Metal Oxide Nanomaterials for Energy Density Improvement in Lithium-Ion and Solid-State Batteries ^†

Abstract

Metal oxide nanomaterials have emerged as transformative materials in the quest to enhance the energy density and overall performance of lithium-ion batteries (LIBs) and solid-state batteries (SSBs). Their unique properties—including their large surface areas and short ion diffusion pathways—make them ideal for next-generation energy storage technologies. In LIBs, the high surface-to-volume ratio of metal oxide nanomaterials significantly enlarges the active interfacial area and shortens the lithium-ion diffusion paths, leading to an improved high-rate performance and enhanced energy density. Transition metal oxides (TMOs) such as nickel oxide (NiO), copper oxide (CuO), and zinc oxide (ZnO) have demonstrated significant theoretical capacities, while binary systems like NiCuO offer further improvements in cycling stability and energy output. Additionally, layered lithium-based TMOs, particularly those incorporating nickel, cobalt, and manganese, have shown remarkable promise in achieving high specific capacities and long-term stability. The synergistic integration of metal oxides with carbon-based nanostructures, such as carbon nanotubes (CNTs), enhances the electrical conductivity and structural durability further, leading to a superior electrochemical performance in LIBs. In SSBs, the use of oxide-based solid electrolytes like garnet-type Li₇La₃Zr₂O₁₂ (LLZO) and sulfide-based electrolytes has facilitated the development of high-energy-density systems with excellent ionic conductivity and chemical stability. However, challenges such as high interfacial resistance at the electrode–electrolyte interface persist. Strategies like the application of lithium niobate (LiNbO₃) coatings have been employed to enhance interfacial stability and maintain electrochemical integrity. Furthermore, two-dimensional (2D) metal oxide nanomaterials, owing to their high active surface areas and rapid ion transport, have demonstrated considerable potential to boost the performance of SSBs. Despite these advancements, several challenges remain. Morphological optimization of nanomaterials, improved interface engineering to reduce the interfacial resistance, and solutions to address dendrite formation and mechanical degradation are critical to achieving the full potential of these materials.

1. Introduction

High-energy-density storage technologies play a pivotal role in advancing modern applications, ranging from electric vehicles (EVs) and portable electronics to large-scale grid storage systems. In the context of EVs, higher energy density directly translates into extended driving ranges, reduced charging frequency, and improved overall vehicle efficiency, thereby accelerating the adoption of sustainable transportation solutions [1,2,3]. Similarly, portable electronic devices such as smartphones, laptops, and wearable technologies demand compact, lightweight, and energy-dense batteries that can sustain prolonged usage without frequent recharging [1,3,4]. Beyond consumer applications, grid storage systems also rely heavily on energy-dense storage solutions to balance energy supply and demand, support peak load management, and integrate intermittent renewable energy sources like solar and wind into the power network more efficiently [1,2,5]. Collectively, these diverse needs increase the importance of continuous innovation in energy storage systems capable of delivering higher capacities, improved efficiency, and sustainable operation. Lithium-ion batteries (LIBs) remain the dominant energy storage technology due to their relatively high energy density and efficiency; however, their limitations hinder further progress. One of the foremost concerns is safety, as conventional LIBs employ flammable liquid electrolytes, which can cause thermal runaway, leakage, and even catastrophic fires under mechanical stress or overcharging conditions [6,7]. Another major issue is their limited energy density, as the theoretical capacity of graphite anodes (372 mAh g⁻¹) imposes a ceiling on energy storage potential, restricting the performance of LIBs in applications that demand long-lasting power [7,8]. LIBs are often constrained by long charging times, which limits their convenience, particularly for EVs and high-demand consumer electronics [4]. Solid-state lithium-ion batteries (SSLIBs) have emerged as a promising alternative to conventional LIBs, offering significant improvements in performance, safety, and reliability. By replacing liquid electrolytes with solid-state counterparts, SSLIBs enable the use of lithium metal anodes, which exhibit a theoretical capacity nearly an order of magnitude higher than graphite, thus significantly increasing the achievable energy density [6,7,9]. The absence of flammable liquid components dramatically enhances safety, eliminating leakage and reducing the risk of thermal runaway [6,7,9]. In addition, solid-state electrolytes exhibit superior thermal and electrochemical stability, resulting in longer life cycle, greater reliability, and the potential for compact designs with higher volumetric efficiency [6,9]. Among the strategies for improving the performance of LIBs and SSLIBs, metal oxide nanomaterials have attracted growing attention due to their abundance, versatility, and electrochemical potential. Metal oxides are relatively abundant and cost-effective, making them feasible candidates for scalable battery production without heavy reliance on scarce critical materials [10,11]. More importantly, their tunable structure at the nanoscale provides opportunities to optimize key electrochemical properties, including electron conductivity, ion diffusion pathways, and structural stability during cycling [10,11]. Many transition metal oxides, such as NiO, CuO, and ZnO, exhibit high theoretical capacities that far exceed traditional graphite-based anodes, thereby offering a pathway to substantially increase energy density in next-generation batteries [8,10,11]. Collectively, these attributes establish metal oxide nanomaterials as a pivotal research direction for advancing both LIBs and SSLIBs to achieve higher energy density, safety, and commercial viability.

