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May 14 2025In-depth analysis of the five major failure modes of lithium iron phosphate batteries, including capacity attenuation, internal resistance increase, and thermal runaway, reveals key influencing factors, and provides practical mitigation strategies.
Lithium iron phosphate batteries (LiFePO₄ batteries) have become the mainstream choice for electric vehicles and energy storage systems due to their high safety, long cycle life and environmental friendliness. However, LiFePO₄ batteries still face performance degradation and failure problems in practical applications. Understanding their failure modes and mechanisms is the key to optimizing LiFePO₄ battery design and extending its service life.
1. Five failure modes of lithium iron phosphate batteries
(1) Capacity attenuation
Performance: The available capacity of lithium iron phosphate batteries gradually decreases with the cycle or storage time.
Mechanism:
Degradation of the positive electrode material structure: LiFePO₄ may undergo local phase changes during the cycle (such as Fe³⁰ is reduced to Fe²⁺), resulting in obstruction of the lithium ion diffusion channel; lattice distortion is aggravated at high temperatures, and ionic conductivity is reduced.
Loss of negative electrode active material: The volume expansion of the graphite negative electrode (about 10%) causes particle rupture, and excessive growth of the SEI film consumes active lithium.
Electrolyte decomposition: Under high pressure or high temperature, the electrolyte is oxidized to generate inert substances such as Li₂CO₃, which increases the interface impedance.
(2) Increased internal resistance
Performance: LiFePO4 battery polarization is enhanced, and the charge and discharge efficiency decreases.
Mechanism:
Increased interface impedance: SEI thickens, metal lithium deposits to form a high impedance layer; LiF insulator on the surface of LiFePO₄ hinders charge transfer.
Current collector corrosion: HF in the electrolyte corrodes the aluminum current collector, and the contact resistance increases.
Deterioration of electrode structure: Particle rupture or binder aging destroys the conductive network.
(3) Thermal runaway
Performance: The temperature of the lithium iron phosphate battery rises sharply, causing combustion or explosion.
Mechanism:
Internal short circuit: Dendrite growth pierces the diaphragm, causing a sudden increase in local current.
Thermal decomposition of electrolyte: When the temperature exceeds 120°C, EC/DMC decomposes and produces gas, and the diaphragm melts, exacerbating the short circuit.
Positive oxygen release: LiFePO₄ releases oxygen at extremely high temperatures (>300°C), reacting with the electrolyte to release heat.
(4) End of cycle life
Performance:The capacity of lithium iron phosphate battery decays to less than 80% of the rated value.
Mechanism:
Lithium inventory loss: SEI repair consumes lithium ions, and the irreversible phase change of the positive electrode reduces the lithium embedding sites.
Active material failure: Electrode pulverization or conductive agent failure, the effective reaction area is reduced.
Electrolyte depletion: Side reactions consume electrolyte, and lithium ion transmission medium is insufficient.
(5) Storage aging
Performance: The capacity of lithium iron phosphate batteries decreases irreversibly after long-term storage.
Mechanism:
Self-discharge reaction: Micro-short circuit causes Fe²⁺ to oxidize to Fe³⁺, consuming active lithium.
Continuous growth of SEI: SEI thickens during storage, increasing impedance.
Metal lithium precipitation: High-temperature storage triggers lithium metal deposition, increasing the risk of short circuit.
Performance: The available capacity of lithium iron phosphate batteries gradually decreases with the cycle or storage time.
Mechanism:
Degradation of the positive electrode material structure: LiFePO₄ may undergo local phase changes during the cycle (such as Fe³⁰ is reduced to Fe²⁺), resulting in obstruction of the lithium ion diffusion channel; lattice distortion is aggravated at high temperatures, and ionic conductivity is reduced.
Loss of negative electrode active material: The volume expansion of the graphite negative electrode (about 10%) causes particle rupture, and excessive growth of the SEI film consumes active lithium.
Electrolyte decomposition: Under high pressure or high temperature, the electrolyte is oxidized to generate inert substances such as Li₂CO₃, which increases the interface impedance.
