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Capacity loss
Capacity loss
Capacity loss
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Capacity loss or capacity fading is a phenomenon observed in rechargeable battery usage where the amount of charge a battery can deliver at the rated voltage decreases with use.[1][2]

In 2003 it was reported the typical range of capacity loss in lithium-ion batteries after 500 charging and discharging cycles varied from 12.4% to 24.1%, giving an average capacity loss per cycle range of 0.025–0.048% per cycle.[3]

Stress factors

[edit]

Capacity fading in Li-ion batteries occurs by a multitude of stress factors, including ambient temperature, discharge C-rate, and state of charge (SOC).

Capacity loss is strongly temperature-dependent. Aging rates increase as temperatures rise or fall above or below 25 °C. [4][5]

Capacity loss is C-rate sensitive and higher C-rates lead to a faster capacity loss on a per cycle. Chemical mechanisms of degradation in a Li-ion battery dominate capacity loss at low C-rates, whereas, mechanical degradation dominates at high C-rates.[6][7]

Graphite/LiCoO2 battery capacity degradation is reported to be affected by mean SOC as well as the change in SOC (ΔSOC) during the cycling operation. For the first 500 equivalent full cycles mean SOC is found to have a major effect on the capacity fade of cells as compared to ΔSOC. However, towards the end of the testing (600~800 equivalent cycles) ΔSOC becomes the major factor affecting the capacity loss rate of the cells.[8]

See also

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References

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Capacity loss

View on Grokipedia
from Grokipedia
Capacity loss, also known as capacity fading, refers to the irreversible reduction in a rechargeable battery's ability to store and deliver its nominal amount of charge over time, resulting from chemical, physical, and mechanical degradation processes that increase unusable inactive material within the cell from the moment of manufacture. This phenomenon is observed across various battery chemistries, but it is most prominently studied in lithium-ion batteries, where it manifests as a linear decline primarily driven by , calendar aging, and operational stresses like deep discharges. In lithium-ion batteries, the dominant mechanisms of capacity loss include the loss of lithium inventory (LLI), caused by the growth of the solid electrolyte interphase (SEI) layer and lithium plating on the , as well as the loss of active material (LAM) due to electrode cracking, particle pulverization, and electrolyte decomposition. These processes not only diminish the battery's (SOH)—defined as the ratio of actual to nominal capacity, typically expressed as a —but also correlate strongly with internal resistance increases, with a negative Pearson's (r < -0.8) observed in over 97% of tested cells across nickel-manganese-cobalt (NMC), nickel-cobalt-aluminum (NCA), and -iron-phosphate (LFP) chemistries. For instance, high-energy-density lithium-ion batteries such as NMC and NCA typically retain about 80% of their initial capacity after 300–500 full charge-discharge cycles, whereas LFP batteries can retain 80% after thousands of cycles, marking a practical end-of-life (EOL) threshold often set between 70% and 80% SOH for applications like electric vehicles. Capacity loss impacts battery performance by reducing energy density, extending charge times due to diminished charge transfer efficiency, and lowering overall system reliability, particularly in high-demand sectors such as electric vehicles (EVs), renewable energy storage, and consumer electronics. In EVs, for example, degradation can shorten driving range and necessitate earlier replacements, influencing lifecycle costs and sustainability. In consumer electronics, such as laptops, batteries typically last 2-5 years with regular use before significant capacity loss leads to an inability to hold a charge, requiring the device to remain constantly plugged in. Mitigation strategies include avoiding full discharges, implementing partial charging regimens (e.g., maintaining 20–80% state-of-charge), and using advanced battery management systems to monitor and balance cells, which can extend usable life by minimizing stress factors like high temperatures and overcharging. While some capacity fade is inevitable and linear with age, ongoing research focuses on material innovations, such as improved electrolytes and electrode designs, to slow degradation rates and enhance long-term performance.

