lithium-ion cell before closing Generally, the negative electrode of a conventional lithium-ion cell is made from
graphite. The positive electrode is typically a metal
oxide or phosphate. The
electrolyte is a
lithium salt in an
organic solvent. The negative electrode (which is the
anode when the cell is discharging) and the positive electrode (which is the
cathode when discharging) are prevented from shorting by a separator. The electrodes are connected to the powered circuit through two pieces of metal called current collectors. The positive electrode is generally one of three materials: a layered
oxide (such as
lithium cobalt oxide), a
polyanion (such as
lithium iron phosphate) or a
spinel (such as lithium
manganese oxide). More experimental materials include
graphene-containing electrodes, although these remain far from commercially viable due to their high cost. Lithium reacts vigorously with water to form
lithium hydroxide (LiOH) and
hydrogen gas. Thus, a non-aqueous electrolyte is typically used, and a sealed container rigidly excludes moisture from the battery pack. The non-aqueous electrolyte is typically a mixture of organic carbonates such as
ethylene carbonate and
propylene carbonate containing
complexes of lithium ions.
Ethylene carbonate is essential for making solid electrolyte interphase on the carbon anode, but since it is solid at room temperature, a liquid
solvent (such as
propylene carbonate or
diethyl carbonate) is added. The electrolyte salt is almost always
lithium hexafluorophosphate (), which combines good
ionic conductivity with chemical and electrochemical stability. The
hexafluorophosphate anion is essential for
passivating the aluminium current collector used for the positive electrode. A titanium tab is ultrasonically
welded to the aluminium current collector. Other salts like
lithium perchlorate (),
lithium tetrafluoroborate (), and
lithium bis(trifluoromethanesulfonyl)imide () are frequently used in research in tab-less
coin cells, but are not usable in larger format cells, often because they are not compatible with the aluminium current collector. Copper (with a
spot-welded nickel tab) is used as the current collector at the negative electrode. Current collector design and surface treatments may take various forms: foil, mesh, foam (dealloyed), etched (wholly or selectively), and coated (with various materials) to improve electrical characteristics. Depending on materials choices, the
voltage,
energy density, life, and safety of a lithium-ion cell can change dramatically. Current effort has been exploring the use of
novel architectures using
nanotechnology to improve performance. Areas of interest include nano-scale electrode materials and alternative electrode structures.
Electrochemistry The reactants in the electrochemical reactions in a lithium-ion cell are the materials of the electrodes, both of which are compounds containing lithium atoms. Although many thousands of different materials have been investigated for use in lithium-ion batteries, only a very small number are commercially usable. All commercial Li-ion cells use intercalation compounds as active materials. The negative electrode is usually graphite, although
silicon is often mixed in to increase the capacity. The electrolyte is usually
lithium hexafluorophosphate, dissolved in a mixture of
organic carbonates. A number of different materials are used for the positive electrode, such as
LiCoO2,
LiFePO4, and
lithium nickel manganese cobalt oxides. During cell discharge the negative electrode is the anode and the positive electrode the cathode: electrons flow from the anode to the cathode through the external circuit. An oxidation
half-reaction at the anode produces positively charged lithium ions and negatively charged electrons. The oxidation half-reaction may also produce uncharged material that remains at the anode. Lithium ions move through the electrolyte; electrons move through the external circuit toward the cathode where they recombine with the cathode material in a reduction half-reaction. The electrolyte provides a conductive medium for lithium ions but does not partake in the electrochemical reaction. The reactions during discharge lower the
chemical potential of the cell, so discharging transfers
energy from the cell to wherever the electric current dissipates its energy, mostly in the external circuit. During charging these reactions and transports go in the opposite direction: electrons move from the positive electrode to the negative electrode through the external circuit. To charge the cell the external circuit has to provide electrical energy. This energy is then stored as chemical energy in the cell (with some loss, e. g., due to
coulombic efficiency lower than 1). Both electrodes allow lithium ions to move in and out of their structures with a process called
insertion (
intercalation) or
