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Lithium hexafluorophosphate

Lithium hexafluorophosphate (Li PF₆) is an inorganic lithium salt consisting of lithium cations and hexafluorophosphate anions, with the chemical formula LiPF₆ and a molecular weight of 151.91 g/mol. It appears as a white to off-white, hygroscopic crystalline powder that is highly sensitive to moisture and heat, readily decomposing in the presence of water to form hydrogen fluoride (HF) and phosphorus oxyfluoride (POF₃). With a density of approximately 1.5 g/cm³ and thermal decomposition occurring around 200 °C, LiPF₆ exhibits good solubility in polar organic solvents such as ethylene carbonate and dimethyl carbonate, but only slight solubility in water due to its reactivity.^[1]^[2]^[3] LiPF₆ is the predominant electrolyte salt in commercial lithium-ion batteries (LIBs), where it dissociates into Li⁺ and PF₆⁻ ions to provide high ionic conductivity—typically enabling conductivities of 5–15 mS/cm in carbonate-based solvents—and electrochemical stability over a wide voltage window of 0–5 V versus Li/Li⁺. This stability arises from the weakly coordinating nature of the PF₆⁻ anion, which minimizes unwanted side reactions at the electrode-electrolyte interface, thereby enhancing battery cycle life and safety. Its CAS number is 21324-40-3, and it is produced industrially via the reaction of lithium fluoride (LiF) with phosphorus pentafluoride (PF₅) in anhydrous conditions.^[4]^[5]^[1] Despite its advantages, LiPF₆ poses handling challenges due to its corrosiveness and toxicity; it is classified as acutely toxic if swallowed or in contact with skin (H301, H311) and causes severe skin burns and eye damage (H314), necessitating inert atmosphere storage and protective equipment during use. Ongoing research explores alternative salts to address LiPF₆'s thermal instability above 60 °C in electrolytes, which can lead to HF generation and capacity fade in LIBs. Nonetheless, its cost-effectiveness and performance have solidified its role in powering consumer electronics, electric vehicles, and grid storage systems worldwide.^[1]^[2]^[3]

Properties

Physical properties

Lithium hexafluorophosphate (LiPF₆) appears as a white, crystalline, hygroscopic powder that readily absorbs moisture from the atmosphere.^[1] The compound has a molecular weight of 151.91 g/mol.^[1] Key physical properties are summarized in the following table:

Property	Value
Density (at 20°C)	1.5 g/cm³
Melting point	200°C (with decomposition)

These properties influence its handling, requiring storage in dry, inert conditions to prevent moisture-induced degradation.^[6] LiPF₆ exhibits high solubility in non-aqueous polar solvents commonly used in electrolyte formulations, such as ethylene carbonate, dimethyl carbonate, and propylene carbonate, achieving concentrations up to 1-2 M, which is typical for lithium-ion battery applications.^[7] In contrast, it is insoluble in water, as contact leads to rapid hydrolysis rather than true dissolution.

Chemical properties

Lithium hexafluorophosphate (LiPF₆) is an ionic compound that readily dissociates into Li⁺ and PF₆⁻ ions when dissolved in polar aprotic solvents such as carbonate esters, facilitating its role as a conducting salt in electrolytes. This dissociation enables high ionic conductivity, with values reaching up to 10.9 mS/cm for 1 M solutions in ethylene carbonate/dimethyl carbonate (1:1 v/v) mixtures at 25°C.^[8]^[9] LiPF₆ exhibits significant sensitivity to hydrolysis in the presence of trace moisture, undergoing reaction to produce hydrogen fluoride (HF) and other byproducts. The primary hydrolysis pathway is given by the equation:

\text{LiPF}_6 + \text{H}_2\text{O} \rightarrow \text{LiF} + \text{POF}_3 + 2\text{HF}

This reaction generates corrosive HF, which can further degrade electrolyte components and electrode materials.^[10] The thermal decomposition of LiPF₆ is autocatalytic and initiates above 60–80°C in electrolyte solutions, often accelerated by impurities or moisture, leading to the formation of lithium fluoride (LiF) and phosphorus pentafluoride (PF₅). In humid conditions, PF₅ reacts further to yield additional HF. Under dry inert atmospheres, pure LiPF₆ remains stable up to approximately 107°C, with complete decomposition occurring around 200°C via the simplified pathway:

