltage and outstanding reaction kinetics receive much attention. However, it is a great challenge to develop p-type materials with oxygen atom as the active center and the electrochemical performance of the few reported examples needs significant improvement. Herein, 1,3,5-tri(benzofuran-2-yl)benzene (TBFB) was elaborately designed and facilely synthesized through one-step Suzuki coupling reaction from commercially available raw reagents. When used as p-type electrode material for LIBs, it was found that TBFB with poor solubility can be effectively in situ electropolymerized during the charging process, forming more insoluble polymers. Experimental results demonstrate that TBFB electrode achieves a high specific capacity of 179.1 mAh g−1 and an ultralong cycle life of 8000 cycles. This work manifests the electrochemical performance of p-type organic electrode materials with oxygen atom as active center can be effectively enhanced by rational molecular design and in situ electropolymerization method.

On the role of ultrathin lithium metal anodes produced by thermal evaporation

Lithium metal anodes (LMAs) are the preferred option for the next generation of lithium batteries, where high energy density and longer cycle life are required. A new battery design eliminating the LMA in the discharged state provides the highest achievable energy density with reduced safety hazards, though irreversible Li losses impede the practical application of the anode-free concept. In this work, by using an ultrathin layer (<5 μm) of lithium, which is deposited by thermal evaporation on copper current collectors, a reduction on the energy barrier of lithium nucleation during the plating process is demonstrated. Furthermore, the metallic lithium deposited over the charge step provides a homogeneous layer, fairly reducing the dendritic growth and the generation of dead lithium. Finally, a functional solid electrolyte interphase (SEI) with Li2O and LiOH as predominant species, gives greater protection to the anode/electrolyte interface, leading to a more stable cycling of the battery. These insights provide a solid starting point for future studies that may lead to practical design changes to improve stability and extend the battery life of lithium metal batteries.

Alleviated volume changes of germanium anode via facile chemical confinement strategy

Germanium (Ge) anode shows great promise in overcoming unsatisfied capacity and dendrite formation concerns facing conventional graphite anodes in next generation lithium ion batteries. However, volume changes during repeated alloying and de-alloying cycles seriously impair structural stability and cycle lifespan. In this work, a facile chemical confinement strategy has been firstly proposed to alleviate volume changes of Ge anode. Benefited from strong binding interaction between Ge and ZnS, discrete Ge nanoparticle can be successfully encapsulated within thin protective ZnS shell and N-doped carbon layer (Ge-ZnS@N-C) after two-step carbonization and sulfurization of polydopamine-coating Zn2GeO4 nanorod precursors. In contrast, bulk Ge aggregates and hollow N-doped carbon nanotubes can be formed without chemical confinement of ZnS. The as-prepared Ge-ZnS@N-C sample displays multifold structural merits, including nanosized Ge particles with highly electrochemical activity, sufficient pores and functional groups that facilitate ion diffusion. Besides, protective ZnS shell and N-doped carbon layer can suppress volume changes of Ge nanoparticles and guarantee high electrode reversibility, demonstrated by a series of in-situ and ex-situ experiments. The as-synthesized Ge-ZnS@N-C anodes exhibit stable long-cycle performance (1389.7 mAh/g after 450 cycles at a current density of 0.5 A/g) and excellent rate performance (548.5 and 397.8 mAh/g at 5.0 and 8.0 A/g, respectively).

Stress-Relieving Carboxylated Polythiophene/Single-Walled Carbon Nanotube Conductive Layer for Stable Silicon Microparticle Lithium-Ion Battery Anodes

