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Review

Recent Advances in Phase Change Materials for Thermal Management of Lithium-Ion and Emerging X-Ion Batteries: A Review

by
Ya-Chu Chang
Department of Mechanical Engineering, Chinese Culture University, Taipei 11114, Taiwan
Symmetry 2026, 18(5), 803; https://doi.org/10.3390/sym18050803
Submission received: 2 April 2026 / Revised: 1 May 2026 / Accepted: 2 May 2026 / Published: 8 May 2026
(This article belongs to the Section F: Engineering and Materials)
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Abstract

The rapid global transition toward electric vehicles (EVs) demands lithium-ion battery (LIB) systems that ensure both extreme performance and uncompromising safety. However, the inherent thermal asymmetry within battery packs—driven by non-uniform heat generation and localized hotspots—remains a critical bottleneck, accelerating degradation and triggering thermal runaway. Phase change materials (PCMs) have emerged as pivotal thermal buffers due to their high latent heat capacity and ability to maintain passive thermal symmetry. This review provides a comprehensive analysis of recent advancements in PCM-based battery thermal management systems (BTMSs), transitioning from material-level nanostructural enhancements to system-level hybrid architectures. Unlike traditional reviews, we critically evaluate how the integration of multidimensional conductive fillers and advanced encapsulation technologies resolves the trade-offs between energy density and thermal response rates. Furthermore, the synergistic coordination between PCMs and active cooling strategies (liquid, air, and heat pipes) is synthesized to provide a roadmap for achieving global thermal equilibrium under extreme fast-charging (XFC) conditions.

1. Introduction

1.1. The Rise of Electric Vehicles and the Global Decarbonization Agenda

The global transition toward electric vehicles (EVs) has accelerated significantly over the past decade, primarily propelled by the urgent necessity to mitigate greenhouse gas (GHG) emissions and reduce global dependence on fossil fuels. Road transportation has been consistently identified as a major contributor to climate change, with traditional internal combustion engine vehicles (ICEVs) substantially intensifying global warming due to their heavy reliance on petroleum [1,2]. Consequently, adopting low-carbon mobility options has become a critical mitigation pathway. Research indicates that EVs, particularly battery electric vehicles (BEVs), can significantly lower lifecycle and operational emissions by reducing tailpipe pollutants to zero, cutting both local air pollution and total transport-sector CO2 output [3,4]. When integrated with renewable electricity systems, BEVs can achieve 60–80% lower lifecycle emissions compared to ICEVs [5]. Furthermore, widespread EV adoption supports energy independence by potentially reducing fossil fuel demand by up to 90% in national fleets under aggressive adoption scenarios [6,7]. Driven by strong policy incentives [8], rapid technological improvements [5], and the United Nations Sustainable Development Goals (SDGs) [2], the exponential growth of the EV market represents a fundamental shift in the global transportation sector.

1.2. Lithium-Ion Batteries as the Standard Power Source

At the core of this electric mobility revolution are lithium-ion batteries (LIBs), which have unequivocally become the dominant power source for modern EVs. The widespread adoption of LIBs—accounting for 90–95% of the global market—is primarily attributed to their superior specific energy density (150–250 Wh/kg) and volumetric energy density (up to 300 Wh/L), which are essential for enabling extended and practical driving ranges [8,9,10,11]. In addition to high energy capacity, LIBs exhibit a remarkably low self-discharge rate of 2–8% per month [12], ensuring reliable energy retention during vehicle storage and intermittent driving. This characteristic is significantly superior to other systems such as NiMH or lithium-polymer batteries [13,14]. Furthermore, automotive-grade LIBs are engineered for long cycle durability, typically providing 1000 to 4500 charge–discharge cycles [9] and retaining 80% depth-of-discharge capacity after 1000 cycles [15], translating to an expected EV service life of 8–10 years [16]. Coupled with a high charge–discharge efficiency of 90–99% [12,17] and robust power density for fast-charging demands [9,18], LIBs possess the optimal electrochemical characteristics required for sustainable transportation.

1.3. The Critical Challenge of Thermal Management

Despite their distinct advantages, the performance, safety, and longevity of LIBs are highly susceptible to operating temperatures. Both extreme ambient temperatures and internal thermal gradients present severe thermal management challenges. At elevated temperatures, batteries experience accelerated degradation due to electrolyte decomposition, rapid solid electrolyte interphase (SEI) layer growth, and electrode corrosion, which collectively increase internal resistance and capacity fade [19]. More critically, localized and asymmetric heat accumulation can trigger exothermic side reactions, gas generation, and pressure rise, escalating into catastrophic thermal runaway and posing severe fire or explosion hazards [20,21]. Conversely, low-temperature environments severely impair LIB functionality; reduced ionic mobility and increased internal resistance lead to sharp declines in available power and energy output [19,22,23]. Charging under such cold conditions fosters lithium plating and dendrite formation, which can pierce the separator and cause internal short circuits [24,25]. Moreover, spatial thermal asymmetry (i.e., temperature non-uniformity) within battery modules accelerates localized aging, with even minor thermal gradients (e.g., 5 °C) significantly reducing overall pack power capacity and reliability [22,26,27]. Therefore, maintaining LIBs within a narrow, optimal thermal window and ensuring strict thermal symmetry is not merely beneficial, but strictly imperative for modern EVs. This critical requirement has necessitated the development of advanced thermal management systems. Recently, the integration of Phase Change Materials (PCMs) has emerged as a highly promising passive cooling strategy to absorb latent heat and restore global thermal symmetry across the battery pack, which will be the primary focus of this review. While this review primarily focuses on the application of PCMs in commercial LIBs for electric vehicles, the fundamental thermal management principles, material enhancement strategies, and hybrid architectures discussed herein are highly generalizable to emerging X-ion systems (e.g., sodium-ion and potassium-ion batteries), which face analogous Joule heating and thermal runaway challenges.