extraction (
deintercalation), respectively. As the lithium ions "rock" back and forth between the two electrodes, these batteries are also known as "rocking-chair batteries" or "swing batteries" (a term given by some European industries). The following equations exemplify the chemistry (left to right: discharging, right to left: charging). The negative electrode half-reaction for the graphite is : LiC6 C6 + Li+ + e^- The positive electrode half-reaction in the lithium-doped cobalt oxide substrate is : CoO2 + Li+ + e- LiCoO2 The full reaction being : LiC6 + CoO2 C6 + LiCoO2 The overall reaction has its limits. Overdischarging supersaturates
lithium cobalt oxide, leading to the production of
lithium oxide, possibly by the following irreversible reaction: : Li+ + e^- + LiCoO2 -> Li2O + CoO
Overcharging up to 5.2
volts leads to the synthesis of cobalt (IV) oxide, as evidenced by
x-ray diffraction: : LiCoO2 -> Li+ + CoO2 + e^- The cell's energy is equal to the voltage times the charge. Each gram of lithium represents
Faraday's constant/6.941, or 13,901 coulombs. At 3 V, this gives 41.7 kJ per gram of lithium, or 11.6 kWh per kilogram of lithium. This is slightly more than the
heat of combustion of
gasoline; however, lithium-ion batteries as a whole are still significantly heavier per unit of energy due to the additional materials used in production. Note that the cell voltages involved in these reactions are larger than the potential at which an
aqueous solutions would
electrolyze.
Discharging and charging During discharge, lithium ions () carry the
current within the battery cell from the negative to the positive electrode, through the non-
aqueous electrolyte and separator diaphragm. During charging, an external electrical power source applies an over-voltage (a voltage greater than the cell's own voltage) to the cell, forcing electrons to flow from the positive to the negative electrode. The lithium ions also migrate (through the electrolyte) from the positive to the negative electrode where they become embedded in the porous electrode material in a process known as intercalation. Energy losses arising from electrical
contact resistance at interfaces between
electrode layers and at contacts with current collectors can be as high as 20% of the entire energy flow of batteries under typical operating conditions. The charging procedures for single Li-ion cells, and complete Li-ion batteries, are slightly different: • A single Li-ion cell is charged in two stages: •
Constant current (CC) •
Constant voltage (CV) • A Li-ion battery (a set of Li-ion cells in series) is charged in three stages: •
Constant current • Balance (only required when cell groups become unbalanced during use) •
Constant voltage During the
constant current phase, the charger applies a constant current to the battery at a steadily increasing voltage, until the top-of-charge voltage limit per cell is reached. During the
balance phase, the charger/battery reduces the charging current (or cycles the charging on and off to reduce the average current) while the
state of charge of individual cells is brought to the same level by a balancing circuit until the battery is balanced. Balancing typically occurs whenever one or more cells reach their top-of-charge voltage before the other(s), as it is generally inaccurate to do so at other stages of the charge cycle. This is most commonly done by passive balancing, which
dissipates excess charge as heat via
resistors connected momentarily across the cells to be balanced. Active balancing is less common, more expensive, but more efficient, returning excess energy to other cells (or the entire pack) via a
DC-DC converter or other circuitry. Balancing most often occurs during the constant voltage stage of charging, switching between charge modes until complete. The pack is usually fully charged only when balancing is complete, as even a single cell group lower in charge than the rest will limit the entire battery's usable capacity to that of its own. Balancing can last hours or even days, depending on the magnitude of the imbalance in the battery. During the
constant voltage phase, the charger applies a voltage equal to the maximum cell voltage times the number of cells in series to the battery, as the current gradually declines towards 0, until the current is below a set threshold of about 3% of initial constant charge current. Periodic topping charge about once per 500 hours. Top charging is recommended to be initiated when voltage goes below Failure to follow current and voltage limitations can result in excessive coulombic heating of the battery, and in the case of overcharge to voltages higher than designed can lead to an explosion. Charging temperature limits for Li-ion are stricter than the operating limits. Lithium-ion chemistry performs well at elevated temperatures but prolonged