Sodium-ion battery

A sodium-ion cell (size18650)
Specific energy	0.27-0.72MJ/kg (75–200W·h/kg)
Energy density	250–375 W·h/L
Cycle durability	"thousands"[1] ofcycles
Nominal cell voltage	3.0-3.1 V

Sodium-ion batteries (NIBs,SIBs, orNa-ion batteries) are several types ofrechargeable batteries, which usesodiumions (Na⁺) as theircharge carriers. In some cases, itsworking principle andcell construction are similar to those oflithium-ion battery (LIB) types, but it replaceslithium withsodium as theintercalatingion. Sodium belongs to the samegroup in theperiodic table as lithium and thus has similarchemical properties. However, in some cases, such as aqueous batteries, SIBs can be quite different from LIBs.

SIBs received academic and commercial interest in the 2010s and early 2020s, largely due to lithium's high cost, uneven geographic distribution, and environmentally-damaging extraction process. An obvious advantage of sodium is its natural abundance,^[2] particularly insaltwater. Another factor is thatcobalt,copper andnickel are not required for many types of sodium-ion batteries, and more abundantiron-based materials (such as NaFeO2 with the${\displaystyle {\text{Fe}}_3^{+}/{\text{Fe}}_4^{+}}$ redox pair)^[3] work well in${\displaystyle {\text{Na}}^{+}}$ batteries. This is because theionic radius of Na⁺ (116 pm) is substantially larger than that of Fe²⁺ and Fe³⁺ (69–92 pm depending on thespin state), whereas the ionic radius of Li⁺ is similar (90 pm). Similar ionic radii of lithium and iron result in their mixing in the cathode material during battery cycling, and a resultant loss of cyclable charge. A downside of the larger ionic radius of Na⁺ is a slowerintercalation kinetics of sodium-ion electrode materials.^[4]

The development of${\displaystyle {\text{Na}}^{+}}$ batteries started in the 1990s.After three decades of development, NIBs are at a critical moment of commercialization. Several companies such as HiNa and CATL in China, Faradion in the United Kingdom, Tiamat in France,Northvolt in Sweden,^[5] andNatron Energy in the US, are close to achieving the commercialization of NIBs, with the aim of employing sodium layered transition metal oxides (NaxTMO2), Prussian white (aPrussian blue analogue^[6]) or vanadium phosphate as cathode materials.^{[improper synthesis?][7][8][9][10][11][12][13]}

Sodium-ion accumulators are operational for fixed electricalgrid storage, butvehicles using sodium-ionbattery packs are not yet commercially available. However,CATL, the world's biggest lithium-ion battery manufacturer, announced in 2022 the start of mass production of SIBs. In February 2023, the ChineseHiNA Battery Technology Company, Ltd. placed a 140 Wh/kg sodium-ion battery in an electric test car for the first time,^[14] and energy storage manufacturer Pylontech obtained the first sodium-ion battery certificate^{[clarification needed]} fromTÜV Rheinland.^[15]

Sodium-ion battery development took place in the 1970s and early 1980s. However, by the 1990s, lithium-ion batteries had demonstrated more commercial promise, causing interest in sodium-ion batteries to decline.^[16][17] In the early 2010s, sodium-ion batteries experienced a resurgence, driven largely by the increasing cost of lithium-ion battery raw materials.^[16] Also, the number of patent families reached the number of non-patent publication after ca. 2020, which usually signify the fact that the technology reached the commercialization stage.

SIB cells consist of acathode based on a sodium-based material, ananode (not necessarily a sodium-based material) and a liquidelectrolyte containing dissociated sodium salts inpolarprotic oraprotic solvents. During charging, sodium ions move from the cathode to the anode while electrons travel through the external circuit. During discharge, the reverse process occurs.^{[citation needed]}

Due to the physical and electrochemical properties of sodium, SIBs require different materials from those used for LIBs.^[18]