2. Mechanisms of Heat Generation and Thermal Asymmetry

2.1. Fundamental Heat Generation Sources

During charge and discharge cycles, the inherent electrochemical and physical processes within the battery generate a substantial amount of heat. This heat originates from three primary sources: (1) Reversible Entropic Heat (Qrev); (2) Irreversible Ohmic Heat (Qohm); and (3) Irreversible Polarization Heat (Qpol) [25,26,27,28].

2.1.1. Quantitative Thermal Behaviors and the Role of Cell Geometry

The total heat generation density (W/m3) is highly sensitive to the specific battery chemistry and applied C-rate. For instance, in high-energy-density nickel-rich chemistries (e.g., NCM811), the internal heat generation during extreme fast charging (XFC) or high-rate discharge (>3C) can rapidly exceed 50 kW/m3.
Cell geometry further dictates the manifestation of spatial thermal asymmetry. Cylindrical cells (e.g., 21,700) inherently suffer from severe anisotropic thermal conductivity due to their spiral structure; their axial thermal conductivity can reach 20–30 W/m·K, whereas radial conductivity remains extremely low (0.2–3.4 W/m·K), driving severe radial temperature gradients. Conversely, prismatic and pouch cells tend to accumulate localized hotspots near the electrode tabs due to concentrated current densities at high rates.

2.1.2. Dynamical Shift of Heat Sources

As dynamically depicted in Figure 1, the balance between these heat sources shifts significantly across the State of Charge (SOC) spectrum. At low C-rates, reversible entropic heat accounts for a notable proportion of the thermal profile [25]. However, as the operating conditions escalate to high C-rates (3C to 5C), the irreversible ohmic and polarization heat exponentially overwhelm the system [26,27,28], becoming the absolute primary drivers of rapid temperature spikes and triggering profound spatial thermal asymmetry.

2.2. High-Temperature Risks and Thermal Runaway Cascade

For optimal electrochemical performance and longevity, the operating temperature of an LIB should ideally be maintained within a narrow symmetric window of 20 °C to 40 °C [29], with spatial temperature variations (ΔT) kept strictly below 5 °C [30] across the module. Operating outside this envelope accelerates severe degradation mechanisms.
As illustrated in Figure 2, prolonged exposure to elevated temperatures accelerates the growth of the solid electrolyte interphase (SEI), consumes active lithium inventory, and promotes transition metal dissolution, leading to irreversible capacity loss [31,32].
More critically, when localized hotspots cause the internal temperature to exceed safety thresholds (typically >80–120 °C), the SEI layer begins to autonomously decompose [31]. This initiates a cascading chain reaction: the separator melts (around 130 °C for PE/PP materials), leading to widespread internal short circuits, electrolyte vaporization, and oxygen release from the cathode [32,33]. As meticulously mapped in Figure 3, this sequential cascade culminates in thermal runaway (TR), a catastrophic event where local temperatures can surge past 500–800 °C within seconds [34,35]. Various studies and models have extensively investigated these cascading failure mechanisms and heat generation dynamics [36,37,38,39,40,41,42,43,44]. Therefore, employing advanced BTMS to rapidly dissipate heat and suppress localized temperature spikes is non-negotiable for EV safety.

2.3. Low-Temperature Issues and Lithium Plating

Conversely, low-temperature conditions critically impair the electrochemical and transport processes within LIBs. As temperatures drop below 15 °C, electrolyte viscosity increases sharply, severely hindering lithium-ion migration and suppressing ionic conductivity [48,49,50,51,52,53,54,55,56,57,58]. This sluggish ion transport elevates charge-transfer resistance, reduces power output, and creates thermodynamic conditions favorable for lithium plating during charging [59,60,61,62,63]. Plating risk is further exacerbated by high SOC and fast-charging protocols, causing lithium ions to deposit as metallic lithium rather than intercalating into the anode [64,65,66]. The accumulation of plated lithium can evolve into dendritic structures that pierce the separator, causing internal short circuits (ISCs) [62,67,68,69]. Furthermore, plated lithium is highly reactive with the electrolyte; this exothermic reaction significantly lowers the thermal runaway onset temperature to 50–110 °C, transforming low-temperature degradation into a severe safety hazard during subsequent operation or heating [70,71,72].

3. PCMs for Battery Thermal Management System

3.1. Fundamental Working Principle of PCMs

Phase change materials (PCMs) function as highly effective passive thermal buffers within battery thermal management systems (BTMSs) by exploiting their intrinsic ability to absorb and release substantial quantities of latent heat during solid–liquid phase transitions. When the operational temperature of the battery exceeds the melting point of the PCM, the material undergoes an endothermic melting process. During this transition, the PCM absorbs significant excess heat while maintaining a nearly isothermal state, thereby preventing rapid temperature spikes and ensuring thermal stability within the battery pack. Because this mechanism relies entirely on the spontaneous thermodynamic phase change, PCM-based systems offer a passive cooling solution that requires no external energy input, making them structurally compact and highly energy-efficient for electric vehicle applications. Furthermore, this buffering effect is bidirectional; during low-temperature conditions or after the battery cools, the liquid PCM solidifies, releasing its stored latent heat to provide gentle preheating and prevent undercooling (Figure 4) [73]. Consequently, the integration of PCMs successfully delays the onset of thermal runaway and maintains the battery within its optimal thermal window, even under aggressive charging or discharging scenarios.