Silicon is one of the most promising anode materials for next generation Lithium ion batteries (LIBs) on account of its ultrahigh specific capacity (4200 mAh g-1) and relatively low working potential of 0.3 V (vs. Li+/Li). However, practical commercial implementation of silicon poses a great challenge due to technical difficulties such as low conductivity (10-5-10-3 S cm-1), low initial Coulombic efficiency (50-80%) and stress-induced fracture, along with SEI accumulation due to severe volume changes (~400%) inherent in silicon-based anodes.To address these challenges and advance the next generation of LIBs, we present poly[3-(potassium-4-butanoate)thiophene] (PPBT) and single-walled carbon nanotube (SWNT) coated silicon microparticles (Si MPs) (PPBT/SWNT@Si MPs) as active materials for highly stable Si-based anodes for LIB systems. The water-soluble conjugated polymer, PPBT, was selected for its ability to serve as an ion and electron conducting physical/chemical linker (10-5 S cm-1 vs. PVDF; ~ 10-8 S cm-1) to the surface of various high capacity anode active materials systems. In consideration of current practical requirements for Si-based anode materials, Si MPs were selected as starting materials due to their lower surface area than the nanoscale analogs, a characteristic that can further improve LIB bulk capacity. In addition, Si MPs are known to have high initial Coulombic efficiency and industrial compatibility. With the help of PPBT, which facilitates unraveling of entangled single-walled carbon nanotubes, SWNTs were successfully attached to the surface of the active materials. PPBT carboxylate substituents were found to be chemically bound to the Si MP surface, providing an electrochemically conductive environment in intimate contact with the 1D SWNTs and Si MPs.Due to facilitated ion/electron transport kinetics, PPBT/SWNT@SiMP anodes exhibited superior capacity retention and higher reversible capacities, even at a high current density of 8 A g-1, compared to bare Si MP anodes. Improved initial Coulombic efficiency and stable cycling performance over 300 cycles were achieved. In situ Raman spectroscopy was employed to investigate the evolution of stress on the SWNTs during lithiation/delithiation, which elucidated the mechanism underlying the enhancement in PPBT/SWNT@Si MP anode cycling performance. The single-walled carbon nanotubes within the PPBT/SWNT@Si MP anodes consistently exhibited reversible stress recovery and 45 % less tensile stress variation after the 10th cycle than SWNT@Si MP control anodes fabricated by direct mixing of the microparticles with SWNTs to create SWNT@Si MPs.Combined, the results suggest that a well-developed conductive interface can enhance the rate performance, and improve electrode stability and Coulombic efficiency. Furthermore, the PPBT/SWNT coating directly bound to the Si MP surface provides for efficient stress relaxation of Si-based electrodes, resulting in reversible lithiation/delithiation, low electrode resistance, and reduced SEI layer formation.

Strategies and Perspectives on Enhancing Energy Density in Lithium-Ion Batteries

The rapidly growing demand for clean energy transportation and storage systems emphasizes the need for the development of large-scale lithium-ion batteries. Achieving this goal requires a comprehensive approach that considers not only technical aspects but also social, environmental, and economic perspectives. Specifically, the next-generation batteries should exhibit high energy and power densities, long-term cycle stability, and the efficient utilization of low-cost, abundant raw materials. The cathode material is the key determinant of these requirements. This presentation will introduce progress and strategies for enhancing cathode materials and their corresponding cell performances. These strategies include goals to enable reversible redox reaction processes through elemental and compositional choices, as well as crystal structural variations ranging from order to disorder. Furthermore, we combine these with advanced characterization techniques to understand the correlation between material properties and electrochemical behavior at multiple length and depth scales. The discussion also delves into a deeper understanding of the fundamental mechanisms of performance, coupled with advancements in new materials. Overall, the presentation aims to provide valuable insights into the strategy for developing the next generation of lithium-ion batteries.

Optimizing the Electrolyte Additive Content in Practical Li-Ion Cells with Si-Dominant Anodes

Due to their high capacity, Silicon (Si) anodes are very promising for the next generation of lithium-ion batteries. However, Si materials suffer from a high volume expansion, which cause cracking and accumulated growth of the solid electrolyte interphase (SEI), resulting in low coulombic efficiencies and lifetime of the Si anodes. Applying additives in the electrolyte is a facile and straightforward approach to improve the composition of the SEI and reduce cracking. For Si-containing anodes, fluoroethylene carbonate (FEC) and vinylene carbonate (VC) are considered the most effective electrolyte additives. The salt lithium difluorophosphate (LiDFP) is known to improve the interphases of cathode materials and graphite when applied as additive, but has been poorly investigated for Si anodes. In our study, we combine VC, FEC, and a variation of LiDFP concentrations to investigate the effect on Si-dominant anodes in detail. We conducted detailed electrochemical testing in half coin cells and Si/NCM pouch cells, including long-term cycling, rate capability tests, potential monitoring of the anode and electrochemical impedance spectroscopy. For the latter two, we applied a novel perforated reference electrode concept, which allows for broad and precise measurement in pouch cells, while avoiding a blocking effect of the lithium ions. Furthermore, post-mortem analysis was conducted to gain detailed insights into the SEI formation and microstructure influenced by the different additive concentrations.