Fundamentals

Definition

Capacity loss, also known as capacity fading, refers to the progressive and often irreversible reduction in the amount of charge a rechargeable battery can store and deliver at its rated voltage over time or through repeated charge-discharge cycles. This decline arises from various degradation processes that diminish the battery's active material availability or lithium-ion transport efficiency, leading to a shorter runtime for a given load. The nominal capacity of a battery, denoted as QQ, is fundamentally defined by the relation Q=I×tQ = I \times t, where II is the discharge current and tt is the discharge time; capacity loss manifests as a consistent decrease in this QQ value with aging or cycling. Capacity loss is distinct from related degradation phenomena such as efficiency loss or power fade. Efficiency loss typically involves a drop in coulombic efficiency, reflecting the mismatch between charge input and output due to side reactions, whereas power fade stems from increased internal resistance that limits the battery's ability to deliver high currents or rates. In contrast, capacity loss focuses exclusively on the erosion of the battery's total deliverable charge storage, independent of rate or round-trip energy recovery. The phenomenon was first prominently observed in nickel-cadmium batteries during the 1970s, where capacity reductions were frequently misattributed to a "memory effect" from incomplete discharges, though true fading involved electrode degradation and electrolyte issues. Since the commercialization of lithium-ion batteries in the early 1990s, capacity loss has become a central focus of research, driven by the need to extend cycle life for applications like electric vehicles and portable electronics, with studies emphasizing solid-electrolyte interphase growth as a primary culprit.

Measurement and Quantification

Capacity loss in batteries is primarily assessed through standardized cycling protocols that involve repeated full charge and discharge operations. The most common technique is the constant current (CC) charge-discharge cycling test, where the battery is charged to its full capacity and then discharged at a fixed current rate, such as 1C (equivalent to the current that fully discharges the battery in one hour), while monitoring the delivered discharge capacity over successive cycles. This method allows for direct tracking of capacity fade by comparing the discharge capacity at each cycle against the initial value, providing a reliable baseline for evaluating degradation in lithium-ion and other rechargeable systems. Key metrics derived from these tests quantify the extent of capacity loss in a standardized manner. The capacity retention ratio (CR) is calculated as
CR=QnQ0×100%\text{CR} = \frac{Q_n}{Q_0} \times 100\%
where QnQ_n is the discharge capacity at cycle nn and Q0Q_0 is the initial discharge capacity; this ratio expresses the percentage of original capacity remaining after cycling. Cycle life is typically defined as the number of full cycles until CR drops to 80%, marking a common threshold for end-of-life in practical applications. For lithium-ion batteries, empirical data from early comprehensive reviews indicate typical loss rates of 0.025–0.048% per cycle after 500 cycles, corresponding to overall losses of 12.4–24.1% at that point, with end-of-life often reached at approximately 20% total capacity loss (80% retention). For more nuanced evaluation, advanced techniques like electrochemical impedance spectroscopy (EIS) enable differentiation between reversible and irreversible capacity loss components. EIS applies a small alternating current perturbation across a range of frequencies to measure the battery's impedance spectrum, revealing contributions from processes such as solid electrolyte interphase (SEI) growth (associated with irreversible lithium loss) versus reversible charge transfer or diffusion limitations. This separation aids in isolating permanent degradation from recoverable effects, enhancing predictive models for battery health without relying solely on cycling data.