exposure to heat reduces battery life. Li‑ion batteries offer good charging performance at cooler temperatures and may even allow "fast-charging" within a temperature range of . Charging should be performed within this temperature range. At temperatures from 0 to 5 °C charging is possible, but the charge current should be reduced. During a low-temperature (under 0 °C) charge, the slight temperature rise above ambient due to the internal cell resistance is beneficial. High temperatures during charging may lead to battery degradation and charging at temperatures above 45 °C will degrade battery performance, whereas at lower temperatures the internal resistance of the battery may increase, resulting in slower charging and thus longer charging times. The rate increases with temperature and state of charge. A 2004 study found that for most cycling conditions self-discharge was primarily time-dependent; however, after several months of stand on open circuit or float charge, state-of-charge dependent losses became significant. The self-discharge rate did not increase monotonically with state-of-charge, but dropped somewhat at intermediate states of charge. Self-discharge rates may increase as batteries age. In 1999, self-discharge per month was measured at 8% at 21 °C, 15% at 40 °C, 31% at 60 °C. By 2007, monthly self-discharge rate was estimated at 2% to 3%, and 2–3% by 2016. By comparison, the self-discharge rate for
NiMH batteries dropped, as of 2017, from up to 30% per month for previously common cells to about 0.08–0.33% per month for
low self-discharge NiMH batteries, and is about 10% per month in
NiCd batteries.
Cathode Transition metal oxides (TMOs) are widely used as cathode materials in lithium-ion batteries as the variable oxidation state of transition metal cations allows oxides of these metals to reversibly host lithium ions (Li⁺) and undergo efficient redox (reduction-oxidation) reactions. While Oxygen ions are commonly assumed to remain in a 2- oxidation state, the role of oxygen redox in facilitating the lithium insertion is now recognized as instrumental in the performance of lithium ion battery cathodes. The layered or framework structures of TMOs allow Li⁺ insertion/extraction during charging/discharging, while their transition metals and oxygen anions participate in electron transfer, enabling high energy density and stability. Three classes of cathode materials in lithium-ion batteries have been commercialized: (1) layered oxides, (2) spinel oxides and (3) oxoanion complexes. All of them were discovered by John Goodenough and his collaborators. Several other first-row (3d)
transition metals also form layered LiMO2 salts. Some can be directly prepared from
lithium oxide and M2O3 (e.g. for M=Ti, V, Cr, Co, Ni), while others (M= Mn or Fe) can be prepared by
ion exchange from NaMO2. LiVO2, LiMnO2 and LiFeO2 suffer from structural instabilities (including mixing between M and Li sites) due to a low energy difference between octahedral and tetrahedral environments for the metal ion M. For this reason, they are not used in lithium-ion batteries. Similarly, LiCrO2 shows reversible lithium (de)intercalation around 3.2 V with 170–270 mAh/g. However, its
cycle life is short, because of
disproportionation of Cr4+ followed by translocation of Cr6+ into tetrahedral sites. On the other hand, NaCrO2 shows a much better cycling stability. LiTiO2 shows Li+ (de)intercalation at a voltage of ~1.5 V, which is too low for a cathode material. These problems leave and as the only practical layered oxide materials for lithium-ion battery cathodes. The cobalt-based cathodes show high theoretical specific (per-mass) charge capacity, high volumetric capacity, low self-discharge, high discharge voltage, and good cycling performance. Unfortunately, they suffer from a high cost of the material. For this reason, the current trend among lithium-ion battery manufacturers is to switch to cathodes with higher Ni content and lower Co content. In addition to a lower (than cobalt) cost, nickel-oxide based materials benefit from the two-electron redox chemistry of Ni: in layered oxides comprising nickel (such as nickel-cobalt-manganese
NCM and nickel-cobalt-aluminium oxides
NCA), Ni cycles between the oxidation states +2 and +4 (in one step between +3.5 and +4.3 V), remain in +4 and 3+, respectively. Thus increasing the Ni content increases the cyclable charge. For example, NCM111 shows 160 mAh/g, while (NCM811) and (NCA) deliver a higher capacity of ~200 mAh/g. NCM and NCA batteries are collectively called ternary lithium batteries. It is worth mentioning so-called "lithium-rich" cathodes that can be produced from traditional NCM (, where M=Ni, Co, Mn) layered cathode materials upon cycling them to voltages/charges corresponding to Li:M2O4 adopts a cubic lattice, which allows for three-dimensional lithium-ion diffusion. Manganese cathodes are attractive because manganese is less expensive than cobalt or nickel. The operating voltage of Li-LiMn2O4 battery is 4 V, and ca. one lithium per two Mn ions can be reversibly extracted from the tetrahedral sites, resulting in a practical capacity of 3+ is not a stable oxidation state, as it tends to