2. Lithium-Ion and Solid-State Batteries: Energy Density

The comparison of energy density between lithium-ion batteries (LIBs) and solid-state batteries (SSBs) is central to understanding their technological potential and future role in energy storage. Commercial LIBs currently achieve specific energy densities ranging from approximately 90 to 300 Wh/kg [12,13,14]. Through advanced electrode design and innovative manufacturing processes, certain experimental LIBs have reported much higher values, reaching up to 711.3 Wh/kg and 1653.65 Wh/L [15]. However, such performance remains largely at the laboratory or prototype stage and is not yet commercially viable. SSBs are projected to achieve significantly higher gravimetric and volumetric energy densities, typically in the range of 400–500 Wh/kg [12,16,17]. The key enabler of this advancement is the use of solid electrolytes, which allow the safe integration of lithium metal anodes—materials with a much higher specific capacity than conventional graphite anodes. Some theoretical configurations of SSBs are expected to reach energy densities as high as 500 Wh/kg and 1000 Wh/L, thereby positioning SSBs as a disruptive alternative to current LIBs [15]. Several factors influence these differences in energy density. The electrolyte type is particularly critical; solid-state electrolytes (SSEs) permit higher-capacity lithium metal anodes and contribute directly to improved safety and performance [12,17,18]. Material innovations, such as lithium-rich manganese-based cathodes and ultrathin lithium anodes, have also been central to increasing the achievable energy density of both LIBs and SSBs [14,19]. Yet, the promise of SSBs is hindered by interfacial challenges, including unstable electrode–electrolyte contact and lithium dendrite formation, which negatively impact both cycle life and safety [18,20,21]. Both LIBs and SSBs continue to face technical challenges. For LIBs, the main barriers involve optimization of electrode chemistries and battery designs to further increase energy density within established safety limits [13]. Meanwhile, SSBs encounter difficulties associated with high production costs, materials processing, and the suppression of dendritic lithium growth [12,17]. Despite these obstacles, ongoing progress in thin lithium films, novel composite cathodes, and stable solid electrolytes suggests that SSBs are likely to become the next-generation standard for high-performance energy storage [15,20,21].

Compared to liquid electrolytes, solid-state electrolytes (SSEs) demonstrate superior thermal and electrochemical stability, making them more suitable for next-generation energy storage systems. Thermally, SSEs—such as oxide-based (e.g., LLZO) and sulfide-based materials—exhibit high resistance to heat and are non-flammable, significantly reducing the risk of thermal runaway under abuse conditions. This contrasts with conventional liquid electrolytes, which are often composed of volatile and flammable organic solvents that decompose or ignite at elevated temperatures, leading to safety hazards such as leakage, combustion, and explosions [22,23,24]. In terms of electrochemical stability, SSEs offer a broader stability window, allowing them to operate effectively at high voltages and enabling compatibility with high-energy cathode materials. This stability is particularly critical in maintaining interface integrity during long-term cycling [23,25,26]. In contrast, liquid electrolytes typically have narrower electrochemical windows, which can promote side reactions, dendrite formation, and internal short circuits, especially under high-voltage or fast-charging conditions [27,28,29]. From a safety perspective, SSEs are inherently non-volatile and non-flammable, eliminating leakage and significantly lowering fire risk. These attributes are particularly vital for lithium metal-based systems, for which safety remains a key limitation [22,23,25,30]. On the other hand, liquid electrolytes are known for their flammability and potential for hazardous gas release, posing serious risks in large-scale or high-energy applications [27,28]. However, SSEs have historically faced limitations in ionic conductivity, especially at room temperature, where liquid electrolytes maintain an advantage [29,31]. To address this, recent advancements in composite and hybrid SSEs—which combine polymers, ceramics, or gels—have significantly improved ionic conductivity while retaining thermal and electrochemical advantages [29,32].

3. Metal Oxide Nanomaterials for Energy Density Improvement

Metal oxide nanomaterials have emerged as pivotal contributors to the advancement of energy storage technologies, particularly in applications where enhanced energy density is essential. Their unique physicochemical properties—stemming from their nanoscale dimensions, tunable surface chemistry, and large surface area—make them highly effective in improving the performance of lithium-ion batteries (LIBs), supercapacitors, and solid-state batteries (SSBs), among other devices [33]. One of the primary advantages of metal oxide nanomaterials lies in their high capacitance and energy density. Bimetallic and multimetal oxide systems, such as MnCo₂O₄, FeCo₂O₄, and NiCo₂O₄, outperform single-metal oxides in terms of electrochemical activity due to synergistic interactions between constituent metals, which lead to improved redox activity and electron transport [34,35]. Compared with carbon-based materials, the surface area of metal oxide nanomaterials is generally lower; however, their higher intrinsic electrochemical activity and ability to participate in multi-electron redox reactions often compensate for this limitation, resulting in superior specific capacities in many battery applications. These materials exhibit high specific capacitance and are widely utilized in high-performance supercapacitors and LIBs. The integration of metal oxides with carbon-based nanostructures such as carbon nanotubes (CNTs) and graphene has further unlocked new frontiers in electrochemical performance. These composites significantly enhance electronic conductivity, structural flexibility, and cycling stability. For instance, CNT–metal oxide hybrids serve as efficient cathode materials by providing a conductive network and mitigating volume expansion during charge/discharge cycles [36]. Additionally, hybrid materials based on carbon and metal oxides demonstrate superior lithium storage capacity, fast charge transfer, and mechanical robustness [37]. In solid-state batteries (SSBs), nanomaterials enhance ion transport and interfacial contact, both of which are critical for achieving high energy densities. Nanostructured oxides help suppress dendritic lithium growth, stabilize electrode/electrolyte interfaces, and improve electrochemical safety [9]. In particular, 2D metal oxide nanosheets such as TiO₂ or MnO₂ offer a combination of a large surface area, chemical stability, and flexibility, making them attractive for electrodes in a variety of energy storage systems. For LIB applications, metal oxides like CoO, Fe₂O₃, and V₂O₅—when combined with conductive carbon matrices—enable faster lithium-ion diffusion and better capacity retention. Nanoscale structuring of these oxides facilitates shorter diffusion pathways and increases the interfacial contact area, collectively enhancing rate capability and long-term cycling performance [11,37]. In the realm of supercapacitors, metal oxide/graphene composites offer significantly improved energy density and specific capacitance. Notable examples include flexible hybrid supercapacitors using Ti₃C₂Tx MXene and NiCo₂O₄@rGO, which have demonstrated excellent energy densities and prolonged cycling life in solid-state systems [38,39]. Nanostructures can act as hosts or protective frameworks that stabilize lithium deposition, prevent dendrite formation, and improve overall battery safety and efficiency [40]. One of the fundamental roles of nanostructured oxides in SSBs is improving solid–solid contact and facilitating efficient ionic transport. In conventional SSBs, the absence of liquid electrolytes leads to poor interfacial contact between the solid electrolyte and electrodes. To counteract this, engineering covalently bonded interfaces between inorganic solid electrolytes (ISEs) and electrodes has proven effective. This approach not only minimizes interfacial resistance but also enhances electrochemical stability, leading to better cycling performance [41]. Additionally, the use of metal–organic frameworks (MOFs) infused with ionic liquids can create “nanowetted” interfaces that promote continuous and highly conductive pathways for Li⁺ ions. These MOF-based interfaces exhibit high ionic conductivity and are especially effective at minimizing interfacial losses in SSBs [42]. Interface engineering between oxide cathodes and solid electrolytes is another critical domain where metal oxide nanomaterials play a transformative role. For example, surface reconstruction techniques that generate a perovskite nanolayer on LiCoO₂ cathodes significantly stabilize the cathode–electrolyte interface (CEI), preventing structural collapse during high-voltage operation [43]. Furthermore, applying protective coatings such as lithium niobate (LiNbO₃) on Ni-rich layered oxide cathodes enhances their compatibility with sulfide-based solid electrolytes and suppresses interfacial degradation, thereby boosting cycling stability and rate performance [44,45]. Stabilizing high-capacity cathode materials like lithium-rich layered oxides (LLOs) is another area where oxide nanostructures offer notable advantages. Doping strategies involving high-valence elements such as tantalum (Ta) have shown promise in tuning the electronic structure of transition metals. This leads to stronger metal-oxygen bonds, which help stabilize lattice oxygen and suppress detrimental oxygen evolution reactions during cycling [46]. Likewise, inducing a surface rock-salt phase through interphase engineering has been demonstrated to enhance the structural integrity of Co-free LLOs and reduce parasitic side reactions [47]. Protective coatings and buffer layers composed of oxide materials are equally vital for extending the lifespan and performance of SSBs. For instance, thin layers of aluminum oxide (Al₂O₃) applied to NMC811 cathodes serve a dual role, acting both as a protective barrier against reactive species in the solid electrolyte and as a stabilizer of surface chemistry to limit phase transformations [48]. Computational studies have further identified polyanionic oxide coatings such as lithium hydrogen phosphate (LiH₂PO₄) and lithium titanium phosphate (LiTi₂(PO₄)₃) as optimal candidates for cathode surface protection, owing to their high electrochemical stability and ionic conductivity [49].