Mechanisms

Chemical Degradation

Chemical degradation in lithium-ion batteries primarily involves irreversible electrochemical reactions that alter the composition of electrode and electrolyte materials, leading to capacity loss through the consumption of active lithium and impedance buildup. These processes occur at the electrode-electrolyte interfaces, where side reactions form insulating layers or soluble species that disrupt ion transport and active material utilization. These chemical degradation mechanisms are particularly prominent during the charging phase, with primary contributors including solid electrolyte interphase (SEI) layer growth, lithium plating on the anode, loss of active material in the cathode, and electrolyte decomposition. Higher C-rates, typically above 0.5–1C, exacerbate these mechanisms by increasing heat generation and overpotentials, which particularly promote lithium plating and accelerate overall degradation. A key mechanism is the formation of the solid electrolyte interphase (SEI) on the anode surface during initial charging, where reduction of electrolyte solvents and salts consumes lithium ions to create a passivation layer composed of inorganic components like Li2O, LiF, and Li2CO3, alongside organic polymers. This initial SEI growth results in irreversible capacity loss, as the incorporated lithium cannot be reversibly cycled, with typical first-cycle losses ranging from 5-15% in graphite anodes. The SEI continues to grow over cycles due to ongoing solvent diffusion and reduction at the SEI-electrode interface, further depleting active lithium and increasing cell impedance. The thickness growth rate of the SEI follows an Arrhenius dependence on temperature, expressed as: d(SEI)dt∝exp⁡(−EaRT)\frac{d(\text{SEI})}{dt} \propto \exp\left(-\frac{E_a}{RT}\right) where EaE_a is the activation energy (typically 20-50 kJ/mol for SEI reactions), RR is the gas constant, and TT is the temperature in Kelvin; this exponential relationship underscores how elevated temperatures accelerate SEI expansion and associated capacity fade. Electrolyte decomposition arises from oxidative side reactions at the cathode-electrolyte interface, particularly under high-voltage conditions exceeding 4.2 V vs. Li/Li+, where solvents like ethylene carbonate undergo oxidation to produce gases (e.g., CO2, O2) and insoluble polymeric byproducts that deposit on electrode surfaces. These decomposition products increase internal resistance by blocking lithium-ion pathways and can trigger further catalytic reactions, exacerbating capacity loss over extended cycling. In high-voltage lithium-ion batteries, such reactions are intensified, leading to accelerated capacity fade over cycling. Cathode dissolution involves the leaching of transition metal ions from the cathode structure into the electrolyte, driven by chemical disproportionation or acid attack from decomposition products like HF. For instance, in spinel LiMn2O4 cathodes, Mn^{3+} ions disproportionate in the presence of trace water or protons, releasing soluble Mn^{2+} that migrates to the anode, deposits, and catalyzes SEI thickening. This dissolution not only reduces active cathode material but also promotes parasitic reactions, with studies showing Mn leaching that contributes to capacity loss in manganese-based systems. In graphite anodes, lithium plating—though often linked to fast charging—is a primary degradation mechanism during charging, especially at higher C-rates (>0.5–1C), where increased overpotentials and heat lead to metallic lithium deposition on the anode surface instead of intercalation, chemically reacting with the electrolyte to form additional SEI components such as Li2CO3 through reduction of carbonate solvents, further consuming lithium and leading to irreversible capacity loss.

Mechanical Degradation

Mechanical degradation in lithium-ion batteries arises from physical stresses induced by repeated volume changes during charge-discharge cycles, leading to structural damage that reduces the effective active material available for electrochemical reactions. These stresses primarily manifest as cracking, pulverization, and delamination, which isolate portions of the electrode from conductive pathways and contribute to overall capacity loss. Unlike chemical processes, mechanical degradation emphasizes the mechanical integrity of electrode components under cyclic strain. A prominent example occurs in silicon-based anodes, where lithiation and delithiation cause extreme volume expansion of up to 300%, resulting in pulverization of the active material. This expansion generates internal stresses that fracture silicon particles, leading to loss of electrical contact and significant capacity fade, often 20–50% within the first 100 cycles for unmodified silicon anodes. The pulverized fragments become electrically isolated, further exacerbating the degradation over time. In cathode materials such as nickel-manganese-cobalt (NMC) oxides, repeated cycling induces microfractures within particles due to anisotropic volume changes during lithium insertion and extraction. These cracks propagate with each cycle, increasing internal impedance by exposing fresh surfaces to electrolyte and isolating active sites from the current collector. The resulting structural breakdown reduces the cathode's ability to sustain high-capacity operation, with intragranular cracking observed early in cycle life contributing to progressive performance decline. Delamination at the interface between the active electrode layer and the current collector represents another critical mechanical failure mode, particularly under high-rate conditions where accelerated strain amplifies adhesive weaknesses. This detachment reduces the effective electrode area, as portions of the active material lose electrical connectivity to the foil, leading to uneven current distribution and accelerated capacity loss. High C-rates exacerbate this by intensifying mechanical stresses during rapid lithiation. Comparatively, lithium iron phosphate (LFP) cathodes exhibit minimal volume change (approximately 6.5%) during cycling, resulting in substantially lower mechanical degradation than graphite anodes, which experience about 10–12% expansion.

