Lithium-ion battery
cycles
V |
A lithium-ion or Li-ion battery is a type of
There are at least 12 different chemistries of Li-ion batteries, see List of battery types
The invention and commercialization of Li-ion batteries may have had one of the greatest impacts of all technologies in human history,[10] as recognized by the 2019 Nobel Prize in Chemistry. More specifically, Li-ion batteries enabled portable
Lithium-ion cells can be manufactured to optimize energy or power density.
Lithium-ion batteries can be a safety hazard if not properly engineered and manufactured because they have flammable electrolytes that, if damaged or incorrectly charged, can lead to explosions and fires. Much progress has been made in the development and manufacturing of safe lithium-ion batteries.
Research areas for lithium-ion batteries include extending lifetime, increasing energy density, improving safety, reducing cost, and increasing charging speed,[20][21] among others. Research has been under way in the area of non-flammable electrolytes as a pathway to increased safety based on the flammability and volatility of the organic solvents used in the typical electrolyte. Strategies include aqueous lithium-ion batteries, ceramic solid electrolytes, polymer electrolytes, ionic liquids, and heavily fluorinated systems.[22][23][24][25]
History
Research on rechargeable Li-ion batteries dates to the 1960s; one of the earliest examples is a CuF
2/Li battery developed by
2 is sensitive to moisture and releases toxic H
2S gas on contact with water. More prohibitively, the batteries were also prone to spontaneously catch fire due to the presence of metallic lithium in the cells. For this, and other reasons, Exxon discontinued the development of Whittingham's lithium-titanium disulfide battery.[26]
In 1980, working in separate groups Ned A. Godshall et al.,[27][28][29] and, shortly thereafter, Koichi Mizushima and John B. Goodenough, after testing a range of alternative materials, replaced TiS
2 with lithium cobalt oxide (LiCoO
2, or LCO), which has a similar layered structure but offers a higher voltage and is much more stable in air. This material would later be used in the first commercial Li-ion battery, although it did not, on its own, resolve the persistent issue of flammability.[26]
These early attempts to develop rechargeable Li-ion batteries used lithium metal anodes, which were ultimately abandoned due to safety concerns, as lithium metal is unstable and prone to
In 1985, Akira Yoshino at Asahi Kasei Corporation discovered that petroleum coke, a less graphitized form of carbon, can reversibly intercalate Li-ions at a low potential of ~0.5 V relative to Li+ /Li without structural degradation.[34] Its structural stability originates from the amorphous carbon regions in petroleum coke serving as covalent joints to pin the layers together. Although the amorphous nature of petroleum coke limits capacity compared to graphite (~Li0.5C6, 0.186 Ah g–1), it became the first commercial intercalation anode for Li-ion batteries owing to its cycling stability.
in 1987,
Significant improvements in energy density were achieved in the 1990s by replacing the soft carbon anode first with hard carbon and later with graphite. In 1990, Jeff Dahn and two colleagues at Dalhousie University (Canada) reported reversible intercalation of lithium ions into graphite in the presence of ethylene carbonate solvent (which is solid at room temperature and is mixed with other solvents to make a liquid), thus finding the final piece of the puzzle leading to the modern lithium-ion battery.[35]
In 2010, global lithium-ion battery production capacity was 20 gigawatt-hours.[36] By 2016, it was 28 GWh, with 16.4 GWh in China.[37] Global production capacity was 767 GWh in 2020, with China accounting for 75%.[38] Production in 2021 is estimated by various sources to be between 200 and 600 GWh, and predictions for 2023 range from 400 to 1,100 GWh.[39]
In 2012, John B. Goodenough, Rachid Yazami and Akira Yoshino received the 2012 IEEE Medal for Environmental and Safety Technologies for developing the lithium-ion battery; Goodenough, Whittingham, and Yoshino were awarded the 2019 Nobel Prize in Chemistry "for the development of lithium-ion batteries".[40] Jeff Dahn received the ECS Battery Division Technology Award (2011) and the Yeager award from the International Battery Materials Association (2016).
In April 2023,
Design
Generally, the negative electrode of a conventional lithium-ion cell is graphite made from carbon. The positive electrode is typically a metal oxide or phosphate. The electrolyte is a lithium salt in an organic solvent.[45] 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.[46] The electrodes are separated from external electronics with a piece of metal called a current collector.[47]
The negative and positive electrodes swap their electrochemical roles (anode and cathode) when the cell is charged. Despite this, in discussions of battery design the negative electrode of a rechargeable cell is often just called "the anode" and the positive electrode "the cathode".
In its fully lithiated state of LiC6, graphite correlates to a theoretical capacity of 1339 coulombs per gram (372 mAh/g).[48] 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).[49] More experimental materials include graphene-containing electrodes, although these remain far from commercially viable due to their high cost.[50]
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.[51] Ethylene carbonate is essential for making solid electrolyte interphase on the carbon anode,[52] 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[
4), lithium tetrafluoroborate (LiBF
4), and lithium bis(trifluoromethanesulfonyl)imide (LiC
2F
6NO
4S
2) are frequently used in research in tab-less coin cells, but are not usable in larger format cells,[53] often because they are not compatible with the aluminum 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.[47]
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.[54]
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
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
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).[56][57]
The following equations exemplify the chemistry (left to right: discharging, right to left: charging).