3.2. Conventional Phase Change Materials and Their Inherent Limitations

Conventional PCMs utilized in BTMSs are primarily categorized into organic compounds (paraffin waxes and fatty acids) and inorganic compounds (salt hydrates), each possessing distinct thermophysical properties (Table 1).
Paraffin waxes represent the most extensively investigated class due to their high chemical stability, cost-effectiveness, and tunable melting temperatures of 20–70 °C, compatible with LIB operational ranges. However, their widespread application is hindered by inherently low thermal conductivity 0.2–0.3 W/m · K, leakage issues in the molten state, and flammability, which could exacerbate ignition risks during severe thermal runaway. Fatty acids serve as bio-based, environmentally friendly organic alternatives offering high latent heat and a broad spectrum of melting points. Nevertheless, they similarly suffer from higher material costs and severe physical instability, as their susceptibility to liquid leakage during the melting phase remains a critical bottleneck for standalone applications (Figure 5) [74,80]. Conversely, inorganic salt hydrates exhibit superior thermal conductivity and higher latent heat capacities while being inherently non-flammable. Despite these advantages, salt hydrates are prone to supercooling, phase separation, and potential corrosiveness, often necessitating complex encapsulation strategies to prevent free water release and ensure long-term cyclic stability inside battery packs.
While pure PCMs provide substantial latent heat absorption, their independent application in electric vehicle BTMSs is severely restricted by several inherent thermophysical bottlenecks. The primary limitation is their intrinsically low thermal conductivity (typically 0.2–0.3 W/m · K for organic PCMs), which impedes rapid heat transfer from the battery surface to the PCM matrix [82,83,84]. This sluggish thermal diffusion causes a delayed melting front, allowing localized hotspots to develop under high C-rate charging or discharging operations before the phase transition can effectively engage [85,86]. Furthermore, pure organic PCMs are highly susceptible to liquid leakage post-melting [83,87], structurally weak against repeated thermal cycling [88,89], and inherently flammable [87]. Consequently, pure PCMs cannot independently sustain the rapid, high-flux heat dissipation required to prevent thermal runaway in EV battery modules [90], necessitating the implementation of robust material enhancement strategies.

4. PCM Enhancement Strategies for Battery Thermal Management

4.1. Integration of Multidimensional Conductive Fillers

To overcome the severe thermal conduction barrier of pure PCMs, formulating composite PCMs (CPCMs) via the integration of highly thermally conductive additives has become a primary enhancement strategy. These additives range from low-dimensional nanomaterials to macroscopic 3D frameworks, each providing specific pathways to accelerate heat dissipation and resolve spatial thermal asymmetry. The key enhancements provided by these fillers are summarized in Table 2.
At the micro- and nanoscale, 1D carbon nanotubes (CNTs) and 2D materials (e.g., graphene and silicene) are widely incorporated due to their exceptional intrinsic conductivities. CNTs establish nanoscale phonon transport pathways that significantly diminish interfacial thermal resistance. Figure 6 illustrates the molecular dynamics simulation of CNT integration within a PCM matrix, demonstrating these transport pathways. Furthermore, 2D transition metal carbides (MXenes, specifically Ti3C2Tx) improve thermal conductivity by over 120% and impart V-0 level flame retardancy [91,92,93,94,95].
To establish continuous thermal highways at the macroscopic level, 3D conductive skeletons such as expanded graphite (EG) and metallic foams are utilized, as detailed in Table 3. EG establishes a continuous 3D porous carbon network that amplifies in-plane thermal conductivity by up to 16.5 times. As illustrated in Figure 7, when EG is further wrapped with graphene films, the macroscopic 3D framework can achieve an ultra-high in-plane thermal conductivity of 30.75 W/m·K [91]. Similarly, metal foams can enhance effective thermal conductivity by up to 1751% and reduce melting duration by over 55%.
Table 3. Mechanisms and thermal improvements of conductive additives in PCMs.
Table 3. Mechanisms and thermal improvements of conductive additives in PCMs.
AdditiveClassificationPrimary Enhancement MechanismKey Thermal & Physical ImprovementsCitations
Expanded graphite (EG)3D porous carbon networkHigh in-plane heat transfer and leakage suppression via adsorption.7–16x increase in thermal conductivity; efficient leakage suppression.[107,108,109,110]
Carbon nanotubes (CNTs)1D nanofillersNanoscale phonon transport and reduced interfacial resistance.Up to 4x conductivity boost; synergistic effects with graphene.[111,112,113,114]
Metal foams (Al, Cu, Ni)3D metallic skeletonContinuous macroscopic 3D skeleton minimizing thermal resistance.>10x conductivity increase; 41–55% reduction in melting time.[115,116,117,118,119]
Despite these profound thermal improvements, the integration of conductive fillers introduces critical trade-offs in BTMS design. A fundamental paradox exists between thermal conductivity and energy buffering capacity: increasing the mass fraction of conductive additives or the density of metal foams inherently displaces the PCM, thereby decreasing the total latent heat capacity (J/g) of the composite. Moreover, while dense metallic foams provide optimal thermal transport, they substantially increase the overall weight and parasitic mass of the BTMS, negatively impacting the pack-level specific energy density of the EV. Consequently, optimal filler integration requires a rigorous engineering balance between achieving a sufficient thermal response rate for fast-charging and minimizing the associated weight and latent-heat penalties.
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Figure 6. Molecular dynamics simulation model illustrating the integration of carbon nanotubes (CNTs) within a PCM matrix, creating nanoscale phonon transport pathways for thermal conductivity enhancement [112].
Figure 6. Molecular dynamics simulation model illustrating the integration of carbon nanotubes (CNTs) within a PCM matrix, creating nanoscale phonon transport pathways for thermal conductivity enhancement [112].
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Figure 7. Microstructural architecture of advanced 3D composite PCMs (e.g., graphene/expanded graphite networks). By constructing this continuous macroscopic thermal highway, the composite achieves an ultra-high thermal conductivity (up to 30.75 W/m·K), facilitating rapid heat dissipation and radiative cooling to effectively prevent localized thermal saturation [91].
Figure 7. Microstructural architecture of advanced 3D composite PCMs (e.g., graphene/expanded graphite networks). By constructing this continuous macroscopic thermal highway, the composite achieves an ultra-high thermal conductivity (up to 30.75 W/m·K), facilitating rapid heat dissipation and radiative cooling to effectively prevent localized thermal saturation [91].
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To systematically evaluate the frontier of current material designs, a quantitative benchmarking analysis of various composite PCMs (CPCMs) is presented in Table 4. This comparative evaluation highlights the fundamental trade-off between volumetric/gravimetric latent heat retention and effective thermal conductivity.
As benchmarked below, while pure PCMs offer maximum thermal buffering capacity, their severe insulative nature renders them inadequate for high-rate applications. The integration of high-density metallic foams drastically shifts the performance towards the high-conductivity regime, but at a severe expense of the latent heat capacity due to volume displacement. Advanced carbonaceous architectures, such as graphene networks and expanded graphite, currently occupy the optimal material frontier. They offer a highly balanced enhancement—maximizing the thermal response rate (up to 30.75 W/m·K) without excessively penalizing the energy buffering capability (>150 J/g) required for long-duration EV thermal management.