Influencing Factors

Environmental Influences

Temperature plays a critical role in lithium-ion battery capacity loss, with optimal performance occurring around 25°C where degradation rates are minimized. Elevated temperatures above 30°C accelerate chemical reaction kinetics, roughly doubling the capacity fade rate for every 10°C increase due to enhanced electrolyte decomposition and solid electrolyte interphase (SEI) growth. For instance, lithium-ion cells stored at 40°C experience 15-25% capacity loss after one year, compared to approximately 5% at 25°C, highlighting the exponential sensitivity to heat. In electric vehicles, prolonged high temperatures accelerate permanent battery degradation by speeding up chemical reactions such as SEI layer growth, electrolyte breakdown, and calendar aging, leading to faster capacity loss; real-world data from a study of over 10,000 vehicles shows an average degradation of 1.8% per year overall, noticeably faster in hot climates. Early models like the Nissan Leaf with passive cooling suffered significant degradation in hot areas, but modern liquid-cooled EVs fare better. Conversely, sub-zero temperatures below 0°C promote lithium plating on the anode, where metallic lithium deposits instead of intercalating into the graphite, leading to irreversible capacity reduction and potential dendrite formation that risks internal short circuits. Humidity exposure exacerbates capacity loss through water ingress into the battery, particularly in non-hermetic designs, triggering hydrolysis of the electrolyte salt lithium hexafluorophosphate (LiPF₆) to form hydrofluoric acid (HF) via the reaction H₂O + LiPF₆ → POF₃ + 2HF + LiF. This acidic byproduct corrodes electrode materials, dissolves transition metals from the cathode, and thickens the SEI layer, accelerating overall degradation. Pouch cells, with their flexible polymer-aluminum laminate packaging, are especially vulnerable to moisture penetration compared to sealed cylindrical or prismatic cells, which offer better barrier properties against environmental humidity. Atmospheric pressure has minor direct influences on capacity loss under standard conditions, but deviations such as low-pressure environments (e.g., high altitudes) or vacuum storage can alter gas evolution from electrolyte and SEI decomposition, potentially increasing internal pressure buildup or reducing cell efficiency. For example, reducing pressure from 96 kPa to 30 kPa during storage leads to measurable capacity degradation due to enhanced gas release and altered electrochemical dynamics. High-pressure storage, conversely, may suppress gas expansion but offers limited benefits for long-term stability. Long-term calendar aging, or capacity fade during storage without cycling, primarily stems from self-discharge and continuous SEI growth on the anode, driven by residual reactions at the electrode-electrolyte interface. This process consumes cyclable lithium, reducing available capacity over time. A common semi-empirical model for quantifying calendar aging capacity loss QlossQ_{\text{loss}} is given by Qloss=k×t×exp⁡(−EaRT),Q_{\text{loss}} = k \times t \times \exp\left(-\frac{E_a}{RT}\right), where kk is the rate constant, tt is storage time, EaE_a is the activation energy, RR is the gas constant, and TT is the absolute temperature; this Arrhenius-based formulation captures the temperature-dependent acceleration of SEI formation.