Metal oxide nanomaterials have gained significant attention as critical enablers for enhancing unique physicochemical properties, such as a large surface area, tunable structures, and electrochemical versatility, making them highly effective in addressing current challenges related to energy density, conductivity, and cycling stability. By leveraging nanostructuring strategies, researchers have been able to improve ion transport, optimize electrode–electrolyte interfaces, and enhance long-term durability, ultimately contributing to the advancement of next-generation energy storage devices [9,50].

(A)

Large Surface Area and Short Diffusion Paths: One of the primary advantages of metal oxide nanomaterials is their inherently large surface area, which significantly increases electrode–electrolyte contact, enabling more efficient ion exchange. Their short diffusion paths further facilitate rapid lithium-ion transport, leading to enhanced charge and discharge kinetics [30]. This property is especially important in SSBs, where sluggish ion movement and interfacial resistance often limit performance. For example, garnet-type electrolytes such as Li₇La₃Zr₂O₁₂ (LLZO) exhibit not only fast ionic conductivity but also chemical and thermal stability, making them promising candidates for high-performance solid-state batteries [51].

(B)

Enhanced Electrochemical Properties: Beyond ion transport, metal oxides also improve the electrochemical properties of battery electrodes. Their ability to accommodate multiple redox reactions allows for higher specific capacities compared to conventional carbon anodes. Moreover, their catalytic activity and structural robustness contribute to superior rate capability and cycling stability. Recent studies have demonstrated that incorporating layered transition metal oxides, such as LiNi_0.6Mn_0.2Co_0.2O₂, in composite cathodes can increase cathode utilization efficiency and enhance long-term cycling stability in SSB systems [21]. These advances underscore the role of interface engineering and structural design in maximizing the benefits of metal oxide nanomaterials.

(C)

Nanocomposites with Carbon-Based Materials: To overcome the intrinsic drawbacks of many metal oxides, such as low electronic conductivity and volume changes during cycling, researchers have developed nanocomposites that combine metal oxides with carbon-based materials. Carbon nanotubes (CNTs), graphene oxide (GO), and reduced graphene oxide (rGO) provide conductive frameworks that enhance electron transport and mechanical resilience [52]. For example, hybrid nanocomposites of Co₃O₄–ZnO integrated with g-C₃N₄, GO, and Ag have demonstrated improved electrochemical activity, delivering higher energy density and better cycling performance compared to pure oxides. These composite designs effectively address conductivity limitations while ensuring structural integrity during repeated charge–discharge cycles.

(D)

Incorporation of Carbon Nanostructures: Carbon nanostructures, particularly CNTs and rGO, play a vital role in further improving the performance of oxide-based systems. Their high conductivity and flexibility provide reinforcement against mechanical stress while enabling uniform ion–electron pathways throughout the electrode. For instance, the integration of rGO with FeS₂ cathodes has significantly enhanced ion–electron transport kinetics, resulting in higher rate performance and improved interfacial contact in all-solid-state batteries [53]. Similarly, dual-carbon frameworks combined with sulfide-based electrolytes such as Li₇P₃S₁₁ have exhibited superior cycling stability and rate capabilities, highlighting the synergistic effects of carbon–oxide hybrid architectures [53].