The negative electrode half-reaction for the graphite is[58][59]
The positive electrode half-reaction in the lithium-doped cobalt oxide substrate is
The full reaction being
The overall reaction has its limits. Overdischarging supersaturates lithium cobalt oxide, leading to the production of lithium oxide,[60] possibly by the following irreversible reaction:
The transition metal in the positive electrode, cobalt (Co), is reduced from Co4+
to Co3+
during discharge, and oxidized from Co3+
to Co4+
during charge.
The cell's energy is equal to the voltage times the charge. Each gram of lithium represents
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 (Li+
) carry the
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.[63]
The charging procedures for single Li-ion cells, and complete Li-ion batteries, are slightly different:
- 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
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 4.05 V/cell. [dubious ]
Failure to follow current and voltage limitations can result in an explosion.[66][67]
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 5 to 45 °C (41 to 113 °F).
Batteries gradually self-discharge even if not connected and delivering current. Li-ion rechargeable batteries have a self-discharge rate typically stated by manufacturers to be 1.5–2% per month.[69][70]
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.[71] Self-discharge rates may increase as batteries age.[72] In 1999, self-discharge per month was measured at 8% at 21 °C, 15% at 40 °C, 31% at 60 °C.[73] By 2007, monthly self-discharge rate was estimated at 2% to 3%, and 2[7]–3% by 2016.[74]
By comparison, the self-discharge rate for
Cathode
There are three classes of commercial cathode materials in lithium-ion batteries: (1) layered oxides, (2) spinel oxides and (3) oxoanion complexes. All of them were discovered by
(a) Layered Oxides
Several other first-row (3d)
Similarly, LiCrO2 shows reversible lithium (de)intercalation around 3.2 V with 170-270 mAh/g.[78] However, its cycle life is short, because of disproportionation of Cr4+ followed by translocation of Cr6+ into tetrahedral sites.[79] On the other hand, NaCrO2 shows a much better cycling stability.[80] LiTiO2 shows Li+ (de)intercalation at a voltage of ~1.5 V, which is too low for a cathode material.
These problems leave LiCoO
2 and LiNiO
2 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.[81] For this reason, the current trend among lithium-ion battery manufacturers is to switch to cathodes with higher Ni content and lower Co content.[82]
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),[83][76] cobalt- between +2 and +3, while Mn (usually >20%) and Al (typically, only 5% is needed)[84] remain in +4 and 3+, respectively. Thus increasing the Ni content increases the cyclable charge. For example, NCM111 shows 160 mAh/g, while LiNi0.8Co0.1Mn0.1O2 (NCM811) and LiNi0.8Co0.15Al0.05O2 (NCA) deliver a higher capacity of ~200 mAh/g.[85]
It is worth mentioning so-called "lithium-rich" cathodes, that can be produced from traditional NCM (LiMO2, where M=Ni, Co, Mn) layered cathode materials upon cycling them to voltages/charges corresponding to Li:M<0.5. Under such conditions a new semi-reversible redox transition at a higher voltage with ca. 0.4-0.8 electrons/metal site charge appears. This transition involves non-binding electron orbitals centered mostly on O atoms. Despite significant initial interest, this phenomenon did not result in marketable products because of the fast structural degradation (O2 evolution and lattice rearrangements) of such "lithium-rich" phases.[86]
(b) Cubic oxides (spinels)
An important improvement of Mn spinel are related cubic structures of the
LiV2O4 operates as a lower (ca. +3.0V) voltage than LiMn2O4, suffers from similar durability issues, is more expensive, and thus is not considered of practical interest.[90]
(c) Oxoanionic/olivins
Around 1980
Although numerous oxoanions (
Technology | Company | Target application | Benefit |
---|---|---|---|
Lithium nickel manganese cobalt oxide NMC, LiNixMnyCozO2 |
Imara Corporation, | Electric vehicles, power tools, grid energy storage | Good specific energy and specific power density |
Lithium nickel cobalt aluminium oxide NCA, LiNiCoAlO2 |
Electric vehicles, power tools, grid energy storage | High specific energy, good life span | |
Lithium nickel cobalt manganese aluminum oxide NCMA, LiNi 0.89Co 0.05Mn 0.05Al 0.01O 2 |
LG Chem,[100] Hanyang University[101] | Electric vehicles, grid energy storage | Good specific energy, improved long-term cycling stability, faster charging |
Lithium manganese oxide LMO, LiMn2O4 |
LG Chem,[102] NEC, Samsung,[103] Hitachi,[104] Nissan/AESC,[105] EnerDel[106] | cell phone, laptop
|
|
Lithium iron phosphate LFP, LiFePO4 |
PHEV conversions
|
moderate density (2 A·h outputs 70 amperes) High safety compared to Cobalt / Manganese systems. Operating temperature >60 °C (140 °F) | |
Lithium cobalt oxide LCO, LiCoO2 |
Sony first commercial production[110][111] | Broad use, laptop | High specific energy |
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.[112]
These materials are used because they are abundant, electrically conducting and can intercalate lithium ions to store electrical charge with modest volume expansion (~10%).[113] 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.[114] Low voltage is the key requirement for anodes; otherwise, the excess capacity is useless in terms of energy density.