4.2. Advanced Encapsulation Technologies

Encapsulation is a fundamental strategy designed to eradicate liquid leakage and bolster structural durability by confining the PCM core within a protective polymeric or inorganic shell. This isolation ensures that the phase transition occurs in a closed environment, preventing chemical degradation and ensuring cyclic reliability. The distinct characteristics of micro- and macro-encapsulation are summarized in Table 5.
A critical comparison of these encapsulation strategies reveals that the selection involves complex engineering trade-offs regarding thermal efficiency and cost. Micro-encapsulation offers a high surface-to-volume ratio, which facilitates rapid heat absorption; however, the cumulative interfacial thermal resistance of millions of individual shells can impede overall heat flux into the PCM core. Furthermore, the shell material typically accounts for 10–30% of the total capsule weight, imposing a significant loading limitation that reduces the effective latent heat capacity of the system. From a structural cost perspective, the complex chemical synthesis required for micro-encapsulation (e.g., in situ polymerization) is generally more expensive than mechanical alternatives.
In contrast, macro-encapsulation employs larger, rigid containers—often 3D-printed or metallic—which provide immense design flexibility for module-level integration. While macro-encapsulation has a lower specific surface area for heat transfer, it allows for the direct integration of extended heat-transfer structures, such as metallic fins, to overcome the core’s low thermal conductivity. The relative weight of the macro-shell is often lower than that of micro-shells for the same volume of PCM, allowing for higher energy buffering density. Therefore, while micro-encapsulation is better suited for flexible coatings or slurries, macro-encapsulation remains the preferred choice for large-scale EV battery packs where structural robustness and cost-effectiveness are paramount.

4.3. Shape-Stabilization via Porous Matrices

Beyond traditional encapsulation, shape-stabilized PCMs (SSPCMs) utilize the physical confinement capabilities of highly porous scaffolds—such as carbon foam, metallic matrices, and melamine aerogels—to immobilize the liquid phase. The fundamental mechanism relies on strong capillary forces, surface tension, and pore–wall interfacial interactions, which trap the molten PCM within the interconnected hierarchical pore networks (Figure 8 [135,136,137,138]). Because these matrices possess extraordinarily high specific surface areas (e.g., up to 485 m2/g for carbon aerogels), they permit extremely high PCM loading fractions, thereby preserving maximum latent heat capacity [138,139]. The integration of these rigid or semi-flexible porous skeletons not only amplifies the overall thermal conductivity but also dramatically improves the compressive strength and mechanical fatigue resistance of the composite (Figure 9 [140,141,142,143,144]). Consequently, SSPCMs can effectively maintain battery operating temperatures well below critical safety thresholds (e.g., 30–40 °C under 3C–5C discharge), significantly delaying the onset of thermal runaway [125,126,128]. The physicochemical mechanisms and performance advantages of shape-stabilization using 3D porous matrices are quantitatively summarized in Table 6.
An analysis of these scaffolding materials reveals that their selection significantly influences the practical engineering applicability of the BTMS. Specifically, carbon-based scaffolds (e.g., carbon aerogels and expanded graphite [140]) offer superior chemical inertness and low density, which is essential for maintaining the high gravimetric energy density of EVs. However, their intrinsic brittleness can lead to structural failure under high-vibration automotive environments. In contrast, metallic matrices (e.g., copper or aluminum foams [142]) provide unmatched mechanical robustness and thermal conductivity but introduce significant weight penalties and potential corrosion risks when used with certain salt-hydrate PCMs. Alternatively, polymeric or hybrid aerogels (e.g., melamine-based) present a promising middle ground by offering both flexibility and cost-effectiveness, although their lower thermal stability often necessitates the integration of additional flame-retardant additives to ensure safety under extreme temperature excursions.