4. Factors Influencing Energy Density in Batteries

The capacity of electrode materials is a primary determinant of energy density. Different materials possess varied intrinsic properties that significantly affect performance. For example, cathode materials such as LiMn₂O₄, LiFePO₄, LiCoO₂, LiV₆O₁₃, and LiTiS₂ exhibit unique capacities and voltage profiles that influence overall energy density [54]. High-specific-modulus materials—like LiCoO₂ combined with aqueous lithium–air systems—are proposed as promising candidates for achieving higher energy outputs. The incorporation of nanostructured electrode materials can dramatically enhance performance by expanding the contact area between electrode and electrolyte, thereby improving charge/discharge rates, reducing impedance growth, and facilitating more effective utilization of active materials [55]. Equally important is the electrode/electrolyte interface, which plays a critical role in determining internal resistance and power delivery. High interface resistance can lead to significant voltage drops, ultimately reducing power density and energy efficiency [56]. Therefore, optimizing this interface to minimize Ohmic losses is crucial. This can be achieved through the introduction of modification layers—such as reduced graphene oxide (rGO) applied to separators—which not only stabilize the interface but also preserve energy density and enable higher sulfur loading, particularly in lithium–sulfur systems [57]. Another major factor is ionic and electronic transport, which is largely dictated by the electrode’s internal structure. Parameters such as porosity, pore size distribution, and tortuosity strongly influence how effectively ions can travel through the electrode matrix [58]. Enhancing ion mobility directly contributes to increased efficiency, power density, and by extension, usable energy density. One promising approach to this challenge is the fabrication of vertically aligned electrode architectures, which reduce tortuosity and provide more direct ion pathways. These designs—achieved via techniques like templating, direct growth, or microfabrication—have shown considerable promise in enhancing charge transport [59].

The incorporation of nanostructured electrode materials is highlighted as a strategy to enhance performance by increasing the electrode–electrolyte contact area and improving charge/discharge rates. Additionally, the use of modification layers, such as reduced graphene oxide (rGO), stabilizes the electrode–electrolyte interface and reduces Ohmic losses, thereby preserving energy density. Another solution proposed is the fabrication of vertically aligned electrode architectures, which reduce tortuosity and enable more efficient ion transport. These design strategies directly address the key limitations discussed, offering practical pathways to improve both energy and power density in batteries.

5. Anode Applications of Metal Oxide Nanomaterials

Transition metal oxides (TMOs) such as Fe₂O₃, Co₃O₄, MnO₂, NiO, and TiO₂ have garnered significant attention as potential anode materials for lithium-ion batteries (LIBs) due to their high theoretical capacities, natural abundance, and versatile electrochemical properties [60,61,62,63,64]. These materials primarily function through two main electrochemical mechanisms: conversion reactions and intercalation reactions. In the conversion mechanism, the metal oxide is reduced to its corresponding metallic nanoparticles and lithium oxide during lithiation, with the reverse process occurring during delithiation. This reaction mechanism, while enabling high capacity, is typically accompanied by drastic volume changes that can degrade structural integrity and reduce cycle life [61,65]. On the other hand, TMOs like TiO₂ can operate through an intercalation mechanism, where lithium ions are reversibly inserted into the lattice without destroying the structure, thus ensuring higher cyclic stability, albeit at the cost of reduced specific capacity [61,65].

To address the inherent issue of volume expansion during the charge/discharge cycles, researchers have explored several strategies aimed at improving the mechanical stability, electrical conductivity, and electrochemical reversibility of TMO-based anodes. One widely adopted approach is nanostructuring the materials into forms such as hollow spheres, nanowires, or nanosheets. These nanostructures can effectively buffer the volume changes and facilitate lithium-ion diffusion by shortening transport paths. For example, hollow Co_xFe_3−xO₄ spheres anchored onto carbon nanotubes exhibit improved rate capability and cycling performance due to their internal void space accommodating volume expansion [64]. Similarly, SnO₂ nanowires have demonstrated robust mechanical properties and enhanced cycling behavior by maintaining structural integrity through repeated lithiation and delithiation processes [66]. Another crucial design strategy involves the development of carbon composites, where TMOs are integrated with conductive carbonaceous materials such as graphene, carbon nanotubes, or carbon coatings. These composites not only improve electron transport across the electrode but also provide mechanical flexibility that counters structural disintegration. For instance, Fe₃O₄@graphene/carbon (Fe₃O₄@G/C) composites show markedly enhanced cycle life and capacity retention due to the synergistic effects between the metal oxide and graphene layers [63]. Similarly, hollow CuO particles encapsulated within nitrogen-doped carbon nanosheets have demonstrated high stability and capacity due to the confinement and conductivity provided by the carbon matrix [67]. Other works, such as CuO/reduced graphene oxide (rGO) anode composites, further illustrate how carbon-based frameworks contribute to both electrochemical activity and mechanical resilience [68]. Doping is another technique used to fine-tune the electrochemical performance of TMOs. Incorporating heteroatoms or secondary metals into the oxide lattice can modify the electronic structure, improve lithium-ion diffusion kinetics, and enhance thermal and structural stability. For example, manganese-doped Co₃O₄ combined with carbon coating significantly enhances cycling stability and rate capability, compared to its undoped counterpart [62]. Additionally, the use of core–shell structures has emerged as a compelling method to manage mechanical stress and maintain the structural integrity of anode materials. In such architectures, the active TMO core is encapsulated within a protective and conductive shell—typically made of carbon—forming a composite that buffers volume changes while enabling efficient charge transport. Performance benefits were noted with SnO₂ coated with polyaniline (PANI), where the uniform polymer shell acted as both a binder and a flexible buffer [69].