disproportionate into insoluble Mn4+ and soluble Mn2+. LiMn2O4 can also intercalate more than 0.5 Li per Mn at a lower voltage around +3.0 V. However, this results in an irreversible
phase transition due to
Jahn-Teller distortion in Mn3+:t2g3eg1, as well as
disproportionation and dissolution of Mn3+. An important improvement of Mn spinel are related cubic structures of the LiMn1.5Ni0.5O4 type, where Mn exists as Mn4+ and Ni cycles reversibly between the
oxidation states +2 and +4.
Oxoanionic Around 1980
Manthiram discovered that
oxoanions (
molybdates and
tungstates in that particular case) cause a substantial positive shift in the redox potential of the metal-ion compared to oxides. In addition, these oxoanionic cathode materials offer better stability/safety than the corresponding oxides. However, they also suffer from poor electronic conductivity due to the long distance between redox-active metal centers, which slows down the electron transport. This necessitates the use of small (less than 200 nm) cathode particles and coating each particle with a layer of electronically-
conducting carbon. This reduces the
packing density of these materials. Although numerous combinations of oxoanions (
sulfate,
phosphate,
silicate) with various metals (mostly Mn, Fe, Co, Ni) have been studied,
LiFePO4 is the only one that has been commercialized. Although it was originally used primarily for
stationary energy storage due to its lower energy density compared to layered oxides, it has begun to be widely used in electric vehicles since the 2020s.
Anode Negative electrode materials are traditionally constructed from graphite and other carbon materials, although newer silicon-based materials are being increasingly used (see
Nanowire battery). In 2016, 89% of lithium-ion batteries contained graphite (43% artificial and 46% natural), 7% contained amorphous carbon (either soft carbon or
hard carbon), 2% contained lithium titanate (LTO) and 2% contained silicon or tin-based materials. These materials are used because they are abundant, electrically conducting and can intercalate lithium ions to store electrical charge with modest volume expansion (~10%). Graphite is the dominant material because of its low intercalation voltage and excellent performance. Various alternative materials with higher capacities have been proposed, but they usually have higher voltages, which reduces energy density. Low voltage is the key requirement for anodes; otherwise, the excess capacity is useless in terms of energy density. As graphite is limited to a maximum capacity of 372 mAh/g summarizes early research on silicon-based anodes for lithium-ion secondary cells. In particular, Hong Li et al. showed in 2000 that the electrochemical insertion of lithium ions in silicon
nanoparticles and silicon nanowires leads to the formation of an amorphous Li–Si alloy. The same year, Bo Gao and his doctoral advisor, Professor Otto Zhou described the cycling of electrochemical cells with anodes comprising silicon nanowires, with a reversible capacity ranging from at least approximately 900 to 1500 mAh/g. Diamond-like carbon coatings can increase retention capacity by 40% and cycle life by 400% for lithium based batteries. To improve the stability of the lithium anode, several approaches to installing a protective layer have been suggested. Silicon is beginning to be looked at as an anode material because it can accommodate significantly more lithium ions, storing up to 10 times the electric charge, however this alloying between lithium and silicon results in significant volume expansion (ca. 400%), Silicon has been used as an anode material but the insertion and extraction of \scriptstyle Li+ can create cracks in the material. These cracks expose the Si surface to an electrolyte, causing decomposition and the formation of a solid electrolyte interphase (SEI) on the new Si surface (crumpled graphene encapsulated Si nanoparticles). This SEI will continue to grow thicker, deplete the available \scriptstyle Li+, and degrade the capacity and cycling stability of the anode. In addition to carbon- and silicon- based anode materials for lithium-ion batteries, high-entropy metal oxide materials are being developed. These conversion (rather than intercalation) materials comprise an alloy (or subnanometer mixed phases) of several metal oxides performing different functions. For example, Zn and Co can act as electroactive charge-storing species, Cu can provide an electronically conducting support phase and MgO can prevent pulverization.