Operational Parameters

Operational parameters encompass the controllable usage patterns of lithium-ion batteries, including charge and discharge rates, state of charge (SOC) ranges, cycle depths, and voltage limits, all of which directly modulate the rate of capacity loss during active operation. These factors influence degradation acceleration by altering the stress on electrode materials and electrolytes, with optimized management extending battery lifespan significantly. Unlike environmental conditions, operational parameters allow for proactive adjustments to minimize fade while maintaining performance. Charge and discharge rates, quantified as C-rates (where 1C corresponds to full capacity discharge in one hour), profoundly affect capacity retention. At low C-rates (<0.5C), degradation is predominantly driven by prolonged exposure favoring chemical processes, such as solid electrolyte interphase growth. During charging, primary mechanisms include SEI layer growth, lithium plating on the anode, loss of active material in the cathode, and electrolyte decomposition. Higher C-rates (>0.5–1C) elevate these by increasing heat and overpotentials, promoting plating especially at high rates, and frequent DC fast charging in heat worsens this degradation. In contrast, very high C-rates (>2C) impose additional mechanical stresses, including particle cracking and lithium plating, resulting in accelerated capacity fade. For instance, studies on commercial -ion cells demonstrate that capacity loss is significantly accelerated at 3C compared to 1C due to these intensified stresses. Effective SOC management is crucial for mitigating degradation, as sustained high SOC levels (>80%) promote cathode dissolution and electrolyte oxidation, hastening capacity loss. Operating within a narrower SOC window of 20-80% substantially alleviates these effects, with research indicating that losses in this range can be roughly half those experienced over full 0-100% SOC swings. The depth of SOC variation, or ΔSOC (equivalent to , DOD), further influences long-term performance, particularly in later cycles, where smaller swings reduce cumulative stress on active materials. Cycle depth and frequency also determine degradation trajectories, with shallower cycles preserving capacity better than deep ones. For example, cycling at 50% DOD typically achieves 1200-2000 cycles before significant fade, compared to only about 500 cycles at 100% DOD, as deeper discharges amplify mechanical and chemical wear. Frequent shallow cycling thus favors extended in applications like electric vehicles. Overcharge and over-discharge represent critical voltage abuses that induce immediate capacity loss through irreversible side reactions, such as gas generation and damage. These events can result in 10-20% capacity reduction shortly after occurrence, underscoring the importance of battery management systems to prevent such excursions. High rates during these abuses exacerbate the damage, linking back to mechanical cracking observed in broader degradation studies.

Mitigation Strategies

Material and Design Innovations

Advancements in materials have focused on alternatives to traditional to mitigate expansion and associated capacity fade. Silicon- composites incorporate silicon's high theoretical capacity while blending with to buffer expansion stresses, resulting in extended cycle life. For instance, employing as a buffering in these composites increases battery life by 20%, from 540 to 650 cycles under constant-gap conditions, by maintaining and reducing pressure variations during cycling. metal , offering higher , are protected with coatings such as of Al₂O₃ to suppress dendrite growth and accommodate changes, enhancing cycling stability; thicker coatings (150 cycles of deposition) significantly outperform thinner ones by stabilizing interfaces and reducing capacity loss over repeated cycles. Cathode innovations emphasize doping Ni-rich nickel-manganese-cobalt (NMC) structures to enhance structural integrity against dissolution and phase transitions. Aluminum and magnesium dopants stabilize the layered framework, improving resistance to cracking and dissolution. Mg substitution in LiNi₀.₉Co₀.₀₅Mn₀.₀₅O₂, for example, extends the cycle life to 80% state-of-health retention at approximately 600 cycles for 2 mol% doping, compared to 230 cycles for undoped variants, by suppressing lattice distortions. Similarly, Al doping in Ni-rich reduces polarization and enhances rate capability, leading to superior cyclability over undoped materials through strengthened interatomic bonds. Electrolyte modifications via additives promote a robust solid electrolyte interphase (SEI) to minimize irreversible lithium consumption. (VC) and fluoroethylene carbonate (FEC) preferentially reduce to form stable polymeric components like poly(VC) and LiF, yielding a thinner, less porous SEI that passivates the surface. This reduces initial capacity loss from 10-15% to less than 5% by curbing decomposition and gas during formation . Transitioning to solid-state electrolytes, such as sulfide-based variants (e.g., Li₅.₄PS₄.₄Cl₁.₆), eliminates liquid-phase decomposition entirely, providing high ionic conductivity (up to 20 mS cm⁻¹) and achieving 80% capacity retention after 200 cycles with high active material loadings, while interface engineering further mitigates resistive layers. Cell architecture innovations target reduced internal resistance and mechanical stress to curb degradation pathways. Tabless electrode designs distribute current more uniformly across the surface, lowering impedance and generation that exacerbate fade. In Tesla's 4680 cells, this tabless configuration, combined with dry , enables a 16% increase in and pack-level efficiency, indirectly reducing degradation through minimized thermal and mechanical stresses during operation. In electric vehicles, modern designs incorporate liquid cooling systems to effectively manage high temperatures, mitigating accelerated degradation observed in earlier models like the first-generation Nissan Leaf, which used passive air cooling and suffered significant capacity loss in hot climates (e.g., up to 4.2% annual degradation rate). Real-world data indicates an average EV battery degradation of 1.8% per year overall, with faster rates in hot climates, particularly when combined with frequent DC fast charging; liquid-cooled systems in contemporary EVs, such as Tesla models, fare better by maintaining optimal temperatures and reducing fade. Three-dimensional architectures further alleviate stress by accommodating volume changes, promoting even plating and extending overall cell longevity.