6. Cathode Applications of Metal Oxide Nanomaterials

Metal oxide nanomaterials serve as crucial components in cathodes for both lithium-ion batteries (LIBs) and all-solid-state lithium batteries (ASSLBs), particularly in systems that aim to achieve high voltage and energy density. Among the most widely studied cathode materials are high-voltage spinel and layered oxides, including LiCoO₂ (LCO), LiNiₓMnᵧCo_zO₂ (NMC), and LiMn₂O₄ (LMO). Each offers distinct electrochemical properties and engineering challenges. LiCoO₂, a layered oxide cathode, has been a mainstay in LIB technology due to its high volumetric energy density and relatively stable cycling behavior. However, it suffers from structural instability and safety risks when operated at high voltages, leading to capacity fading and possible thermal runaway [69,70]. To address growing demands for higher capacities, researchers have shifted focus to Ni-rich layered oxides such as LiNi_0.8Mn_0.1Co_0.1O₂ (NCM811), which provide increased capacity and lower cobalt content, reducing both material cost and ethical concerns. Despite their advantages, these materials face interfacial instability and mechanical degradation in solid-state systems, particularly due to side reactions with sulfide-based electrolytes and stress-induced microcracking [71,72,73,74]. Meanwhile, LiMn₂O₄, a spinel-type oxide, offers robust thermal stability and operates at higher voltages (~4.0 V), but it is prone to capacity fading caused by Mn²⁺ dissolution and structural disintegration during cycling [11,70]. To enhance the stability of these cathode materials, surface coating techniques have emerged as vital interventions. Coatings with metal oxides such as LiNbO₃ can suppress side reactions, stabilize electrode–electrolyte interfaces, and improve electrochemical performance. For example, a LiNbO₃ coating on NCM811 cathodes has demonstrated improved discharge capacity and rate performance in ASSLB configurations [74]. In addition, advanced computational studies support the efficacy of binary halides and ternary oxides—such as Li₂MoO₄ and LiAl₅O₈—as interfacial stabilizers, reducing interfacial resistance and enhancing compatibility between high-voltage cathodes and lithium halide or sulfide solid electrolytes [75]. Beyond coatings, nanoengineering has played a transformative role in improving cathode performance. Nanostructuring, such as the development of electrospun lithium metal oxide nanofibers, increases surface area and shortens lithium-ion diffusion paths, which is critical for high-rate and long-cycle applications. These nanoarchitectures enable better ion accessibility, reduced strain during cycling, and enhanced reaction kinetics [76,77]. Additionally, integrating carbon nanotubes (CNTs) with metal oxides has proven effective in boosting both mechanical flexibility and electrical conductivity. CNT–metal oxide composites mitigate volume expansion, preserve structural integrity, and enable higher capacity retention, making them suitable for next-generation LIBs and ASSLBs [11,36,78]. Despite these advances, interfacial instability remains a key challenge in solid-state configurations. High interfacial resistance between oxide cathodes and sulfide electrolytes leads to limited Li⁺ transport and rapid capacity fading. Strategies such as surface passivation, gradient interfaces, and composite architectures are actively being explored to overcome these hurdles [3,71,72,79]. Achieving long-term electrochemical stability requires mitigation of parasitic reactions such as oxygen evolution at high voltage and irreversible phase transitions, which affect both safety and capacity [69,73,80].

7. Interface Engineering and Morphological Optimization with Metal Oxide Nanomaterials in Lithium-Ion Batteries (LIBs) and Solid-State Batteries (SSBs)

Morphological optimization plays a pivotal role in improving the efficiency and reliability of LIBs and SSBs. For instance, MnO₂@TiO₂ heterostructures synthesized using sol–gel techniques enhance lithium storage and electron transport due to improved surface reaction kinetics and intimate interface contact between the oxide components [68]. Similarly, yolk-shell-structured high-entropy oxides (HEOs) such as (CrMnFeCoNi)₃O₄ exhibit superior capacity retention and cycling stability compared to traditional nanoparticle morphologies, primarily because their internal voids accommodate volume fluctuations during repeated charge–discharge processes [81]. Furthermore, cobalt-free lithium-rich layered oxides (LROs) with radial architectures promote rapid lithium-ion diffusion and mitigate mechanical strain, leading to higher discharge capacities and improved structural integrity in long-term cycling [82]. These examples highlight how morphology-controlled synthesis is essential for enabling high-performance electrodes in next-generation batteries.

Interface engineering is another critical strategy for optimizing the stability and performance of batteries using metal oxide nanomaterials. One effective approach is polymer coating of solid electrolytes. For example, Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) coated with poly-dioxolane (P-DOL) forms stable LiF-rich interfacial layers, suppressing dendritic growth and enhancing cycling stability [83]. In addition, incorporating ceramic fillers such as lithium lanthanum titanate (LLTO) into polymer matrices improves ionic conductivity while simultaneously stabilizing the electrode–electrolyte interface [84]. Metal oxide nanoparticles (MONPs) integrated into porous polyethylene micro-layers (PEMLs) further lower interfacial resistance and improve coulombic efficiency by facilitating more homogeneous Li plating/stripping processes [85]. Collectively, these engineering strategies demonstrate how careful design at the electrode–electrolyte interface can extend battery lifespan and reliability. Safety and long-term stability remain critical challenges for LIBs and SSBs, and metal oxide nanomaterials provide promising solutions. Solid-state electrolytes (SSEs) inherently offer better safety by suppressing lithium dendrite growth and enhancing thermal resistance. However, poor ionic conductivity and interfacial decomposition often limit their practical application. Incorporating ZnO nanoparticles into poly(ethylene oxide)-based composite solid electrolytes has been shown to enhance ionic conductivity while stabilizing the interface, resulting in improved cycling performance [86]. Beyond this, protective coatings and hydrophobic bioinspired layers offer corrosion resistance and stability in air, providing a longer shelf life and safer operation [84]. Finally, broader strategies addressing thermal hazards—such as modifying material compositions and engineering safer electrode/electrolyte structures—are essential for mitigating risks associated with solid-state lithium-metal batteries [87]. These findings reinforce the importance of oxide nanomaterials in ensuring not only high performance but also operational safety.