Electrolyte Liquid electrolytes in lithium-ion batteries consist of lithium
salts, such as lithium hexafluorophosphate|, lithium tetrafluoroborate|, LiFSI, LiTFSI or lithium perchlorate| in an
organic solvent, such as
ethylene carbonate,
dimethyl carbonate, and
diethyl carbonate. A liquid electrolyte acts as a conductive pathway for the movement of cations passing from the negative to the positive electrodes during discharge. Typical conductivities of liquid electrolyte at room temperature () are in the range of 10
mS/cm, increasing by approximately 30–40% at and decreasing slightly at . The combination of linear and cyclic carbonates (e.g.,
ethylene carbonate (EC) and
dimethyl carbonate (DMC)) offers high conductivity and
solid electrolyte interphase (SEI)-forming ability. While EC forms a stable SEI, it is not a liquid at room temperature, only becoming a liquid with the addition of additives such as the previously mentioned DMC or
diethyl carbonate (DEC) or
ethyl methyl carbonate (EMC). Organic solvents easily decompose on the negative electrodes during charge. When appropriate
organic solvents are used as the electrolyte, the solvent decomposes on initial charging and forms a solid layer called the solid electrolyte interphase, which is electrically insulating, yet provides significant ionic conductivity, behaving as a solid electrolyte. The interphase prevents further decomposition of the electrolyte after the second charge as it grows thick enough to prevent electron tunneling after the first charge cycle. For example,
ethylene carbonate is decomposed at a relatively high voltage, 0.7 V vs. lithium, and forms a dense and stable interface. Composite electrolytes based on POE (poly(oxyethylene)) provide a relatively stable interface. It can be either solid (high molecular weight) and be applied in dry Li-polymer cells, or liquid (low molecular weight) and be applied in regular Li-ion cells.
Room-temperature ionic liquids (RTILs) are another approach to limiting the flammability and volatility of organic electrolytes.
Solid electrolyte interphase (SEI) The term solid electrolyte interphase was first coined by Peled in 1979 to describe the layer of insoluble products deposited on alkali and alkaline earth cathodes in non-aqueous batteries (NAB). However, Dey and Sullivan had noted previously in 1970 that graphite, in a lithium metal half cell using
propylene carbonate (PC), reduced the electrolyte during discharge at a rate which linearly increased with the current. They proposed that the following reaction was taking place: :C4H6O3 + 2e- -> CH3-CH=CH2 + CO3^{2-} The same reaction was later proposed by Fong et al in 1990, where they theorized that the carbonate ion was reacting with the lithium to form
lithium carbonate, which was then forming a passivating layer on the surface of the graphite. PC is not commonly used in batteries today as the molecules can intercalate into the graphite layers and react with the lithium there to form propylene and acts to delaminate the graphite. The insulating properties of the SEI allow the battery to reach more extreme voltage gaps without simply reducing the electrolyte. This ability of the SEI to improve the voltage window of batteries was discovered almost by accident but plays a vital role in high voltage batteries today.
Solid electrolytes Recent advances in battery technology involve using a solid as the electrolyte material. The most promising of these are ceramics. Solid ceramic electrolytes are mostly lithium metal
oxides, which allow lithium-ion transport through the solid more readily due to the intrinsic lithium. The main benefit of solid electrolytes is that there is no risk of
leaks, which is a serious safety issue for batteries with liquid electrolytes. Solid ceramic electrolytes can be further broken down into two main categories: ceramic and glassy.