Operational Management Techniques

Operational management techniques for mitigating capacity loss in lithium-ion batteries primarily involve strategies implemented through battery management systems (BMS) to optimize charging, discharging, and environmental conditions during use. These approaches focus on controlling key operational parameters such as (SoC), (DoD), current rates, and temperature to reduce stress-induced degradation mechanisms like solid electrolyte interphase (SEI) growth and lithium plating. By dynamically adjusting these parameters, capacity retention can be improved by 20-80% depending on the application, though trade-offs with energy throughput or charging speed often arise. SoC and DoD management are foundational techniques, as high SoC during storage accelerates calendar aging through increased SEI formation, while deep discharges exacerbate cyclic aging via mechanical stress on electrodes. Storing batteries at low SoC (near 0%) minimizes capacity loss compared to higher levels, with experimental data showing the lowest fade rates at this condition. Cycling around mid-range SoC (45-55%) and limiting the usable capacity to 60-70% of nominal can extend cycle life by reducing voltage extremes that promote side reactions. For instance, restricting SoC to 20-80% in systems has been shown to halve capacity loss over 350 cycles compared to full-range operation. Advanced BMS using can further optimize DoD (e.g., maintaining 35-37% average) under uncertain loads, achieving 5.97% capacity loss after 350 cycles versus 11.51% with traditional . Charging protocols represent another critical area, where constant current-constant voltage (CC-CV) methods are often modified to avoid high currents that induce plating and heat generation. Multi-stage constant current (MSCC) charging, involving stepwise reduction in C-rate (e.g., from 2C to 0.5C across five stages), reduces capacity fade by minimizing polarization and plating risks, improving retention by up to 79.6% over standard CC-CV after extended . Similarly, raising the lower to 3 V upon reaching 85% initial capacity prevents nonlinear degradation by limiting anode potential and electrolyte decomposition, increasing total throughput by 16.7-38.1% across different cell chemistries. Low DoD (e.g., <50%) further slows fade, with models indicating that shallow discharges can extend lifetime by factors of 2-5 relative to full DoD. Low C-rates (≤1C) during both charge and discharge are recommended to suppress SEI growth and particle cracking. Thermal management integrates active or passive cooling to maintain temperatures between 15-35°C, as deviations accelerate electrolyte decomposition and electrode instability. Elevated temperatures (>40°C) can double capacity fade rates, while precise control via cooling or phase-change materials in BMS reduces degradation by 30-50% in high-power applications. In battery systems, aging-aware scheduling incorporates degradation models into optimization algorithms, such as mixed-integer with aging cost penalties, extending operational life from 2.4 to 8.6 years by balancing revenue and fade minimization. These techniques collectively enable proactive capacity preservation without hardware changes, though real-time BMS implementation requires accurate state estimation.

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