The morphology of metal oxide nanomaterials can be precisely controlled through a range of synthetic techniques and post-processing methods, each offering unique advantages for tailoring structural, electrochemical, and functional properties. Sol–gel synthesis is among the most widely used methods, enabling fine control over particle size, porosity, and surface area due to its ability to transition from a liquid sol to a solid gel under mild conditions [88]. This method is particularly advantageous for producing uniform nanostructures with tunable pore architecture. Template-assisted methods employ physical or chemical templates to direct nanomaterial growth, facilitating the formation of hierarchical architectures such as nanorods and nanotubes, which are critical for enhancing active surface areas and charge transport pathways [88,89]. Hydrothermal and solvothermal synthesis techniques provide another effective strategy, leveraging high-pressure and high-temperature conditions in sealed environments to produce highly crystalline nanostructures with controlled morphologies. These methods allow precise regulation of parameters such as solvent composition, temperature, and pressure, thereby enabling the fabrication of uniform nanorods and nanoparticles suitable for catalytic and electrochemical applications [90,91]. In addition, nano-engineering strategies, including chemical vapor deposition, electrodeposition, and electroless plating, allow for atomic-level control of size, shape, and crystallinity. These approaches are instrumental in developing advanced materials for sensors, batteries, and catalysis, where structural precision is critical [92,93]. Doping and surface modification techniques further expand the morphological tuning possibilities by introducing foreign atoms or chemical groups that alter electronic, optical, and catalytic properties. For instance, doping nickel oxide with iron has been shown to significantly enhance its electrochemical activity, while surface functionalization modifies interfacial behavior and morphological stability [94].

8. Impact of Metal Oxide Nanomaterials on the Energy Density and Efficiency of Lithium-Ion and Solid-State Batteries: Some Recent Advancements

In LIBs, the introduction of metal oxide nanoparticles (MONPs) such as nickel oxide (NiO), copper oxide (CuO), and zinc oxide (ZnO) significantly increases energy density by offering a higher surface-area-to-volume ratio and superior electrochemical reactivity [10,95]. Among these, binary oxides like NiCuO exhibit synergistic effects that further improve performance, with an initial discharge capacity reaching 691 mAh g⁻¹ and maintaining a retention rate of 49% after 30 cycles [10]. In the context of cathode materials, lithium-rich layered oxides (LLOs) exploit both cationic and anionic redox reactions, which provide higher theoretical capacities and energy density. However, they still face operational challenges such as voltage decay and capacity fading during fast-charging cycles [96]. The efficiency of LIBs can also be significantly improved through the use of MONPs in anode design. NiO nanoparticles, for instance, exhibit lower charge/discharge voltage hysteresis due to stable solid electrolyte interphase (SEI) formation, which enhances energy efficiency [97]. Advanced composite anodes, such as those incorporating silicon@copper oxide@carbon nanofibers (Si@CuO@CNFs), further increase both energy density and cycling stability. These nanostructured materials mitigate the volume expansion of silicon and enhance conductivity, achieving a high reversible capacity of 748.5 mAh g⁻¹ after 800 cycles [98]. In SSBs, metal oxide nanomaterials improve not only energy density but also safety and electrochemical performance. When integrated with solid-state electrolytes (SSEs), MONPs like indium oxide (In₂O₃) and ZnO have been shown to enhance the coulombic efficiency (CE) and capacity retention of anode-free lithium-metal batteries (AFLMBs), achieving CE values close to 99.9% [99]. Coating or incorporating MONPs such as SnO₂ and Al₂O₃ at the interface between the electrode and electrolyte reduces interfacial resistance and SEI thickness, thereby enhancing interfacial contact and battery efficiency [85]. These improvements are crucial in preventing lithium dendrite formation and ensuring longer cycle life. Nanomaterials also contribute to better ion transport and mechanical stability in SSBs, addressing one of the major bottlenecks in their commercial adoption. By enhancing ionic conductivity and interface compatibility, they support faster charge/discharge rates and improved durability [9]. Table 1 provides an overview of recent investigations into metal oxide nanomaterials for energy density enhancement in lithium-ion and solid-state batteries, with emphasis on material composition, performance metrics, and cycling behavior.

Table 1. Recent studies on metal oxide nanomaterials for energy density improvements in lithium-ion and solid-state batteries.

Battery Type	Material	Additive	Energy Density Improvement	Cycle Performance	Other Benefits	Reference
Lithium-ion	Lithium-excess electrode materials	None	Higher energy density via oxide ion redox	Not specified	Improved charge compensation	[100]
Lithium-metal	Anode-free lithium-metal batteries	Al2O3, TiO2, SiO2	Increased specific energy	CE: 99.4% (TiO2), 98.8% (Al2O3); CR: 70% after 36–39 cycles	Improved SEI properties	[101]
Solid-state Li-metal	Garnet-type SSEs	Intermediate layers, alloys, polymer electrolytes	Improved energy density	Not specified	Enhanced ionic conductivity and interface contact	[102]
Lithium-ion	2D metal oxide nanomaterials	None	Higher energy density	Not specified	Improved ion-diffusion and charge-transport kinetics	[103]
Lithium-metal	Anode-free lithium-metal batteries	In2O3, ZnO	Increased specific energy	CE: 99.6% (In2O3), 99.2% (ZnO); CR: 70% within 46–39 cycles	Improved SEI properties	[99]
Lithium-ion	Transition metal oxides	None	High volumetric energy density	Not specified	Long cycle life, high-rate capability	[104]
Lithium-ion	Lithiated transition metal oxides	MOFs, zeolites	Improved energy density	Not specified	Enhanced stability and safety	[105]
Solid-state Li-metal	Solid-state electrolytes	None	Higher energy density	Not specified	Reduced electrolyte thickness	[3]
Solid-state Li-metal	Solid polymer electrolytes	SSZ-13	Improved energy density	Stable cycling performance	Enhanced Li+ conductivity and stability	[106]
Solid-state Li/Na-metal	LLZO-Ta, Na-β″-alumina	SnO2, Al2O3	Improved energy density	CE: 96.3% (LLZO-Ta), 91.9% (Na-β″-alumina)	Reduced interfacial resistance	[85]
Lithium-ion	Iron oxide/carbon composite nanofibers	None	Improved energy density per unit weight and volume	Not specified	Enhanced rate capabilities	[107]
Lithium-organic	Poly (4-vinyl catechol)	Single-ion conducting polymer nanoparticle electrolytes	High initial specific capacity	Stable for 500 cycles	High electrochemical stability	[108]
Lithium-ion	LiMnPO4 nanocrystals	Aloe vera extract	Improved energy density	Capacity retention: 97% (GS), 98% (SS)	Reduced charge transfer resistance	[109]
Solid-state Li-ion	Silicon nanoparticle electrode	MWCNTs	Nearly 100% increase in specific capacity	900 mAh g−1 for 100 cycles	Improved cycling stability	[110]
Solid-state Li-ion	Solid polymer composite electrolytes	Aerosol jet printing	Improved energy density	>85 mAh g−1 at 45 °C, >160 mAh g−1 at 75 °C	Scalable manufacturing method	[111]
Lithium-ion	CeO2/γ-Fe2O3 composite	None	High discharge capacity	Capacity retention over 100 cycles	High performance and environmental sustainability	[112]
Lithium-ion	Silicon nanowires/nanoparticles	None	Improved energy density	Stable SEI layer formation	Enhanced cycling lifetime	[113]
Lithium-ion	Si@NixSi/Ni core–shell electrode	None	High specific capacity	Cycle life: over 5000 cycles	Superior cycling stability	[114]