\text{LiPF}_6 \rightarrow \text{LiF} + \text{PF}_5

This process contributes to capacity fading in lithium-ion batteries at elevated temperatures.^[11]^[12] LiPF₆ demonstrates favorable redox stability, with an electrochemical window spanning approximately 0–5 V versus Li/Li⁺, making it compatible with common cathode and anode materials in lithium-ion batteries. This stability arises from the inertness of both the Li⁺ cation and the PF₆⁻ anion within typical operating potentials, though decomposition can occur at the anodic limit above 4.7 V.^[13] Spectroscopic characterization confirms the structural integrity of LiPF₆. Infrared (IR) spectroscopy reveals a characteristic P–F stretching band at approximately 840 cm⁻¹ for the PF₆⁻ anion. In nuclear magnetic resonance (NMR) spectra, the ¹⁹F signal appears at around –75 ppm, while the ³¹P resonance is observed near –145 ppm, providing markers for purity assessment and decomposition monitoring.^[14]^[15]

Synthesis

Laboratory methods

Lithium hexafluorophosphate (LiPF₆) is commonly synthesized in laboratory settings via the direct reaction of lithium fluoride (LiF) with phosphorus pentafluoride (PF₅) under strictly anhydrous conditions to prevent hydrolysis.^[16] The reaction proceeds as follows:

\ce{LiF + PF5 -> LiPF6}

This process is typically conducted in an aprotic solvent such as acetonitrile at room temperature (20–30 °C) for 4 hours, yielding a white crystalline product.^[17] PF₅ can be generated separately, for instance, by heating calcium fluoride (CaF₂) with phosphorus pentoxide (P₂O₅) at 280 °C for 3 hours prior to introduction into the reaction mixture.^[18] An alternative laboratory route involves the in situ generation of PF₅ from phosphorus pentachloride (PCl₅) and anhydrous hydrogen fluoride (HF), followed by its reaction with LiF.^[19] The initial step is:

\ce{PCl5 + 5HF -> PF5 + 5HCl}

A mixture of PCl₅ and LiF solids is first cooled, then liquid HF is added to facilitate the chloride-fluoride exchange, producing LiPF₆ along with HCl gas, which must be vented safely.^[20] This method allows for controlled small-scale production without needing pre-isolated PF₅ gas. Following synthesis, the crude LiPF₆ is purified by recrystallization from organic solvents such as acetonitrile or diethyl ether under an inert atmosphere to remove impurities like chlorides or unreacted reagents, achieving purities exceeding 99% and yields typically ranging from 70% to 90%.^[21]^[22] Due to its extreme moisture sensitivity, which leads to decomposition into HF and phosphorus oxyfluorides, all laboratory manipulations are performed in a nitrogen-filled glovebox or using Schlenk line techniques to maintain anhydrous, inert conditions.^[19] Equipment must be HF-resistant, such as Teflon (PTFE) or PFA-lined glassware, to avoid corrosion during reactions involving fluoride sources.^[23]

Industrial production

The primary industrial route for lithium hexafluorophosphate (LiPF₆) production involves a continuous two-step process. First, phosphorus pentafluoride (PF₅) is generated by reacting phosphorus pentachloride (PCl₅) with anhydrous hydrogen fluoride (HF) according to the equation PCl₅ + 5HF → PF₅ + 5HCl. This is followed by the reaction of PF₅ gas with solid lithium fluoride (LiF) in a solvent-free or low-solvent environment to form LiPF₆, as described by PF₅ + LiF → LiPF₆. The overall simplified reaction is PCl₅ + LiF + 5HF → LiPF₆ + 5HCl, with byproducts such as HCl recycled to enhance efficiency and reduce costs. This method is favored for its scalability and ability to achieve high yields in continuous flow reactors.^[16] Alternative industrial methods include generating PF₅ from phosphorus pentoxide (P₂O₅) and calcium fluoride (CaF₂) at elevated temperatures (around 280°C), followed by reaction with LiF to produce LiPF₆. These alternatives are explored to minimize reliance on HF and improve sustainability, but the PF₅-LiF route dominates commercial operations.^[24] Global production capacity for LiPF₆ reached approximately 390,000 tons per year by the end of 2024, with projections for continued growth to meet demand exceeding 249,000 metric tons in 2025, primarily driven by the expansion of electric vehicle (EV) markets. As of November 2025, capacity has further increased with new facilities such as Do-Fluoride New Materials' 100,000 tpa plant and Shilei Fluorine Materials' expansion to 36,000 tpa, alongside emerging chloro-free processes using CaF₂ directly for reduced environmental impact. Key producers include Stella Chemifa and Morita Chemical in Japan, as well as major Chinese firms such as Tinci Materials and Do-Fluoride Chemicals, which account for over 70% of global output. Commercial production of LiPF₆ ramped up in the 1990s alongside Sony's commercialization of lithium-ion batteries in 1991, with significant capacity expansions occurring post-2020 to support surging battery demand.^[25]^[26]^[27]^[28]^[29]^[30]^[31]^[32] Process challenges in industrial production include high energy demands of 5-10 MJ per kg, primarily from HF handling and reaction control, with total energy consumption estimated at around 30 GWh annually for a 10,000-ton facility. HF recycling is critical to lower production costs to approximately $10-20 per kg, while stringent impurity control is required to meet battery-grade purity levels exceeding 99.9%, achieved through crystallization and distillation steps. These engineering aspects ensure reliable supply for high-performance applications.^[16]