Technology | Energy density | Durability | Company | Target application | Comments |
---|---|---|---|---|---|
Graphite | 260 Wh/kg | Tesla | The dominant negative electrode material used in lithium ion batteries, limited to a capacity of 372 mAh/g.[48] | Low cost and good energy density. Graphite anodes can accommodate one lithium atom for every six carbon atoms. Charging rate is governed by the shape of the long, thin graphene sheets that constitute graphite. While charging, the lithium ions must travel to the outer edges of the graphene sheet before coming to rest (intercalating) between the sheets. The circuitous route takes so long that they encounter congestion around those edges.[115] | |
Lithium titanate LTO, Li4Ti5O12 |
Toshiba, Altairnano | Automotive (Phoenix Motorcars), electrical grid (PJM Interconnection Regional Transmission Organization control area,[116] United States Department of Defense[117]), bus (Proterra) | Improved output, charging time, durability (safety, operating temperature −50–70 °C (−58–158 °F)).[118] | ||
Hard carbon | Energ2[119] | Home electronics | Greater storage capacity. | ||
Tin/cobalt alloy | Sony | Consumer electronics (Sony Nexelion battery) | Larger capacity than a cell with graphite (3.5 Ah 18650-type cell). | ||
Silicon/carbon | 730 Wh/L 450 Wh/kg |
Amprius[120] | Smartphones, providing 5000 mAh capacity | Uses < 10% with silicon nanowires combined with graphite and binders. Energy density: ~74 mAh/g.
Another approach used carbon-coated 15 nm thick crystal silicon flakes. The tested half-cell achieved 1200 mAh/g over 800 cycles.[121] |
As graphite is limited to a maximum capacity of 372 mAh/g[48] much research has been dedicated to the development of materials that exhibit higher theoretical capacities and overcoming the technical challenges that presently encumber their implementation. The extensive 2007 Review Article by Kasavajjula et al.[122] summarizes early research on silicon-based anodes for lithium-ion secondary cells. In particular, Hong Li et al.[123] 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.[124]
Diamond-like carbon coatings can increase retention capacity by 40% and cycle life by 400% for lithium based batteries.[125]
To improve the stability of the lithium anode, several approaches to installing a protective layer have been suggested.[126] 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%),[113] which causes catastrophic failure for the cell.[127] Silicon has been used as an anode material but the insertion and extraction of 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 , 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.[128]
Electrolyte
Recent advances in battery technology involve using a solid as the electrolyte material. The most promising of these are ceramics.
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.[126]
The ions in the electrolyte diffuse because there are small changes in the electrolyte concentration. Linear diffusion is only considered here. The change in concentration c, as a function of time t and distance x, is
In this equation, D is the
6 electrolyte. The value for ε, the porosity of the electrolyte, is 0.724.[142]
Formats
Lithium-ion batteries may have multiple levels of structure. Small batteries consist of a single battery cell. Larger batteries connect cells in parallel into a module and connect modules in series and parallel into a pack. Multiple packs may be connected in series to increase the voltage.[143]
Cells
Li-ion cells are available in various form factors, which can generally be divided into four types:[144]
- Small cylindrical (solid body without terminals, such as those used in most e-bikes and most electric vehicle battery and older laptop batteries); they typically come in standard sizes.
- Large cylindrical (solid body with large threaded terminals)
- Flat or pouch (soft, flat body, such as those used in cell phones and newer laptops; these are lithium-ion polymer batteries.[145]
- Rigid plastic case with large threaded terminals (such as electric vehicle traction packs)
Cells with a cylindrical shape are made in a characteristic "swiss roll" manner (known as a "jelly roll" in the US), which means it is a single long "sandwich" of the positive electrode, separator, negative electrode, and separator rolled into a single spool. The result is encased in a container. One advantage of cylindrical cells is faster production speed. One disadvantage can be a large radial temperature gradient at high discharge rates.
The absence of a case gives pouch cells the highest gravimetric energy density; however, many applications require containment to prevent expansion when their
Lithium-ion flow batteries have been demonstrated that suspend the cathode or anode material in an aqueous or organic solution.[148][149]
As of 2014, the smallest Li-ion cell was
Batteries may be equipped with temperature sensors, heating/cooling systems, voltage regulator circuits, voltage taps, and charge-state monitors. These components address safety risks like overheating and short circuiting.[153]
Uses
Lithium ion batteries are used in a multitude of applications from consumer electronics, toys, power tools and electric vehicles.[154]
More niche uses include backup power in telecommunications applications. Lithium-ion batteries are also frequently discussed as a potential option for grid energy storage,[155] although as of 2020, they were not yet cost-competitive at scale.[156]
Performance
Specific energy density | 100 to 250 kJ/kg)[157] |
---|---|
Volumetric energy density | 250 to 680 W·h/L (900 to 2230 J/cm3)[2][158] |
Specific power density | 300 to 1500 W/kg (at 20 seconds and 285 W·h/L)[1][failed verification] |
Because lithium-ion batteries can have a variety of positive and negative electrode materials, the energy density and voltage vary accordingly.