Ceramic solid electrolytes are highly ordered compounds with
crystal structures that usually have ion transport channels. Common ceramic electrolytes are lithium
super ion conductors (LISICON) and
perovskites.
Glassy solid electrolytes are
amorphous atomic structures made up of similar elements to ceramic solid electrolytes but have higher
conductivities overall due to higher conductivity at grain boundaries. Both glassy and ceramic electrolytes can be made more ionically conductive by substituting sulfur for oxygen. The larger radius of sulfur and its higher ability to be
polarized allow higher conductivity of lithium. This contributes to conductivities of solid electrolytes are nearing parity with their liquid counterparts, with most on the order of 0.1 mS/cm and the best at 10 mS/cm. An efficient and economic way to tune targeted electrolytes properties is by adding a third component in small concentrations, known as an additive. By adding the additive in small amounts, the bulk properties of the electrolyte system will not be affected whilst the targeted property can be significantly improved. The numerous additives that have been tested can be divided into the following three distinct categories: (1) those used for SEI chemistry modifications; (2) those used for enhancing the ion conduction properties; (3) those used for improving the safety of the cell (e.g. prevent overcharging). Electrolyte alternatives have also played a significant role, for example the
lithium polymer battery. Polymer electrolytes are promising for minimizing the dendrite formation of lithium. Polymers are supposed to prevent short circuits and maintain conductivity.
Dry-processed electrode manufacturing Dry electrode manufacturing is a solvent-free electrode preparation process that serves as an alternative to the traditional slurry coating method for lithium-ion batteries. Unlike conventional methods requiring liquid solvents such as N-methylpyrrolidone (NMP) to mix active materials, dry electrode technology relies on mechanical mixing, dry coating, and compaction to form a dense electrode structure.
Process The typical preparation of dry electrodes involves three steps: Dry mixing: Active materials, conductive agents, and binders are uniformly blended under solvent-free conditions. Dry coating: The powder mixture is evenly coated onto the current collector surface under shear force. Compression/Calendering: The coated layer is compressed to achieve the target thickness and sufficient mechanical strength.
Advantages The dry electrode process eliminates the need for drying equipment, NMP recovery systems, or procedures for handling thick slurries since it operates entirely without solvents. Its advantages include: significantly reduced energy consumption and manufacturing costs, elimination of the toxic solvent NMP, enhanced environmental sustainability, and the ability to produce thicker electrodes with higher loading capacities.
PTFE fiberization binder Dry electrodes typically utilize polytetrafluoroethylene (PTFE) as a binder. Under shear stress, PTFE forms a network of elongated fibers that permeates the entire electrode structure. This PTFE fiber network provides the electrode with exceptional mechanical strength, flexibility, and particle adhesion, thereby compensating for structural deficiencies in the absence of slurry mixing.
Biomass additives Recent studies have introduced biomass additives such as starch, cellulose, and flour to enhance the pore structure and flexibility of electrodes. These additives promote intermolecular crosslinking, reduce tortuosity, and improve electrolyte wettability. For instance, incorporating 1 wt.% flour into PTFE dry electrodes significantly increases mechanical strength, accelerates lithium-ion transport, and enhances high-rate performance. First, high-thickness electrodes may exhibit localized density variations during pressing, leading to reduced cycle life or unstable electrochemical performance. Second, PTFE binders carry higher costs, and while biomass additives help improve pore structure, their ratios require optimization to balance performance and processing stability. Furthermore, scaling up laboratory-scale preparation methods to industrial production necessitates addressing issues such as coating uniformity, consistent pressing, and quality control. Future development directions include: researching low-cost or biodegradable binder alternatives; developing thick electrode designs that balance high energy density with mechanical stability; introducing automated quality monitoring technologies to support mass production; and utilizing advanced characterization methods to optimize pore structure and ion transport properties. These improvements are expected to drive the widespread adoption of dry-process electrode technology in commercial lithium-ion batteries. == Battery designs and formats ==