4.4. Economic Feasibility and Commercialization Trade-Offs

While the integration of advanced fillers (e.g., MXene, silicene) and complex macroscopic structures (e.g., metallic foams) significantly enhances thermal performance, it introduces substantial manufacturing complexity and cost constraints. From a commercialization perspective, a rigorous quantitative trade-off must be evaluated between the initial material costs and the long-term economic benefits of extending the battery cycle life. For instance, while MXene exhibits exceptional multi-functional properties (high conductivity and flame retardancy), its synthesis via harsh etching processes remains prohibitively expensive for large-scale EV deployment. Conversely, conventional expanded graphite (EG) offers a highly cost-effective alternative, balancing moderate material costs with satisfactory thermal enhancements. Therefore, the industrial transition of CPCMs relies on developing scalable, low-cost manufacturing pathways that justify the initial BTMS investment by demonstrably preventing premature battery degradation and reducing warranty replacement costs over the EV’s 8-to-10-year lifespan.

5. Hybrid PCM-Based Thermal Management Architectures

5.1. The Mechanistic Necessity: Overcoming Thermal Saturation and the “Thermal Blanket” Effect

While phase change materials possess exceptional latent-heat buffering capabilities, their effectiveness is highly dependent on ambient temperatures and operational loads. Numerous experimental and numerical studies consistently expose their inherent limitations under high-multiplier operating conditions or extreme climates [147,148,149,150,151]. Standalone PCM systems frequently fail to maintain safe battery temperatures during high-rate discharging (e.g., ≥3C), ultra-fast charging, or continuous cycling [147,148,149,150,152].
This failure is mechanistically attributed to “thermal saturation.” Due to the low intrinsic thermal conductivity of organic PCMs, heat removal from the battery surface is severely restricted, causing rapid localized melting and uneven latent heat utilization [147,148,149]. Once the PCM is fully melted, its cooling capability collapses. More critically, the fully liquid PCM begins to act as an insulating layer—often referred to as the “thermal blanket” effect. In this saturated state, it severely hinders further heat dissipation to the external environment and subsequent heat dissipation relies entirely on its low sensible heat, leading to an uncontrolled temperature rise [147,148]. For instance, experiments have demonstrated that pure PCM cooling fails beyond 2C–3C discharge rates, with peak temperatures soaring to 52.8–87.3 °C [153].
Consequently, it is imperative to hybridize PCMs with active cooling or highly conductive secondary pathways to dynamically extract accumulated heat and actively regenerate the PCM’s latent capacity (Table 7). Therefore, resolving the thermal asymmetry caused by localized PCM saturation requires hybrid BTMSs, which introduce asymmetric active cooling mechanisms to restore overall thermal symmetry across the battery module.

5.2. Liquid–PCM Hybrid Architectures

The integration of active liquid cooling with passive PCM buffers is widely recognized as the most effective hybrid strategy to counteract extreme thermal asymmetry in severe operational environments [154]. In this configuration, the PCM acts as an immediate thermal buffer that absorbs transient heat spikes and homogenizes localized hotspots to suppress spatial thermal asymmetry, while the liquid cooling channels actively extract the accumulated bulk heat to prevent complete PCM melting [147]. This synergistic mechanism allows the hybrid system to dramatically outperform pure liquid or standalone PCM configurations by driving the entire battery module toward a state of perfect thermal symmetry. Extensive studies indicate that liquid–PCM hybrids can robustly maintain maximum battery temperatures Tmax between 36 °C and 40 °C, ensuring a highly symmetrical temperature distribution even under aggressive 3C–5C charge/discharge conditions [154,155,156,157]. Furthermore, because the PCM inherently absorbs approximately 40% of the initial asymmetric heat load, the operational demands on the active thermal management system are drastically reduced, enabling up to a 76% decrease in liquid-cooling pumping power and significantly enhancing the overall energy efficiency of the EV (Figure 10) [155].

5.3. Heat Pipes and Highly Conductive PCM Hybrids

For battery packs requiring compact passive or semi-active cooling, coupling PCMs with phase-change heat pipes (HPs) or macroscopic metallic structures (such as fins or metal foams) offers profound thermal improvements by effectively resolving spatial thermal asymmetry. Heat pipes embedded within the PCM matrix serve as ultra-fast thermal bridges; they rapidly transport asymmetrically accumulated internal heat to external heat sinks, substantially extending the operational duration of the PCM before localized saturation occurs (Figure 11) [147]. Experimental evidence demonstrates that PCM–HP hybrids can drastically suppress the maximum pack temperature (e.g., reducing Tmax from 68.9 °C down to 43.2 °C during high-rate discharge [158], driving the module back to a safe, symmetrical thermal state. Similarly, the incorporation of highly conductive metallic fins or metal foams successfully delays thermal saturation by expanding the heat-spreading networks. These macroscopic structures counteract uneven heat generation by ensuring deep and uniform utilization of the PCM’s latent heat, thereby maintaining stringent thermal symmetry across the entire battery pack [159,160].