Applications

Use in lithium-ion batteries

Lithium hexafluorophosphate (LiPF₆) serves as the primary electrolyte salt in lithium-ion batteries, typically dissolved at concentrations of 1.0-1.2 M in mixtures of cyclic and linear carbonates such as ethylene carbonate (EC) with dimethyl carbonate (DMC) or ethyl methyl carbonate (EMC) in ratios like 1:1:1 by volume.^[33]^[34] These formulations deliver ionic conductivities ranging from 5 to 15 mS/cm at room temperature, facilitating efficient lithium-ion (Li⁺) transport.^[35]^[36] In battery operation, LiPF₆ enables Li⁺ shuttling between the graphite anode and cathodes such as lithium cobalt oxide (LiCoO₂) or nickel-manganese-cobalt oxide (NMC), while its partial decomposition during initial charging forms a protective solid electrolyte interphase (SEI) layer on the anode.^[37]^[38] This SEI passivates the electrode surface, preventing further electrolyte breakdown and enabling reversible lithium intercalation.^[39]^[40] Key advantages of LiPF₆ include its high solubility in carbonate solvents, wide electrochemical stability window (up to ~4.5 V vs. Li/Li⁺), and minimal contribution to electrolyte viscosity, which collectively support high-rate performance and energy densities exceeding 250 Wh/kg in commercial NMC-graphite cells.^[41]^[42]^[43] Despite these benefits, LiPF₆'s thermal instability can contribute to runaway reactions at elevated temperatures, prompting the use of additives like vinylene carbonate (VC) to enhance SEI robustness and mitigate risks.^[44]^[45] VC preferentially reduces to form a more stable SEI, improving cycle life to over 1000 cycles with 80% capacity retention in graphite-based cells.^[46]^[47] Variations in LiPF₆ concentration also influence SEI thickness and composition, with optimal levels balancing conductivity and interphase stability for extended battery longevity.^[39]^[48] As of 2025, LiPF₆ dominates the lithium-ion electrolyte salt market, accounting for over 90% of usage due to its proven performance in commercial applications.^[49] Annual global consumption exceeds 150,000 metric tons, closely tied to the production of over 2 TWh of lithium-ion battery capacity for electric vehicles and energy storage.^[50]^[51]^[52]

Other applications

Lithium hexafluorophosphate (LiPF₆) is incorporated into polymer matrices, such as polyethylene oxide (PEO), to form composite solid-state electrolytes that enable safer and more flexible energy storage systems by replacing flammable liquid components. These PEO/LiPF₆ composites achieve ionic conductivities of approximately $10^{-4} S/cm at room temperature, supporting efficient lithium-ion transport while enhancing mechanical flexibility and thermal stability.^[53] In supercapacitors, LiPF₆ is combined with ionic liquids to facilitate high-voltage operation up to 5 V, extending the operational range beyond traditional aqueous electrolytes. For instance, in electric double-layer capacitors (EDLCs) employing activated carbon electrodes, the inclusion of LiPF₆ in ionic liquids like 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI-BF₄) boosts specific capacitance, rate capability, and cycling stability by promoting better ion adsorption at the electrode interface.^[54] LiPF₆ finds limited application in chemical synthesis due to its high cost, primarily serving as a mild fluorinating agent in select organic reactions and as a precursor for deriving other lithium salts through anion exchange or decomposition pathways.^[55] Emerging research applications of LiPF₆ include its use in electrochemical sensors for monitoring lithium-ion transport and decomposition products, as well as in prototypes of lithium-air batteries where it is dissolved in solvents like dimethoxyethane to enable oxygen reduction and evolution reactions. Recent 2020s studies have further investigated concentrated LiPF₆ solutions, such as in methyl acetate, for dual-ion batteries, demonstrating high-capacity performance with stable graphite intercalation at both electrodes.^[56]^[57]