The
Batteries with a lithium iron phosphate positive and graphite negative electrodes have a nominal open-circuit voltage of 3.2 V and a typical charging voltage of 3.6 V. Lithium nickel manganese cobalt (NMC) oxide positives with graphite negatives have a 3.7 V nominal voltage with a 4.2 V maximum while charging. The charging procedure is performed at constant voltage with current-limiting circuitry (i.e., charging with constant current until a voltage of 4.2 V is reached in the cell and continuing with a constant voltage applied until the current drops close to zero). Typically, the charge is terminated at 3% of the initial charge current. In the past, lithium-ion batteries could not be fast-charged and needed at least two hours to fully charge. Current-generation cells can be fully charged in 45 minutes or less. In 2015 researchers demonstrated a small 600 mAh capacity battery charged to 68 percent capacity in two minutes and a 3,000 mAh battery charged to 48 percent capacity in five minutes. The latter battery has an energy density of 620 W·h/L. The device employed heteroatoms bonded to graphite molecules in the anode.[162]
Performance of manufactured batteries has improved over time. For example, from 1991 to 2005 the energy capacity per price of lithium ion batteries improved more than ten-fold, from 0.3 W·h per dollar to over 3 W·h per dollar.[163] In the period from 2011 to 2017, progress has averaged 7.5% annually.[164] Overall, between 1991 and 2018, prices for all types of lithium-ion cells (in dollars per kWh) fell approximately 97%.[165] Over the same time period, energy density more than tripled.[165] Efforts to increase energy density contributed significantly to cost reduction.[166]
Differently sized cells with similar chemistry can also have different energy densities. The
Round-trip efficiency
The table below shows the result of an experimental evaluation of a "high-energy" type 3.0Ah 18650 NMC cell in 2021, round-trip efficiency which compared the energy going into the cell and energy extracted from the cell from 100% (4.2v) SoC to 0% SoC (cut off 2.0v). A roundtrip efficiency is the percent of energy that can be used relative to the energy that went into charging the battery.[167]
C rate | efficiency | estimated charge efficiency | estimated discharged efficiency |
---|---|---|---|
0.2 | 86% | 93% | 92% |
0.4 | 82% | 92% | 90% |
0.6 | 81% | 91% | 89% |
0.8 | 77% | 90% | 86% |
1.0 | 75% | 89% | 85% |
1.2 | 73% | 89% | 83% |
Characterization of a cell in a different experiment in 2017 reported round-trip efficiency of 85.5% at 2C and 97.6% at 0.1C[168]
Lifespan
The lifespan of a lithium-ion battery is typically defined as the number of full charge-discharge cycles to reach a failure threshold in terms of capacity loss or impedance rise. Manufacturers' datasheet typically uses the word "cycle life" to specify lifespan in terms of the number of cycles to reach 80% of the rated battery capacity.[169] Simply storing lithium-ion batteries in the charged state also reduces their capacity (the amount of cyclable Li+) and increases the cell resistance (primarily due to the continuous growth of the solid electrolyte interface on the anode). Calendar life is used to represent the whole life cycle of battery involving both the cycle and inactive storage operations. Battery cycle life is affected by many different stress factors including temperature, discharge current, charge current, and state of charge ranges (depth of discharge).[170][171] Batteries are not fully charged and discharged in real applications such as smartphones, laptops and electric cars and hence defining battery life via full discharge cycles can be misleading. To avoid this confusion, researchers sometimes use cumulative discharge[170] defined as the total amount of charge (Ah) delivered by the battery during its entire life or equivalent full cycles,[171] which represents the summation of the partial cycles as fractions of a full charge-discharge cycle. Battery degradation during storage is affected by temperature and battery state of charge (SOC) and a combination of full charge (100% SOC) and high temperature (usually > 50 °C) can result in a sharp capacity drop and gas generation.[172] Multiplying the battery cumulative discharge by the rated nominal voltage gives the total energy delivered over the life of the battery. From this one can calculate the cost per kWh of the energy (including the cost of charging).
Over their lifespan batteries degrade gradually leading to reduced capacity (and, in some cases, lower operating cell voltage) due to a variety of chemical and mechanical changes to the electrodes.[173]
Several degradation processes occur in lithium-ion batteries, some during cycling, some during storage, and some all the time:[174][175][173] Degradation is strongly temperature-dependent: degradation at room temperature is minimal but increases for batteries stored or used in high temperature (usually > 35 °C) or low temperature (usually < 5 °C) environments.[176] High charge levels also hasten capacity loss.[177] Frequent over-charging (> 90%) and over-discharging (< 10%) may also hasten capacity loss.
In a study, scientists provided 3D imaging and model analysis to reveal main causes, mechanics, and potential mitigations of the problematic degradation of the batteries over charge cycles. They found "[p]article cracking increases and contact loss between particles and carbon-binder domain are observed to correlate with the cell degradation" and indicates that "the reaction heterogeneity within the thick cathode caused by the unbalanced electron conduction is the main cause of the battery degradation over cycling".[178][179][additional citation(s) needed]
The most common degradation mechanisms in lithium-ion batteries include:[180]
- Reduction of the organic carbonate electrolyte at the anode, which results in the growth of Solid Electrolyte Interface (SEI), where Li+ ions get irreversibly trapped, i.e. loss of lithium inventory. This shows as increased ohmic impedance and reduced Ah charge. At constant temperature, the SEI film thickness (and therefore, the SEI resistance and the loss in cyclable Li+) increases as a square root of the time spent in the charged state. The number of cycles is not a useful metric in characterizing this degradation pathway. Under high temperatures or in the presence of a mechanical damage the electrolyte reduction can proceed explosively.