5.4. Air–PCM Hybrid Architectures

Air cooling, characterized by its structural simplicity and low cost, is frequently hybridized with PCMs to overcome its inherently low convective heat transfer coefficient and the severe spatial thermal asymmetry typically induced by uneven airflow from the inlet to the outlet. In an Air–PCM system, forced air convection is utilized not as the primary heat sink for the batteries, but as an active regeneration mechanism for the PCM. By blowing air over the PCM matrix, the system actively dissipates heat during resting periods or lower-load operations, accelerating the solidification process of the molten PCM and preventing cumulative thermal buildup over repeated EV driving cycles (Figure 12) [147,161]. Consequently, this hybrid architecture effectively harmonizes the structurally asymmetric cooling capacity of forced air with the uniform thermal buffering of the PCM, guaranteeing long-term thermal symmetry and stability across the battery module.

6. Conclusion and Future Perspectives

6.1. Conclusion

This review has systematically evaluated the evolution of PCM-based BTMSs, emphasizing the transition from standalone passive buffers to intelligent, multi-functional hybrid systems. A high-level synthesis of current research reveals that while material-level modifications—such as the construction of 3D conductive skeletons and V-0 level flame-retardant composites—have largely addressed the low thermal conductivity and leakage issues of pure PCMs, the ultimate challenge lies in the system-level thermal symmetry.
The findings indicate that the effectiveness of a BTMS is no longer determined by the cooling capacity alone, but by its ability to maintain a symmetric temperature distribution (<5 °C) across large-scale modules during extreme excursions. Hybrid architectures, particularly those coupling PCMs with micro-channel liquid cooling or pulsating heat pipes, offer the most robust solution for next-generation EVs. However, the integration of these systems introduces a “thermal-mass paradox,” where the added weight of cooling components and PCM matrices must be rigorously balanced against the pack-level energy density requirements. In conclusion, the field is shifting from mere “temperature suppression” toward “dynamic thermal equilibrium,” requiring a holistic design approach that considers material durability, structural parasitic mass, and active control synergy.

6.2. Future Perspectives and Research Gaps

Despite the significant progress documented in this review, several critical research gaps remain that must be addressed to facilitate the commercial adoption of PCM-based BTMS in EVs:
  • Long-term Material Durability and Aging: Most current studies focus on short-term thermal cycling (100–500 cycles). There is a profound lack of data regarding the physicochemical stability of composite PCMs (especially organic-inorganic hybrids) over the actual lifespan of an EV (8–10 years). Research into PCM aging mechanisms, sub-cooling effects during long-term storage, and the impact of continuous mechanical vibrations on encapsulation integrity is urgently needed.
  • AI-Driven Thermal Prediction and Digital Twins: The phase transition front within a PCM matrix is highly non-linear and difficult to monitor in real-time. Future research should leverage Machine Learning (ML) and Digital Twin technology to develop predictive thermal models. These models could optimize the “active–passive” switching frequency in hybrid systems, allowing the active cooling pump to trigger preemptively based on predicted latent heat saturation levels.
  • Sustainability and Circular Economy: As the EV market scales, the environmental footprint of PCM synthesis becomes critical. There is a specific research gap in the development of “Bio-based PCMs” derived from agricultural waste and the recyclability of composite PCMs at the end of the battery life. Symmetrizing high performance with environmental sustainability will be a key scientific question.
  • Integration with Next-Generation Battery Chemistries: While this review focuses on LIBs, the thermal requirements for solid-state batteries (SSBs) and sodium-ion batteries are vastly different. Investigating how PCMs can be adapted to provide the specific pressure and high-temperature environments required for SSB interfacial stability represents a nascent and vital research frontier.

Funding

This research received no external funding.

Data Availability Statement

No new data were created or analyzed in this study.

Conflicts of Interest

The author declares no conflicts of interest.