SIBs can usehard carbon, a disordered carbon material consisting of a non-graphitizable, non-crystalline and amorphous carbon. Hard carbon's ability to absorb sodium was discovered in 2000.^[19] This anode was shown to deliver 300 mAh/g with a sloping potential profile above ⁓0.15 Vvs Na/Na⁺. It accounts for roughly half of the capacity and a flat potential profile (a potential plateau) below ⁓0.15 Vvs Na/Na⁺. Such capacities are comparable to 300–360 mAh/g ofgraphite anodes inlithium-ion batteries. The first sodium-ion cell using hard carbon was demonstrated in 2003 and showed a 3.7 V average voltage during discharge.^[20] Hard carbon was the preferred choice ofFaradion due to its excellent combination of capacity, (lower) working potentials, and cycling stability.^[21] Notably, nitrogen-doped hard carbons display even larger specific capacity of 520 mAh/g at 20 mA/g with stability over 1000 cycles.^[22]

In 2015, researchers demonstrated that graphite could co-intercalate sodium in ether-based electrolytes. Low capacities around 100 mAh/g were obtained with relatively high working potentials between 0 – 1.2 Vvs Na/Na⁺.^[23]

One drawback of carbonaceous materials is that, because their intercalation potentials are fairly negative, they are limited to non-aqueous systems.

GrapheneJanus particles have been used in experimental sodium-ion batteries to increaseenergy density. One side provides interaction sites while the other provides inter-layer separation. Energy density reached 337 mAh/g.^[24]

Carbon arsenide (AsC₅) mono/bilayer has been explored as an anode material due to high specific gravity (794/596 mAh/g), low expansion (1.2%), and ultra low diffusion barrier (0.16/0.09 eV), indicating rapid charge/discharge cycle capability, during sodium intercalation.^[25] After sodium adsorption, a carbon arsenide anode maintains structural stability at 300 K, indicating long cycle life.

Numerous reports described anode materials storing sodium via alloy reaction and/or conversion reaction.^[16] Alloying sodium metal brings the benefits of regulating sodium-ion transport and shielding the accumulation of electric field at the tip of sodiumdendrites.^[26] Wang,et al. reported that a self-regulating alloy interface of nickel antimony (NiSb) was chemically deposited on Na metal during discharge. This thin layer of NiSb regulates the uniform electrochemical plating of Na metal, lowering overpotential and offering dendrite-free plating/stripping of Na metal over 100 h at a high areal capacity of 10 mAh cm⁻².^[27]

Many metals and semi-metals (Pb, P, Sn, Ge, etc.) form stable alloys with sodium at room temperature. Unfortunately, the formation of such alloys is usually accompanied by a large volume change, which in turn results in the pulverization (crumbling) of the material after a few cycles. For example, withtin sodium forms an alloyNa
₁₅Sn
₄, which is equivalent to 847 mAh/g specific capacity, with a resulting enormous volume change up to 420%.^[28]

In one study, Li et al. prepared sodium and metallic tinNa
₁₅Sn
₄/Na through a spontaneous reaction.^{[citation needed]} This anode could operate at a high temperature of 90 °C (194 °F) in a carbonate solvent at 1 mA cm⁻² with 1 mA h cm⁻² loading, and the full cell exhibited a stable charge-discharge cycling for 100 cycles at a current density of 2C.^{[citation needed]} (2C means that full charge or discharge was achieved in 0.5 hour). Despite sodium alloy's ability to operate at extreme temperatures and regulate dendritic growth, the severe stress-strain experienced on the material in the course of repeated storage cycles limits cycling stability, especially in large-format cells.

Researchers fromTokyo University of Science achieved 478 mAh/g with nano-sizedmagnesium particles, announced in December 2020.^[29]

In 2024,Dalhousie University researchers enhanced sodium-ion battery performance by replacing hard carbon in the negative electrode with lead (Pb) and single wallcarbon nanotubes (SWCNTs). This combination significantly increased volumetric energy density and eliminated capacity fade in half cells. SWCNTs endured active material connectivity, boosting capacity to 475 mAh/g and reducing losses, compared to 430 mAh/g in Pb cell without SWCNTs.^[30]

Some sodiumtitanate phases such as Na₂Ti₃O₇,^[31][32][33] or NaTiO₂,^[34] delivered capacities around 90–180 mAh/g at low working potentials (< 1 Vvs Na/Na⁺), though cycling stability was limited to a few hundred cycles.