Amorphous titanium dioxide and polyaniline dual modifying silicon for highly enhanced lithium-ion storage

Silicon (Si) anode material is promising in the next generation of lithium-ion batteries (LIBs) with high energy densities for its much higher capacity (4200 mAh/g) than that of commercial graphite (372 mAh/g). However, silicon anode material with low electronic conductivity suffers a huge volume variation and accompanies side reactions during alloyed and de-alloyed process. Here, we design an inner amorphous titanium dioxide (TiO2) and an outer flexible conductive polyaniline (PANI) network dual modified Si@TiO2@PANI material for LIBs, where the TiO2 avoids the side reactions and the PANI network layer buffers the volume expansion and increases the electronic conductivity. The as-prepared Si@TiO2@PANI exhibits a high initial discharge capacity of 3050 mAh/g and maintains 1583 mAh/g after 200 cycles at 0.5 A/g. It even delivers the discharge capacity of 1002 mAh/g after 600 cycles at 1 A/g, as well as an excellent rate ability with discharge capacity of 1890, 1260 and 432 mAh/g at the high current density of 1, 2 and 5 A/g, respectively. Our strategy shows that the innovative design of double buffer layers on Si can synergistically promote stability and accelerate kinetics of Li+ transport, offering novel resolution strategy to enhance the performance of Si-based anodes for LIBs.

SnS nanoflowers as an efficient anode for next generation lithium-ion batteries

Tin (II) Sulfide (SnS) nanoflowers are synthesized by hydrothermal method. The electrochemical performance of SnS nanoflower versus Li/Li+ is studied. X-ray diffraction and X-ray photoelectron spectroscopy results confirms the formation of SnS. Scanning electron microscope images validate the existence of nanoflowers. SnS vs. Li/Li+ half-cell delivers the first charge/discharge capacity of 847.2/853 mAh g−1 at 0.1 C-rate, with a columbic efficiency of 99 %. Differential capacity versus voltage plot reveals intercalation and deintercalation of lithium ions during cycling and also delves the conversion and alloying reaction of SnS anodes. The better electrochemical result could be ascribed to the flower like morphology, which improves lithium diffusion and reaction kinetics.

Rigid-flexible mediated Co-polyimide enabling stable silicon anode in lithium-ion batteries

Silicon is considered as a promising electrode materials for the next generation of lithium-ion batteries. However, it’s commercial applications are hindered by significant volume changes. In this study, copolyimide binders with adjustable rigidity and flexibility were synthesized through simple copolymerization. The rigid segments containing adenine groups (p-APA) provide excellent mechanical strength and interface interaction, while flexible segments containing siloxane bonds and alkane chains (DS-NH2) can buffer volume changes through enhanced mobility and topological entanglement of molecular segments. Optimizing the copolymerization ratio helps minimize damage to the silicon electrode structure and stabilizes solid electrolyte interphase (SEI) growth. Compared to the rigid polyimide binders, rigid-flexible coupling strategy improves cycling stability, remaining a capacity of 2170 mAh/g at 2 A/g after 200 cycles and exhibiting stable cycling for over 750 cycles with a capacity limitation of 1500 mAh/g. The high mass loading silicon anodes, micron-sized silicon oxide electrodes and the full cells also exhibit favorable electrochemical performance. This research provides valuable insights for designing high-performance aromatic polymer binders for high energy density lithium-ion batteries.

Fundamental Understanding of the Low Initial Coulombic Efficiency in SiOx Anode for Lithium-Ion Batteries: Mechanisms and Solutions.

To meet the ever-increasing demand for high-energy lithium-ion batteries (LIBs), it is imperative to develop next-generation anode materials. Compared to conventional carbon-based anodes, Si-based materials are promising due to their high theoretical capacity and reasonable cost. SiOx, as a Si-derivative anode candidate, is particularly encouraging for its durable cycling life, the practical application of which is, however, severely hindered by low initial Coulombic efficiency (ICE) that leads to continuous lithium consumption. What is worse, low ICE also easily triggers a terrible chain reaction causing bad cycling stability. To further develop SiOx anode, researchers have obtained in-depth understandings regarding its working/failing mechanisms so as to further propose effective remedies for low ICE mitigation. In this sense, herein recent studies investigating the possible causes that fundamentally result in low ICE of SiOx, based on which a variety of solutions addressing the low ICE issue are discussed and summarized, are timely summarized. This perspective provides valuable insights into the rational design of high ICE SiOx anodes and paves the way toward industrial application of SiOx as the next generation LIB anode.