- Lithium metal plating also results in the loss of lithium inventory (cyclable Ah charge), as well as internal short-circuiting and ignition of a battery. Once Li plating commences during cycling, it results in larger slopes of capacity loss per cycle and resistance increase per cycle. This degradation mechanism become more prominent during fast charging and low temperatures.
- Loss of the (negative or positive) electroactive materials due to dissolution (e.g. of Mn(3+) species), cracking, exfoliation, detachment or even simple regular volume change during cycling. It shows up as both charge and power fade (increased resistance). Both positive and negative electrode materials are subject to fracturing due to the volumetric strain of repeated (de)lithiation cycles.
- Structural degradation of cathode materials, such as Li+/Ni2+ cation mixing in nickel-rich materials. This manifests as “electrode saturation", loss of cyclable Ah charge and as a "voltage fade".
- Other material degradations. Negative copper current collector is particularly prone to corrosion/dissolution at low cell voltages. PVDF binder also degrades, causing the detachment of the electroactive materials, and the loss of cyclable Ah charge.
These are shown in the figure on the right. A change from one main degradation mechanism to another appears as a knee (slope change) in the capacity vs. cycle number plot.[180]
Most studies of lithium-ion battery aging have been done at elevated (50–60 °C) temperatures in order to complete the experiments sooner. Under these storage conditions, fully charged nickel-cobalt-aluminum and lithium-iron phosphate cells lose ca. 20% of their cyclable charge in 1–2 years. It is believed that the aforementioned anode aging is the most important degradation pathway in these cases. On the other hand, manganese-based cathodes show a (ca. 20–50%) faster degradation under these conditions, probably due to the additional mechanism of Mn ion dissolution.[175] At 25 °C the degradation of lithium-ion batteries seems to follow the same pathway(s) as the degradation at 50 °C, but with half the speed.[175] In other words, based on the limited extrapolated experimental data, lithium-ion batteries are expected to lose irreversibly ca. 20% of their cyclable charge in 3–5 years or 1000–2000 cycles at 25 °C.[180] Lithium-ion batteries with titanate anodes do not suffer from SEI growth, and last longer (>5000 cycles) than graphite anodes. However, in complete cells other degradation mechanisms (i.e. the dissolution of Mn3+ and the Ni3+/Li+ place exchange, decomposition of PVDF binder and particle detachment) show up after 1000–2000 days, and the use titanate anode does not improve full cell durability in practice.
Detailed degradation description
A more detailed description of some of these mechanisms is provided below:
(1) The negative (anode) SEI layer, a passivation coating formed by electrolyte (such as
Depending on the electrolyte and additives,
2CO
3 that increases the film thickness. This increases cell impedance and reduces cycling capacity.[176] Gases formed by electrolyte decomposition can increase the cell's internal pressure and are a potential safety issue in demanding environments such as mobile devices.[174] Below 25 °C, plating of metallic Lithium on the anodes and subsequent reaction with the electrolyte is leading to loss of cyclable Lithium.[176] Extended storage can trigger an incremental increase in film thickness and capacity loss.[174]
Electrolyte degradation mechanisms include hydrolysis and thermal decomposition.
Batteries generate heat when being charged or discharged, especially at high currents. Large battery packs, such as those used in electric vehicles, are generally equipped with thermal management systems that maintain a temperature between 15 °C (59 °F) and 35 °C (95 °F).[190] Pouch and cylindrical cell temperatures depend linearly on the discharge current.[191] Poor internal ventilation may increase temperatures. For large batteries consisting of multiple cells, non-uniform temperatures can lead to non-uniform and accelerated degradation.[192] In contrast, the calendar life of LiFePO
4 cells is not affected by high charge states.[193][194]
Positive SEI layer in lithium-ion batteries is much less understood than the negative SEI. It is believed to have a low-ionic conductivity and shows up as an increased interfacial resistance of the cathode during cycling and calendar aging.[174][175][173]
(2) Lithium plating is a phenomenon in which certain conditions lead to metallic lithium forming and depositing onto the surface of the battery’s anode rather than intercalating within the anode material’s structure. Low temperatures, overcharging and high charging rates can exacerbate this occurrence.[195][196] During these conditions, lithium ions may not intercalate uniformly into the anode material and form layers of lithium ion on the surface in the form of dendrites. Dendrites are tiny needle-like structures that can accumulate and pierce the separator, causing a short circuit can initiate thermal runaway.[174] This cascade of rapid and uncontrolled energy can lead to battery swelling, increased heat, fires and or explosions.[197] Additionally, this dendritic growth can lead to side reactions with the electrolyte and convert the fresh plated lithium into electrochemically inert dead lithium.[195] Moreover, the dendritic growth brought on by lithium plating can degrade the lithium-ion battery and lead to poor cycling efficiency and safety hazards. Some ways to mitigate lithium plating and the dendritic growth is by controlling the temperature, optimizing the charging conditions, and improving the materials used.[198] In terms of temperature, the ideal charging temperature is anywhere between 0 °C to 45 °C, but also room temperature is ideal (20 °C to 25 °C).[199] Advancements in materials innovation requires much research and development in the electrolyte selection and improving the anode resistance to plating. One such materials innovation would be to add other compounds to the electrolyte like fluoroethylene carbonate (FEC) to form a rich LiF SEI.[200] Another novel method would be to coat the separator in a protective shield that essentially “kills” the lithium ions before it can form these dendrites.[201]
(3) Certain manganese containing cathodes can degrade by the Hunter degradation mechanism resulting in manganese dissolution and reduction on the anode.[174] By the Hunter mechanism for LiMn
2O
4, hydrofluoric acid catalyzes the loss of manganese through disproportionation of a surface trivalent manganese to form a tetravalent manganese and a soluble divalent manganese:[174]
- 2Mn3+ → Mn2++ Mn4+
Material loss of the spinel results in capacity fade. Temperatures as low as 50 °C initiate Mn2+ deposition on the anode as metallic manganese with the same effects as lithium and copper plating.