Safety and environmental impact

Health and safety hazards

Lithium hexafluorophosphate (LiPF₆) poses significant health risks primarily due to its reactivity with moisture, which leads to hydrolysis and the release of hydrogen fluoride (HF), a highly corrosive and toxic substance.^[58] Inhalation of LiPF₆ dust or vapors can cause severe respiratory irritation, coughing, and pulmonary edema, while prolonged or repeated exposure may result in damage to bones and teeth through fluoride accumulation.^[59] Skin contact induces severe burns and tissue necrosis, often exacerbated by HF formation, and eye exposure leads to permanent damage including corneal ulceration.^[58] Although acute oral toxicity is relatively low, with an LD₅₀ greater than 50–300 mg/kg in rats, the compound's irritancy remains a primary concern, classifying it as harmful if swallowed.^[59] LiPF₆ is non-flammable under normal conditions but presents reactivity hazards, particularly in lithium-ion battery applications where it can contribute to thermal runaway.^[58] At temperatures above 150°C, such as during battery overheating, LiPF₆ decomposes to phosphorus pentafluoride (PF₅) and HF, generating flammable and explosive gases that intensify fires and release toxic fumes.^[11] This decomposition can occur via simple dissociation in dry conditions or accelerated hydrolysis in moist environments, underscoring the compound's sensitivity to heat and water.^[60] Safe handling requires stringent precautions to mitigate exposure risks. LiPF₆ must be stored in tightly sealed containers under a dry, inert atmosphere like argon to prevent moisture-induced reactions, and operations should occur in well-ventilated fume hoods or dry rooms.^[61] Appropriate personal protective equipment includes HF-resistant gloves, tightly fitting safety goggles, face shields, and full-body protective clothing; respirators with P3 filters are recommended when dust is generated.^[58] For emergencies, immediate rinsing with water is essential for skin or eye contact, followed by application of calcium gluconate gel or injection to neutralize HF effects, with medical attention mandatory.^[59] Regulatory frameworks classify LiPF₆ as a hazardous substance under the Globally Harmonized System (GHS), with designations for skin corrosion (Category 1A), serious eye damage (Category 1), acute oral toxicity (Category 3), and specific target organ toxicity from repeated inhalation exposure (Category 1).^[58] It is transported as a UN 2923 corrosive solid, toxic n.o.s., under Hazard Class 8 with Subsidiary Hazard 6.1.^[59] The Occupational Safety and Health Administration (OSHA) sets a permissible exposure limit of 3 ppm for HF, the key byproduct, as an 8-hour time-weighted average.^[62] Incidents in battery manufacturing illustrate these hazards, where moisture contamination during production has triggered LiPF₆ hydrolysis, leading to HF gas releases and requiring evacuations or emergency responses.^[63] Such events emphasize the critical need for humidity control below 1% in processing environments to avoid quality defects and safety breaches.^[64]