(2) Increased internal resistance
Performance: LiFePO4 battery polarization is enhanced, and the charge and discharge efficiency decreases.
Mechanism:
Increased interface impedance: SEI thickens, metal lithium deposits to form a high impedance layer; LiF insulator on the surface of LiFePO₄ hinders charge transfer.
Current collector corrosion: HF in the electrolyte corrodes the aluminum current collector, and the contact resistance increases.
Deterioration of electrode structure: Particle rupture or binder aging destroys the conductive network.
(3) Thermal runaway
Performance: The temperature of the lithium iron phosphate battery rises sharply, causing combustion or explosion.
Mechanism:
Internal short circuit: Dendrite growth pierces the diaphragm, causing a sudden increase in local current.
Thermal decomposition of electrolyte: When the temperature exceeds 120°C, EC/DMC decomposes and produces gas, and the diaphragm melts, exacerbating the short circuit.
Positive oxygen release: LiFePO₄ releases oxygen at extremely high temperatures (>300°C), reacting with the electrolyte to release heat.
(4) End of cycle life
Performance:The capacity of lithium iron phosphate battery decays to less than 80% of the rated value.
Mechanism:
Lithium inventory loss: SEI repair consumes lithium ions, and the irreversible phase change of the positive electrode reduces the lithium embedding sites.
Active material failure: Electrode pulverization or conductive agent failure, the effective reaction area is reduced.
Electrolyte depletion: Side reactions consume electrolyte, and lithium ion transmission medium is insufficient.
(5) Storage aging
Performance: The capacity of lithium iron phosphate batteries decreases irreversibly after long-term storage.
Mechanism:
Self-discharge reaction: Micro-short circuit causes Fe²⁺ to oxidize to Fe³⁺, consuming active lithium.
Continuous growth of SEI: SEI thickens during storage, increasing impedance.
Metal lithium precipitation: High-temperature storage triggers lithium metal deposition, increasing the risk of short circuit.
2. Key factors affecting the failure of lithium iron phosphate batteries
(1) Temperature: High temperature accelerates side reactions, and low temperature induces dendrite growth.
(2) Charge and discharge rate: High current intensifies polarization, leading to local overheating and stress damage.
(3) Depth of charge and discharge (DOD): Deep cycles (such as 100% DOD) accelerate electrode fatigue.
(4) Voltage window: Overcharge (>3.6V) causes positive electrode oxidation, and overdischarge (<2.0V) causes copper foil corrosion.
(2) Charge and discharge rate: High current intensifies polarization, leading to local overheating and stress damage.
(3) Depth of charge and discharge (DOD): Deep cycles (such as 100% DOD) accelerate electrode fatigue.
(4) Voltage window: Overcharge (>3.6V) causes positive electrode oxidation, and overdischarge (<2.0V) causes copper foil corrosion.
3. Mitigation strategies to extend the life of lithium iron phosphate batteries
(1) Material modification: The carbon coating of the positive electrode improves the conductivity, and the pre-lithiation of the negative electrode compensates for the lithium loss.
(2) Electrolyte optimization: Adding film-forming additives (such as VC) stabilizes SEI and inhibits decomposition.
(3) Thermal management design: The liquid cooling system accurately controls the temperature to avoid extreme temperatures.
(4) BMS strategy: Limit the charge and discharge cut-off voltage to prevent overcharge and overdischarge.
The failure of lithium iron phosphate batteries is the result of the coupling of multiple factors, but through material optimization, process improvement and intelligent management, the reliability and safety of lithium iron phosphate batteries can be further improved, promoting their widespread application in the field of green energy.
(2) Electrolyte optimization: Adding film-forming additives (such as VC) stabilizes SEI and inhibits decomposition.
(3) Thermal management design: The liquid cooling system accurately controls the temperature to avoid extreme temperatures.
(4) BMS strategy: Limit the charge and discharge cut-off voltage to prevent overcharge and overdischarge.
The failure of lithium iron phosphate batteries is the result of the coupling of multiple factors, but through material optimization, process improvement and intelligent management, the reliability and safety of lithium iron phosphate batteries can be further improved, promoting their widespread application in the field of green energy.