2 and LiMn
2O
4 cathodes, the release of oxygen and irreversible capacity loss.[174]
(4) Cation mixing is the main reason for the capacity decline of the Ni-rich cathode materials. As the Ni content in the NCM layered material increases the capacity will increase, which is the result of two-electron of Ni2+/Ni4+ redox reaction (please note, that Mn remains electrochemically inactive in the 4+ state) but, increasing the Ni content results in a significant degree of mixing of Ni2+ and Li+ cations due to the closeness of their ionic radius (Li+ =0.076 nm and Ni2+ =0.069 nm). During charge/discharge cycling, the Li+ in the cathode cannot be easily be extracted and the existence of Ni2+ in the Li layer blocks the diffusion of Li+, resulting in both capacity loss and increased ohmic resistance.[202]
(5) Discharging below 2 V can also result in the dissolution of the copper anode current collector and, thus, in catastrophic internal short-circuiting on recharge.
Recommendations
The
Safety
The problem of lithium-ion battery safety has been recognized even before these batteries were first commercially released in 1991. The two main reasons for lithium-ion battery fires and explosions are related to processes on the negative electrode (cathode). During a normal battery charge lithium ions intercalate into graphite. However, if the charge is forced to go too fast (or at a too low temperature) lithium metal starts plating on the anode, and the resulting dendrites can penetrate the battery separator, internally short-circuit the cell, resulting in high electric current, heating and ignition. In other mechanism, an explosive reaction between the charge anode material (LiC6) and the solvent (liquid organic carbonate) occurs even at open circuit, provided that the anode temperature exceeds a certain threshold above 70°C.[205]
Nowadays, all reputable manufacturers employ at least two safety devices in all their lithium-ion batteries of an 18650 format or larger: a current interrupt (CID) device and a positive temperature coefficient (PTC) device. The CID comprises two metal disks, that make an electric contact with each other. When pressure inside the cell increases, the distance between the two disks increases too and they lose the electric contact with each other, thus terminating the flow of electric current through the battery. The PTC device is made of an electrically conducting polymer. When the current going through the PTC device increases, the polymer gets hot, and its electric resistance rises sharply, thus reducing the current through the battery.[206]
Fire hazard
Lithium-ion batteries can be a safety hazard since they contain a flammable electrolyte and may become pressurized if they become damaged. A battery cell charged too quickly could cause a short circuit, leading to overheating and explosions and fires.[207] A Li-ion battery fire can be started due to (1) thermal abuse, e.g. poor cooling or external fire, (2) electrical abuse, e.g. overcharge or external short circuit, (3) mechanical abuse, e.g. penetration or crash, or (4) internal short circuit, e.g. due to manufacturing flaws or aging.[208][209] Because of these risks, testing standards are more stringent than those for acid-electrolyte batteries, requiring both a broader range of test conditions and additional battery-specific tests, and there are shipping limitations imposed by safety regulators.[66][210][211] There have been battery-related recalls by some companies, including the 2016 Samsung Galaxy Note 7 recall for battery fires.[212][213]
Lithium-ion batteries have a flammable liquid electrolyte.[214] A faulty battery can cause a serious fire.[207] Faulty chargers can affect the safety of the battery because they can destroy the battery's protection circuit. While charging at temperatures below 0 °C, the negative electrode of the cells gets plated with pure lithium, which can compromise the safety of the whole pack.
Around 2010, large lithium-ion batteries were introduced in place of other chemistries to power systems on some aircraft; as of January 2014[update], there had been at least four serious
To reduce fire hazards, research projects are intended to develop non-flammable electrolytes.