Tailoring cathode materials: A comprehensive study on LNMO/LFP blending for next generation lithium-ion batteries

Lithium-ion batteries (LIBs) play a crucial role in diverse applications, including electric vehicles, portable electronics, and grid energy storage, owing to their commendable features, such as high energy density, extended cycle life, and low self-discharge rates. Despite their widespread use, the growing market demands continuous efforts to enhance LIBs performance, particularly in terms of energy density and cycling stability. This paper details the development of a lithium nickel manganese oxide (LNMO - LiNi0·5Mn1·5O4)/lithium iron phosphate (LFP - LiFePO4) blended cathode for high-performance LIBs. The study investigates the impact of blending LFP and LNMO, examining morphological and electrochemical aspects. The usage of resonant acoustic mixing (RAM) technology is demonstrated to be a promising approach to improve the distribution of LFP and LNMO particles, leading to increased electrochemical performance. The blended LNMO/LFP cathode exhibits a specific capacity exceeding 125 mAh g−1 at C/10 and a capacity retention exceeding 80 % after 1000 cycles at 1C versus lithium. Moreover, in a full-cell configuration, the blended electrode displays a capacity retention close to 74 % after 100 cycles, showcasing a nearly 30 % improvement compared to the pure LNMO cathode. This research highlights the potential of blended cathode materials in advancing the capabilities of LIBs.

Eco-Friendly Lithium Separators: A Frontier Exploration of Cellulose-Based Materials.

Lithium-ion batteries, as an excellent energy storage solution, require continuous innovation in component design to enhance safety and performance. In this review, we delve into the field of eco-friendly lithium-ion battery separators, focusing on the potential of cellulose-based materials as sustainable alternatives to traditional polyolefin separators. Our analysis shows that cellulose materials, with their inherent degradability and renewability, can provide exceptional thermal stability, electrolyte absorption capability, and economic feasibility. We systematically classify and analyze the latest advancements in cellulose-based battery separators, highlighting the critical role of their superior hydrophilicity and mechanical strength in improving ion transport efficiency and reducing internal short circuits. The novelty of this review lies in the comprehensive evaluation of synthesis methods and cost-effectiveness of cellulose-based separators, addressing significant knowledge gaps in the existing literature. We explore production processes and their scalability in detail, and propose innovative modification strategies such as chemical functionalization and nanocomposite integration to significantly enhance separator performance metrics. Our forward-looking discussion predicts the development trajectory of cellulose-based separators, identifying key areas for future research to overcome current challenges and accelerate the commercialization of these green technologies. Looking ahead, cellulose-based separators not only have the potential to meet but also to exceed the benchmarks set by traditional materials, providing compelling solutions for the next generation of lithium-ion batteries.

Effect of Varying Temperatures on the Electrochemical Performance of Lithium‐Ion Batteries Using LiNi0.3Mn0.3Co0.3Ti0.1O2 Cathode Materials

AbstractLiNi1/3Mn1/3Co1/3O2 (NMC 111) materials show promise as cathodes for lithium‐ion batteries (LIBs). However, their widespread use is hampered by various technical challenges, including rapid capacity fading and voltage instability. The cathode materials synthesized using the combustion method were annealed at various temperatures ranging from 650 to 900 °C for 24 h. In this study, we identified an optimal annealing temperature of 750 °C for LiNi0.3Mn0.3Co0.3Ti0.1O2 (NMCT) materials. NMCT‐750 exhibits an initial discharge capacity of about 140.1 mAh g−1 and retains the capacity of 91 % after 30th cycles. The good performance of NMCT‐750 is directly attributed to reduced cation mixing and the establishment of a stable structure with small particle sizes. In contrast, higher annealing temperatures (850 °C) lead to a rapid increase in primary particle size and result in poor cycling stability. Therefore, NMCT‐750, annealed at 750 °C, holds great potential as a cathode material for the next generation of LIBs.

Lithium-Ion Dynamic and Storage of Atomically Precise Halogenated Nanographene Assemblies via Bottom-Up Chemical Synthesis.

Graphene has received much scientific attention as an electrode material for lithium-ion batteries because of its extraordinary physical and electrical properties. However, the lack of structural control and restacking issues have hindered its application as carbon-based anode materials for next generation lithium-ion batteries. To improve its performance, several modification approaches such as edge-functionalization and electron-donating/withdrawing substitution have been considered as promising strategies. In addition, group 7A elements have been recognized as critical elements due to their electronegativity and electron-withdrawing character, which are able to further improve the electronic and structural properties of materials. Herein, we elucidated the chemistry of nanographenes with edge-substituted group 7A elements as lithium-ion battery anodes. The halogenated nanographenes were synthesized via bottom-up organic synthesis to ensure the structural control. Our study reveals that the presence of halogens on the edge of nanographenes not only tunes the structural and electronic properties but also impacts the material stability, reactivity, and Li+ storage capability. Further systematic spectroscopic studies indicate that the charge polarization caused by halogen atoms could regulate the Li+ transport, charge transfer energy, and charge storage behavior in nanographenes. Overall, this study provides a new molecular design for nanographene anodes aiming for next-generation lithium-ion batteries.