9. Mechanisms by Which Nanomaterials Enhance Solid-State Battery (SSB) Performance

Nanomaterials, particularly nanostructured oxides, play a transformative role in the performance and safety of solid-state batteries (SSBs) by enhancing ion transport, stabilizing interfaces, and improving electrochemical safety. Their nanoscale features enable improved conductivity, better interfacial contact, and suppression of failure mechanisms, all of which are critical for achieving high energy density in SSBs.

9.1. Enhancement of Ion Transport

One of the central challenges in SSBs is achieving high ionic conductivity in the solid-state electrolyte. Nanomaterials address this in several ways. Nanowires embedded in solid-state electrolytes act as ion-conducting scaffolds. Due to their high aspect ratio and large surface area, they create continuous transport networks that facilitate fast and uniform lithium-ion migration. These structures can also reduce crystallinity and glass transition temperatures, thereby improving polymer segmental motion and enhancing lithium salt dissociation [115]. Incorporating ionic liquids within metal–organic frameworks (MOFs) generates nanowetted interfaces, effectively transforming unstable solid–solid contact into highly conductive and stable interfacial layers. This strategy drastically improves Li+ mobility at the interface [116]. Oxide ceramic nanoparticles, such as cerium–zirconium oxides, can modify ion coordination environments in polymer matrices. This weakens lithium–anion interactions and selectively enhances lithium-ion conduction pathways [117].

9.2. Stabilization of Electrode–Electrolyte Interfaces

A stable interface between the electrolyte and electrodes is crucial to long-term battery performance: Architectural engineering, including the design of three-dimensional or integrated electrode structures, significantly increases interfacial contact area and facilitates efficient lithium-ion transfer [118]. Application of buffer layers and protective coatings—such as Li_1.4Al_0.4Ti_1.6(PO₄)₃ (LATP)—at the cathode–electrolyte interface helps suppress side reactions and maintains interfacial integrity under repeated cycling [118]. Metal oxide nanoparticles (MONPs), when incorporated into electrolytes, can suppress dendritic lithium growth, which is a major source of short circuits in lithium metal-based SSBs. This leads to enhanced coulombic efficiency and interfacial stability [85]. Surface wetting improvements at the lithium metal anode interface—enabled by nanoscale interface engineering—reduce interfacial resistance and enable more uniform lithium deposition [118].

9.3. Improving Electrochemical and Thermal Safety

Nanomaterials contribute significantly to the safety of SSBs by reducing risk factors associated with thermal and chemical instabilities: Surface coatings, such as Li₃VO₄ (LVO), form protective barriers on cathodes, suppressing unwanted side reactions and interface impedance, and improving mechanical robustness [119]. Thermal stability is greatly enhanced through the use of sulfide-based solid electrolytes like Li₄SnS₄. These materials are resistant to decomposition at high temperatures, which prevents exothermic reactions and enhances battery safety [120].

10. Challenges and Limitations of Metal Oxide Nanomaterials in Lithium-Ion and Solid-State Batteries

Despite their numerous advantages, metal oxide nanomaterials also present significant challenges that limit their large-scale application in lithium-ion and solid-state batteries. One of the most pressing issues is volume change and mechanical instability, particularly in all-solid-state lithium metal batteries (ASSLMBs). Lithium metal anodes can undergo dramatic volumetric expansion—up to 1000%—during repeated charge and discharge cycles, leading to mechanical degradation such as interfacial delamination and fracturing of active materials, which ultimately compromises ion transport and battery performance [30]. Additionally, the brittle nature of ceramic solid electrolytes further exacerbates the problem, as their inherently low fracture toughness limits their mechanical integrity under stress. However, incorporating nanostructures like reduced graphene oxide into ceramic electrolytes has shown promise in improving their toughness and overall durability [121].

Another critical limitation is the poor electronic and ionic conductivity inherent in many oxide materials. Although oxide-based solid electrolytes offer excellent thermal and electrochemical stability, they often exhibit high interfacial resistance and insufficient ionic conductivity, hindering their utility in solid-state battery configurations [7,122]. Improving the conductivity at the interface between the electrode and the solid-state electrolyte remains a major focus, with recent work in interface engineering showing some progress [100,123]. Composite electrolytes, which blend oxides with polymers or other conductive materials, have been proposed to overcome this barrier. While such hybrids can enhance both mechanical flexibility and ionic mobility, challenges persist in maintaining compatibility and minimizing interfacial resistance [32,36].