Damaging and overloading
If a lithium-ion battery is damaged, crushed, or is subjected to a higher electrical load without having overcharge protection, then problems may arise. External short circuit can trigger a battery explosion.[220]
If overheated or overcharged, Li-ion batteries may suffer
Voltage limits
Lithium-ion cells are susceptible to stress by voltage ranges outside of safe ones between 2.5 and 3.65/4.1/4.2 or 4.35V (depending on the components of the cell). Exceeding this voltage range results in premature aging and in safety risks due to the reactive components in the cells.[224] When stored for long periods the small current draw of the protection circuitry may drain the battery below its shutoff voltage; normal chargers may then be useless since the battery management system (BMS) may retain a record of this battery (or charger) "failure". Many types of lithium-ion cells cannot be charged safely below 0 °C,[225] as this can result in plating of lithium on the anode of the cell, which may cause complications such as internal short-circuit paths.[citation needed]
Other safety features are required[by whom?] in each cell:[111]
- Shut-down separator (for overheating)
- Tear-away tab (for internal pressure relief)
- Vent (pressure relief in case of severe outgassing)
- Thermal interrupt (overcurrent/overcharging/environmental exposure)
These features are required because the negative electrode produces heat during use, while the positive electrode may produce oxygen. However, these additional devices occupy space inside the cells, add points of failure, and may irreversibly disable the cell when activated. Further, these features increase costs compared to nickel metal hydride batteries, which require only a hydrogen/oxygen recombination device and a back-up pressure valve.[75] Contaminants inside the cells can defeat these safety devices. Also, these features can not be applied to all kinds of cells, e.g., prismatic high current cells cannot be equipped with a vent or thermal interrupt. High current cells must not produce excessive heat or oxygen, lest there be a failure, possibly violent. Instead, they must be equipped with internal thermal fuses which act before the anode and cathode reach their thermal limits.[citation needed]
Replacing the lithium cobalt oxide positive electrode material in lithium-ion batteries with a lithium metal phosphate such as lithium iron phosphate (LFP) improves cycle counts, shelf life and safety, but lowers capacity. As of 2006, these safer lithium-ion batteries were mainly used in electric cars and other large-capacity battery applications, where safety is critical.[226]
Recalls
In 2006, approximately 10 million Sony batteries used in
Non-flammable electrolyte
In 2023, most commercial Li-ion batteries employed alkylcarbonate solvent(s) to assure the formation solid electrolyte interphase on the negative electrode. Since such solvents are readily flammable, there has been active research to replace them with non-flammable solvents or to add fire suppressants. Another source of hazard is hexafluorophosphate anion, which is needed to passitivate the negative current collector made of aluminium. Hexafluorophosphate reacts with water and releases volatile and toxic hydrogen fluoride. Efforts to replace hexafluorophosphate have been less successful.
Supply chain
The electric vehicle supply chain comprises the mining and refining of raw materials and the manufacturing processes that produce lithium ion batteries and other components for electric vehicles. The lithium-ion battery supply chain is a major component of the overall EV supply chain, and the battery accounts for 30–40% of the value of the vehicle.[230] Lithium, cobalt, graphite, nickel, and manganese are all critical minerals that are necessary for electric vehicle batteries.[231] There is rapidly growing demand for these materials because of growth in the electric vehicle market, which is driven largely by the proposed transition to renewable energy. Securing the supply chain for these materials is a major world economic issue.[232] Recycling and advancement in battery technology are proposed strategies to reduce demand for raw materials. Supply chain issues could create bottlenecks, increase costs of EVs and slow their uptake.[230][233]
The battery supply chain faces many challenges. Deposits of critical minerals are concentrated in a small number of countries, mostly in the Global South. Mining these deposits presents dangers to nearby communities because of weak regulation, corruption, and environmental degradation. These communities face human rights violations, environmental justice issues, problems with child labour, and potentially generational legacies of contamination from mining activities. Manufacture of battery technology is largely dominated by China. However burning less petroleum products in vehicles can reduce the environmental impact of the petroleum industry because, as of 2023[update], most petroleum is used in vehicles.[234]In the 1990’s, the
Environmental impact
Extraction of lithium, nickel, and cobalt, manufacture of solvents, and mining byproducts present significant environmental and health hazards.[236][237][238] Lithium extraction can be fatal to aquatic life due to water pollution.[239] It is known to cause surface water contamination, drinking water contamination, respiratory problems, ecosystem degradation and landscape damage.[236] It also leads to unsustainable water consumption in arid regions (1.9 million liters per ton of lithium).[236] Massive byproduct generation of lithium extraction also presents unsolved problems, such as large amounts of magnesium and lime waste.[240]
Lithium mining takes place in North and South America, Asia, South Africa, Australia, and China.[241]
Cobalt for Li-ion batteries is largely mined in the Congo (see also Mining industry of the Democratic Republic of the Congo)
Manufacturing a kg of Li-ion battery takes about 67
Solid waste and recycling
Li-ion battery elements including iron, copper, nickel and cobalt are considered safe for
Accumulation of battery waste presents technical challenges and health hazards.[254] Since the environmental impact of electric cars is heavily affected by the production of lithium-ion batteries, the development of efficient ways to repurpose waste is crucial.[252] Recycling is a multi-step process, starting with the storage of batteries before disposal, followed by manual testing, disassembling, and finally the chemical separation of battery components. Re-use of the battery is preferred over complete recycling as there is less embodied energy in the process. As these batteries are a lot more reactive than classical vehicle waste like tire rubber, there are significant risks to stockpiling used batteries.[255]