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Figure 1. Quantitative comparison of total, reversible, and irreversible heat generation components in lithium-ion batteries across the State of Charge (SOC, x-axis). The sub-panels denote different C-rates ((A): 0.5C, (B): 1C, (C): 2C) and varying State of Health (SOH) conditions (I: SOH = 100%, II: SOH = 90%, III: SOH = 80%). The data clearly illustrates how irreversible heat exponentially becomes the dominant factor under high-rate operations and as the battery degrades [29].
Figure 1. Quantitative comparison of total, reversible, and irreversible heat generation components in lithium-ion batteries across the State of Charge (SOC, x-axis). The sub-panels denote different C-rates ((A): 0.5C, (B): 1C, (C): 2C) and varying State of Health (SOH) conditions (I: SOH = 100%, II: SOH = 90%, III: SOH = 80%). The data clearly illustrates how irreversible heat exponentially becomes the dominant factor under high-rate operations and as the battery degrades [29].
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Figure 2. Mechanistic overview of battery degradation pathways at elevated temperatures. The schematic highlights the vicious cycle among material degradation (e.g., lithium plating and electrolyte decomposition), impedance growth, and the subsequent amplification of heat generation [29].
Figure 2. Mechanistic overview of battery degradation pathways at elevated temperatures. The schematic highlights the vicious cycle among material degradation (e.g., lithium plating and electrolyte decomposition), impedance growth, and the subsequent amplification of heat generation [29].
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Figure 3. Sequential progression of thermal runaway (TR) triggers in lithium-ion batteries. The timeline demonstrates the critical temperature thresholds for various internal failure modes, from initial SEI breakdown to catastrophic cathode decomposition [45,46,47].
Figure 3. Sequential progression of thermal runaway (TR) triggers in lithium-ion batteries. The timeline demonstrates the critical temperature thresholds for various internal failure modes, from initial SEI breakdown to catastrophic cathode decomposition [45,46,47].
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Figure 4. Schematic representation of the bidirectional thermal regulation capability of PCM-based systems, illustrating the dual functions of high-temperature passive cooling and low-temperature latent heat preheating [73].
Figure 4. Schematic representation of the bidirectional thermal regulation capability of PCM-based systems, illustrating the dual functions of high-temperature passive cooling and low-temperature latent heat preheating [73].
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Figure 5. Macroscopic visual comparison demonstrating the critical liquid leakage vulnerability of conventional pure PCMs at elevated temperatures, contrasted with the structural integrity achieved through advanced shape-stabilization techniques [80].
Figure 5. Macroscopic visual comparison demonstrating the critical liquid leakage vulnerability of conventional pure PCMs at elevated temperatures, contrasted with the structural integrity achieved through advanced shape-stabilization techniques [80].
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Figure 8. Schematic representation of the shape-stabilization mechanism using multidimensional carbon matrices (0D, 2D, and 3D expanded graphite). The 3D porous skeleton effectively immobilizes the molten PCM via capillary forces, thoroughly eliminating leakage [138].
Figure 8. Schematic representation of the shape-stabilization mechanism using multidimensional carbon matrices (0D, 2D, and 3D expanded graphite). The 3D porous skeleton effectively immobilizes the molten PCM via capillary forces, thoroughly eliminating leakage [138].
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Figure 9. High-magnification SEM micrograph demonstrating the successful infiltration and physical confinement of PCM within the interconnected hierarchical pores of an expanded graphite (EG) matrix [140].
Figure 9. High-magnification SEM micrograph demonstrating the successful infiltration and physical confinement of PCM within the interconnected hierarchical pores of an expanded graphite (EG) matrix [140].
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Figure 10. Schematic architecture of a hybrid liquid–PCM battery thermal management system (C). The active liquid cooling channels (B) are integrated within the PCM matrix (A) to efficiently extract accumulated bulk heat, thereby preventing PCM thermal saturation during fast charging [154].
Figure 10. Schematic architecture of a hybrid liquid–PCM battery thermal management system (C). The active liquid cooling channels (B) are integrated within the PCM matrix (A) to efficiently extract accumulated bulk heat, thereby preventing PCM thermal saturation during fast charging [154].
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Figure 11. Schematic of a hybrid battery thermal management system integrating phase change materials (PCM) with heat pipes (HPs). The embedded HPs act as ultra-fast thermal bridges, effectively transferring accumulated internal heat from the PCM matrix to an external liquid cold plate, thereby preventing thermal saturation under high-rate operations [152].
Figure 11. Schematic of a hybrid battery thermal management system integrating phase change materials (PCM) with heat pipes (HPs). The embedded HPs act as ultra-fast thermal bridges, effectively transferring accumulated internal heat from the PCM matrix to an external liquid cold plate, thereby preventing thermal saturation under high-rate operations [152].
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Figure 12. Visual overview of hybrid PCM-based thermal management architectures, demonstrating the synergistic mechanisms of combining PCM with active air convection and structural enhancements to regenerate latent heat capacity. Adapted from Ref. [155], “#” represents Battery Number.
Figure 12. Visual overview of hybrid PCM-based thermal management architectures, demonstrating the synergistic mechanisms of combining PCM with active air convection and structural enhancements to regenerate latent heat capacity. Adapted from Ref. [155], “#” represents Battery Number.
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Table 1. Thermophysical characteristics and limitations of conventional PCMs.
Table 1. Thermophysical characteristics and limitations of conventional PCMs.
TypePrimary AdvantagesInherent LimitationsCitations
Paraffin waxesHigh latent heat capacity; excellent chemical stability; low cost; highly tunable melting points.Inherently low thermal conductivity; high flammability; susceptibility to liquid leakage.[73,74,75,76,77]
Salt hydratesSuperior latent heat and thermal conductivity; strictly non-flammable.Phase separation; supercooling effects; corrosive nature; risk of free water release.[73,75,78]