From a manufacturing perspective, the scalability and cost of nanomaterial synthesis are major barriers to commercial deployment. Although nanomaterials have the potential to revolutionize battery performance, their production often involves costly and complex techniques that are not easily scalable. To address this, emerging approaches such as thermal evaporation for producing thin lithium films have been explored to facilitate cost-effective, gigafactory-level production without sacrificing performance [15]. Nevertheless, integrating nanomaterials into large-scale manufacturing while maintaining quality and cost-efficiency remains a critical challenge [9].

Finally, safety, environmental, and recycling concerns also impact the viability of metal oxide nanomaterials in next-generation batteries. Solid-state electrolytes significantly improve battery safety by replacing flammable liquid electrolytes, reducing the risks of leakage and combustion [30,124]. However, issues such as dendrite growth, mechanical degradation, and interfacial instability still pose safety risks [122,125]. Environmentally, solid-state systems are more sustainable, but the environmental impact of synthesizing nanomaterials—especially regarding resource use, toxicity, and recycling—needs to undergo more rigorous life cycle assessment [6].

11. Future Directions for Metal Oxide Nanomaterials in Energy Storage

The future of metal oxide nanomaterials in lithium-ion and solid-state batteries lies in pushing the boundaries of both performance and manufacturability. These materials are valued for their high theoretical capacities—which are often two to three times greater than those of traditional carbon-based electrodes—making them essential for next-generation high-energy-density systems [126]. However, realizing this potential in practice requires addressing persistent issues such as cycling degradation, volume expansion, and poor interface stability. Innovations like binder-free film architectures and core–shell nanostructures have shown promise in mitigating these effects, while strategies to improve interfacial compatibility and suppress dendrite formation are essential for solid-state lithium metal batteries [127]. A rapidly emerging direction involves the use of artificial intelligence (AI) and machine learning (ML) for accelerated material discovery. These tools can predict functional properties like band gap energy with high accuracy, enabling researchers to screen large chemical spaces for optimal oxide nanostructures [128]. AI has also been used to identify key descriptors influencing catalytic and electrochemical performance in metal oxides, thereby facilitating targeted material design [129,130]. AI-driven process control may streamline scale-up and nanomanufacturing, bridging lab-scale breakthroughs with industrial applications [131]. Equally transformative are hybrid nanomaterials, which integrate oxides with carbonaceous or 2D materials such as graphene, MXenes, and polymers. These hybrids offer superior mechanical flexibility, thermal stability, and electrical conductivity. For example, transition metal oxide–graphene composites exhibit enhanced cycle life and conductivity, while MXene-based layers in polymer matrices improve dielectric performance and structural integrity [72,132]. Such synergies pave the way for robust, multifunctional electrodes [133,134].

Looking even further ahead, the concept of 4D nanostructures-materials that respond dynamically to environmental stimuli or damage-holds immense potential. These include self-healing hydrogels and supramolecular systems that can repair mechanical damage or adapt to changes in temperature and electrical stress. Advances in stimuli-responsive elastomers and hydrogels could significantly improve device longevity and reduce maintenance costs [72,135,136,137].

To fully exploit these materials, researchers are integrating them into next-generation solid-state battery architectures. Composite solid electrolytes (CSEs), for example, combine ceramic fillers with polymer matrices to enhance lithium-ion mobility and interfacial stability [138]. In tandem, advancements in Li–O₂ and Na–O₂ solid-state batteries are redefining benchmarks for safety and energy density, highlighting the need for optimized oxide-based electrocatalysts and solid electrolytes [139]. Commercialization and scalability remain critical. While mixed transition metal oxides (MTMOs) provide high structural stability and reversible capacity suitable for mass production, challenges remain in achieving consistent quality and yield at scale [60]. AI and process modeling are poised to facilitate large-scale optimization, from materials synthesis to integration in gigafactory-level production lines [131].

12. Conclusions

Metal oxide nanomaterials have demonstrated remarkable potential in advancing the electrochemical performance, energy density, and safety of both lithium-ion and solid-state batteries. Through nanoscale design, their large surface area-to-volume ratios and short ion diffusion paths significantly enhance lithium-ion transport and charge storage capabilities. Quantitatively, binary transition metal oxides such as NiCuO have achieved initial discharge capacities of approximately 691 mAh g⁻¹ with 49% capacity retention after 30 cycles, while silicon–metal oxide composites such as Si@CuO@CNFs sustain ~748 mAh g⁻¹ after 800 cycles—values that surpass those of conventional carbon-based anodes. In solid-state configurations, metal oxide nanomaterials including In₂O₃ and ZnO have enhanced coulombic efficiencies to 99.2–99.9%, indicating superior electrochemical reversibility and reduced interfacial losses. Garnet-type solid electrolytes such as Li₇La₃Zr₂O₁₂ (LLZO) paired with SnO₂ and Al₂O₃ coatings have further improved interfacial contact, reducing resistance and maintaining CE values above 96%, while promoting higher ionic conductivity and stability. Despite these advancements, challenges persist—particularly mechanical degradation due to volume expansion, high interfacial resistance in ceramic electrolytes, and the scalability of nanomaterial synthesis. Strategies such as composite electrolytes, interface engineering, and surface coatings (e.g., LiNbO₃ layers) have shown promise in mitigating these limitations, enhancing both safety and long-term performance. The integration of metal oxide nanomaterials into LIBs and SSBs enables a transformative leap in energy storage capability combining high theoretical capacities, improved coulombic efficiency, and enhanced thermal and mechanical stability. Future research should focus on scalable synthesis routes, life-cycle sustainability, and advanced interface designs to realize commercial-grade high-energy-density batteries. With optimized nanostructuring and eco-conscious manufacturing, metal oxide nanomaterials hold the key to powering the next generation of safe, durable, and high-performance electrochemical energy systems.