Pyrometallurgical recovery
The pyrometallurgical method uses a high-temperature furnace to reduce the components of the metal oxides in the battery to an alloy of Co, Cu, Fe, and Ni. This is the most common and commercially established method of recycling and can be combined with other similar batteries to increase smelting efficiency and improve thermodynamics. The metal current collectors aid the smelting process, allowing whole cells or modules to be melted at once.[256] The product of this method is a collection of metallic alloy, slag, and gas. At high temperatures, the polymers used to hold the battery cells together burn off and the metal alloy can be separated through a hydrometallurgical process into its separate components. The slag can be further refined or used in the cement industry. The process is relatively risk-free and the exothermic reaction from polymer combustion reduces the required input energy. However, in the process, the plastics, electrolytes, and lithium salts will be lost.[257]
Hydrometallurgical metals reclamation
This method involves the use of aqueous solutions to remove the desired metals from the cathode. The most common reagent is sulfuric acid.[258] Factors that affect the leaching rate include the concentration of the acid, time, temperature, solid-to-liquid-ratio, and reducing agent.[259] It is experimentally proven that H2O2 acts as a reducing agent to speed up the rate of leaching through the reaction:[citation needed]
- 2 LiCoO2 (s) + 3 H2SO4 + H2O2 → 2 CoSO4 (aq) + Li2SO4 + 4 H2O + O2
Once leached, the metals can be extracted through precipitation reactions controlled by changing the pH level of the solution. Cobalt, the most expensive metal, can then be recovered in the form of sulfate, oxalate, hydroxide, or carbonate. [75] More recently recycling methods experiment with the direct reproduction of the cathode from the leached metals. In these procedures, concentrations of the various leached metals are premeasured to match the target cathode and then the cathodes are directly synthesized.[260]
The main issues with this method, however, is that a large volume of solvent is required and the high cost of neutralization. Although it's easy to shred up the battery, mixing the cathode and anode at the beginning complicates the process, so they will also need to be separated. Unfortunately, the current design of batteries makes the process extremely complex and it is difficult to separate the metals in a closed-loop battery system. Shredding and dissolving may occur at different locations.[261]
Direct recycling
Direct recycling is the removal of the cathode or anode from the electrode, reconditioned, and then reused in a new battery. Mixed metal-oxides can be added to the new electrode with very little change to the crystal morphology. The process generally involves the addition of new lithium to replenish the loss of lithium in the cathode due to degradation from cycling. Cathode strips are obtained from the dismantled batteries, then soaked in NMP, and undergo sonication to remove excess deposits. It is treated hydrothermally with a solution containing LiOH/Li2SO4 before annealing.[262]
This method is extremely cost-effective for noncobalt-based batteries as the raw materials do not make up the bulk of the cost. Direct recycling avoids the time-consuming and expensive purification steps, which is great for low-cost cathodes such as LiMn2O4 and LiFePO4. For these cheaper cathodes, most of the cost, embedded energy, and carbon footprint is associated with the manufacturing rather than the raw material.[263] It is experimentally shown that direct recycling can reproduce similar properties to pristine graphite.
The drawback of the method lies in the condition of the retired battery. In the case where the battery is relatively healthy, direct recycling can cheaply restore its properties. However, for batteries where the state of charge is low, direct recycling may not be worth the investment. The process must also be tailored to the specific cathode composition, and therefore the process must be configured to one type of battery at a time.[264] Lastly, in a time with rapidly developing battery technology, the design of a battery today may no longer be desirable a decade from now, rendering direct recycling ineffective.
Human rights impact
Extraction of raw materials for lithium ion batteries may present dangers to local people, especially land-based indigenous populations.[265]
Cobalt sourced from the Democratic Republic of the Congo is often mined by workers using hand tools with few safety precautions, resulting in frequent injuries and deaths.
A study of relationships between lithium extraction companies and indigenous peoples in Argentina indicated that the state may not have protected indigenous peoples' right to free prior and informed consent, and that extraction companies generally controlled community access to information and set the terms for discussion of the projects and benefit sharing.[271]
Development of the
Research
Researchers are actively working to improve the power density, safety, cycle durability (battery life), recharge time, cost, flexibility, and other characteristics, as well as research methods and uses, of these batteries. All-solid-state batteries are being researched as a breakthrough in technological barriers. Currently, all-solid-state batteries are expected to be the most promising next-generation battery, and various companies are working to popularize them.
See also
- Anode-free battery
- Blade battery
- Borate oxalate
- Comparison of commercial battery types
- European Battery Alliance
- Flow battery
- Nanowire battery
- Sodium-ion battery
- Solid-state battery
- Thin-film lithium-ion battery
- VRLA battery
- Ultium
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External links
- Lithium-ion Battery at the Encyclopædia Britannica.
- List of World's Largest Lithium-ion Battery Factories (2020).
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- Degradation Mechanisms and Lifetime Prediction for Lithium-Ion Batteries, NREL, July 2015.
- Impact of Temperature Extremes on Large Format Li-ion Batteries for Vehicle Applications, NREL, March 2013.