Fatty acidsBio-based and eco-friendly; high latent heat; wide customizable melting range.Higher economic cost; severe leakage without proper structural encapsulation.[73,79,80,81]
Table 2. Quantitative comparison of enhancements provided by advanced nanocomposite PCMs.
Table 2. Quantitative comparison of enhancements provided by advanced nanocomposite PCMs.
Composite AdditivePrimary Enhancement MechanismRepresentative Quantitative ImprovementCitations
MXene-based networksCreation of robust 3D bridging networks and flame-retardant barriers.>120% thermal conductivity boost; achieves V-0 level flame retardancy.[91,92,93,94,95]
Graphene & derivativesEstablishment of ultra-high in-plane conductive highways and 3D frameworks.In-plane thermal conductivity reaching 30.75 W/m·K; zero leakage.[96,97,98,99,100,101]
SiliceneSignificant reduction in interfacial thermal resistance; enhanced lattice vibration coupling for microscale heat transport.Significant reduction in interfacial thermal resistance; enhanced lattice coupling.[82,102]
General NanofillersFormation of multidimensional 3D thermal conductive pathways.Improved cell temperature uniformity (ΔT < 5 °C); multi-functional stability.[93,103,104,105,106]
Table 4. Quantitative benchmarking of thermal conductivity vs. latent heat capacity across various PCM configurations.
Table 4. Quantitative benchmarking of thermal conductivity vs. latent heat capacity across various PCM configurations.
Material ConfigurationTypical Effective Thermal Conductivity (W/m·K)Typical Latent Heat Capacity (J/g)Core Engineering Trade-off/Frontier Status
Pure Organic PCMs0.2–0.3200–250Baseline: Maximum energy storage, but insufficient thermal response for XFC.
CPCMs with 1D/2D Nanofillers (e.g., CNTs, MXene)0.5–2.5170–210Moderate Enhancement: Good balance at low mass fractions, but prone to agglomeration.
CPCMs with 3D Metal Foams (e.g., Cu, Al, Ni)2.0–15.0100–160High Conductivity Regime: Excellent heat spreading, but severe latent heat and weight penalties.
CPCMs with 3D Carbon Scaffolds (e.g., EG, Graphene)5.0–30.75150–190Optimal Frontier: Superior in-plane heat transfer with minimal parasitic weight penalty.
Table 5. Comparison of encapsulation strategies for PCM stabilization.
Table 5. Comparison of encapsulation strategies for PCM stabilization.
Enhancement FunctionMicro-Encapsulation
1–1000 μm		Macro-Encapsulation
>1000 μm		Citations
Leakage preventionThin core–shell structure completely confines molten PCM at the microscale.Rigid, sealed structural containers prevent macroscopic fluid outflow.[120,121,122,123]
Structural stabilityStrong shells resist both thermal expansion and mechanical stresses during phase changes.Robust external casings endure long-term cyclic and pack-level mechanical stresses.[124,125,126,127,128,129,130,131,132,133]
Environmental protectionShell securely isolates the PCM core from oxygen and moisture to prevent degradation.Macro-shell prevents internal battery corrosion and physical contamination.[121,122,123,124,125,126,127,128,129,131]
Improved dispersion & integrationMicron-scale dimensions enable highly uniform distribution and dispersion within the matrix.Enables flexible and direct modular integration into battery pack designs.[125,126,127]
Thermal reliabilityMaintains stable latent heat retention and consistent performance over long thermal cycling.Provides high thermal stability suitable for large-format PCM module applications.[128,134]
Table 6. Mechanisms and advantages of shape-stabilization using 3D porous matrices.
Table 6. Mechanisms and advantages of shape-stabilization using 3D porous matrices.
Performance AdvantagePhysicochemical MechanismCitations
Absolute leakage preventionPCM is physically immobilized via strong capillary forces and surface tension within the interconnected pores.[135,136,137]
High thermal capacity loadingLarge pore volumes and hierarchical surface areas enable maximum PCM infiltration and latent heat retention.[138,139]
Thermal conductivity enhancementCarbon or metallic foams establish continuous 3D conductive pathways, drastically accelerating heat transfer.[140,141,142]
Mechanical structural stabilityThe rigid or semi-flexible porous skeleton physically supports the PCM structure, preventing deformation during cycling.[135,143,144]
Thermal safety improvementsAccelerated heat spreading combined with robust structural integrity effectively delays the onset of thermal runaway.[143,145]
Superior temperature uniformityRapid multidirectional heat diffusion minimizes local hotspots and ensures even temperature distribution across cells.[146]
Table 7. Mechanistic limitations of standalone PCMs and the corresponding advantages of hybrid architectures.
Table 7. Mechanistic limitations of standalone PCMs and the corresponding advantages of hybrid architectures.
Limitation of Standalone PCMManifestation in EV Battery OperationAdvantage of Hybrid ArchitectureCitations
Low thermal conductivityRapid localized melting, severe hotspots, and poor temperature uniformity at >3C.Secondary conductive networks (fins, metal foams, heat pipes) establish ultra-fast heat-spreading pathways.[147,154,155,156,157,158,159,160]
Latent heat depletionSudden thermal saturation resulting in a catastrophic loss of cooling functionality.Active fluid loops (liquid/air) continuously extract heat, actively regenerating the PCM’s latent capacity.[147,154,161,162]
Inadequate thermal recoveryCumulative heat buildup during repeated charge/discharge cycles, elevating thermal runaway risks.Active cooling accelerates the resolidification process between successive high-power cycles.[163,164]
Inability to handle fast chargingStandalone passive systems critically fail under extreme 3C–8C fast-charging protocols.Liquid-PCM hybrids robustly suppress peak temperatures below safe thresholds (Tmax < 40 °C).[155,156,157,165]
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Chang, Y.-C. Recent Advances in Phase Change Materials for Thermal Management of Lithium-Ion and Emerging X-Ion Batteries: A Review. Symmetry 2026, 18, 803. https://doi.org/10.3390/sym18050803

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Chang Y-C. Recent Advances in Phase Change Materials for Thermal Management of Lithium-Ion and Emerging X-Ion Batteries: A Review. Symmetry. 2026; 18(5):803. https://doi.org/10.3390/sym18050803

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Chang, Ya-Chu. 2026. "Recent Advances in Phase Change Materials for Thermal Management of Lithium-Ion and Emerging X-Ion Batteries: A Review" Symmetry 18, no. 5: 803. https://doi.org/10.3390/sym18050803

APA Style

Chang, Y.-C. (2026). Recent Advances in Phase Change Materials for Thermal Management of Lithium-Ion and Emerging X-Ion Batteries: A Review. Symmetry, 18(5), 803. https://doi.org/10.3390/sym18050803

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