Environmental considerations

Lithium hexafluorophosphate (LiPF₆) production contributes significantly to greenhouse gas emissions and energy consumption. For an annual output of 10,000 metric tons, the process requires approximately 30 GWh of energy and generates around 80 metric tons of CO₂ equivalent emissions per day, primarily due to raw material extraction and synthesis involving fluorine compounds.^[16] These emissions underscore the need for sustainable manufacturing practices, such as integrating renewable energy sources to mitigate the carbon footprint associated with cathode and electrolyte production.^[65] During use in lithium-ion batteries, LiPF₆ remains stable under normal conditions but decomposes upon exposure to moisture or elevated temperatures, releasing hydrogen fluoride (HF) and phosphoryl fluoride (POF₃). HF is highly corrosive and toxic, posing risks to air and water quality if batteries are damaged or improperly disposed of, while POF₃ can further hydrolyze into additional fluorinated compounds that contaminate ecosystems.^[66] This decomposition is exacerbated in spent batteries, where trace water in electrolytes accelerates the formation of soluble fluorides like LiF, PF₅-derived acids (e.g., HPO₂F₂, H₂PO₃F), and phosphoric acid, which can leach into soil and groundwater.^[67] Environmental toxicity assessments indicate that LiPF₆ and its degradation products exhibit aquatic hazards, with mixtures containing LiPF₆ classified as toxic to aquatic life with long-lasting effects due to bioaccumulation potential of fluorides. Studies on zebrafish embryos have demonstrated developmental toxicity, including apoptosis and morphological abnormalities, at concentrations as low as 10 µM (≈1.5 mg/L), highlighting risks to aquatic organisms from battery waste leachates.^[68] Fluoride ions from decomposed LiPF₆ persist in soil, potentially disrupting microbial communities and plant growth, while airborne HF emissions contribute to atmospheric acidification.^[67] Safety data sheets confirm that while pure LiPF₆ is not classified as persistent, bioaccumulative, or toxic (PBT), its hydrolysis products warrant precautions to prevent environmental release.^[61] Recycling challenges amplify these impacts, as low recovery rates globally lead to landfilling of spent electrolytes, resulting in fluoride diffusion into air and soil. Advanced methods, such as pyrolysis, can recover over 99% of organic solvents and reduce residual fluoride to 0.067%, but scalability remains limited by the volatility and corrosivity of LiPF₆.^[67] In the European Union, the Battery Regulation (2023/1542), effective from 2025, mandates recycling efficiency targets of 70% for lithium-based batteries by 2030 and material recovery requirements, aiming to improve electrolyte management and reduce ecological damage from the growing volume of lithium-ion battery waste.^[69] Improved waste management and fluorine-free electrolyte alternatives are essential to minimize long-term ecological damage.^[70]

References

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[PDF] SAFETY DATA SHEET - Fisher Scientific
Aug 6, 2007 · Corrosive solid, toxic, n.o.s.. Technical Name. Phosphate(1-), hexafluoro-, lithium. Hazard Class. 8. Subsidiary Hazard Class. 6.1.
[57]
LiPF6 Studied With the New TA Instruments TGA Smart-Seal Pan
Under dry conditions, the neat salt decomposes in a single step to lithium fluoride (LiF) and phosphorous pentafluoride (PF5) between 150 – 250 °C. Under wet ...
[58]
[PDF] Material Safety Data Sheet - LTS Research Laboratories
Jun 30, 2015 · Melting Point: 200 °C. Flash Point: N/A. Autoignition Temperature: N/A ... Corrosive solids, toxic, n.o.s. (Lithium hexafluorophosphate).
[59]
https://www.fishersci.com/store/msds?partNumber=AC191260250&countryCode=US&language=en
[60]
[PDF] "Lithium-Ion Batteries Hazard and Use Assessment Final Report."
The most commonly used electrolyte salt (LiPF6) will decompose to form hydrofluoric acid (HF) if mixed with water or exposed to moisture. Cell production and ...
[61]
Lithium-Ion Battery Electrolyte Handling Procedures - Atomfair
Humidity must be kept below 1% to prevent hydrolysis of lithium salts, which is why dry rooms or glove boxes with inert atmospheres (argon or nitrogen) are ...
[62]
Environmental aspects of batteries - ScienceDirect.com
There are safety concerns however when it comes to lithium primary batteries such as the risk of lithium metal contact with water due to leakages, which can ...Missing: contamination | Show results with:contamination
[63]
Elementary Decomposition Mechanisms of Lithium ...
Dec 5, 2022 · In this work, we use density functional theory to explain the decomposition of lithium hexafluorophosphate (LiPF 6 ) salt under SEI formation conditions.
[64]
Recycling of electrolyte from spent lithium-ion batteries - ScienceDirect
LiPF6 is converted into high-value lithium fluoride or lithium carbonate by chemical reaction. The recovery yield of the solvent is 90%. Zeng et al. mixed the ...
[65]
Developmental Toxicity and Apoptosis in Zebrafish: The Impact of ...
Aug 28, 2024 · These findings underscore the environmental and health risks of LiPF6 exposure and highlight the necessity for improved waste management ...
[66]
PFAS-Free Energy Storage: Investigating Alternatives for Lithium-Ion ...
Dec 4, 2024 · Issues like potential toxicity, corrosivity and environmental concerns have sparked interest in fluorine-free alternatives. Of course, these ...