In 2021, researchers from China tried layered structureMoS₂ as a new type of anode for sodium-ion batteries. A dissolution-recrystallization process densely assembled carbon layer-coatedMoS₂ nanosheets onto the surface ofpolyimide-derived N-dopedcarbon nanotubes. This kind of C-MoS₂/NCNTs anode can store 348 mAh/g at 2 A/g, with a cycling stability of 82% capacity after 400 cycles at 1 A/g.^[35]TiS₂ is another potential material for SIBs because of its layered structure, but has yet to overcome the problem of capacity fade, sinceTiS₂ suffers from poor electrochemical kinetics and relatively weak structural stability. In 2021, researchers from Ningbo, China employed pre-potassiatedTiS₂, presenting rate capability of 165.9mAh/g and a cycling stability of 85.3% capacity after 500 cycles.^[36]

Some other materials, such asmercury,electroactive polymers and sodiumterephthalate derivatives,^[37] have also been demonstrated in laboratories, but did not provoke commercial interest.^[21]

Many layeredtransition metal oxides can reversibly intercalate sodium ions upon reduction. These oxides typically have a highertap density and a lower electronicresistivity, than other posode materials (such as phosphates). Due to a larger size of the Na⁺ ion (116 pm) compared to Li⁺ ion (90 pm), cation mixing between Na⁺ and first row transition metal ions (which is common in the case of Li+) usually does not occur. Thus, low-cost iron and manganese oxides can be used for Na-ion batteries, whereas Li-ion batteries require the use of more expensive cobalt and nickel oxides. The drawback of the larger size of Na⁺ ion is its slower intercalation kinetics compared to Li⁺ ion and the presence of multiple intercalation stages with different voltages and kinetic rates.^[4]

A P2-type Na_2/3Fe_1/2Mn_1/2O₂ oxide from earth-abundant Fe and Mn resources can reversibly store 190 mAh/g at average discharge voltage of 2.75 Vvs Na/Na⁺ utilising the Fe^3+/4+redox couple – on par or better than commercial lithium-ion cathodes such as LiFePO₄ or LiMn₂O₄.^[38] However, its sodium deficient nature lowered energy density. Significant efforts were expended in developing Na-richer oxides. A mixed P3/P2/O3-type Na_0.76Mn_0.5Ni_0.3Fe_0.1Mg_0.1O₂ was demonstrated to deliver 140 mAh/g at an average discharge voltage of 3.2 Vvs Na/Na⁺ in 2015.^[39] In particular, the O3-type NaNi_1/4Na_1/6Mn_2/12Ti_4/12Sn_1/12O₂ oxide can deliver 160 mAh/g at average voltage of 3.22 Vvs Na/Na⁺,^[40] while a series of doped Ni-based oxides of thestoichiometry Na_aNi_{(1−x−y−z)}Mn_xMg_yTi_zO₂ can deliver 157 mAh/g in a sodium-ion "full cell" with a hard carbon anode at average discharge voltage of 3.2 V utilising the Ni^2+/4+ redox couple.^[41] Such performance in full cell configuration is better or on par with commercial lithium-ion systems. A Na_0.67Mn_1−xMg_xO₂ cathode material exhibited a discharge capacity of 175 mAh/g for Na_0.67Mn_0.95Mg_0.05O₂. This cathode contained only abundant elements.^[42] Copper-substituted Na_0.67Ni_0.3−xCu_xMn_0.7O₂ cathode materials showed a high reversible capacity with better capacity retention. In contrast to the copper-free Na_0.67Ni_0.3−xCu_xMn_0.7O₂ electrode, the as-prepared Cu-substituted cathodes deliver better sodium storage. However, cathodes with Cu are more expensive.^[43]

Research has also considered cathodes based onoxoanions. Such cathodes offer lower tap density, lowering energy density than oxides. On the other hand, a strongercovalent bonding of the polyanion positively impacts cycle life and safety and increases the cell voltage. Among polyanion-based cathodes, sodium vanadium phosphate^[44] andfluorophosphate^[45] have demonstrated excellent cycling stability and in the latter, an acceptably high capacity (⁓120 mAh/g) at high average discharge voltages (⁓3.6 Vvs Na/Na⁺).^[46] Besides that, sodium manganese silicate has also been demonstrated to deliver a very high capacity (>200 mAh/g) with decent cycling stability.^[47] A French startup TIAMAT develops Na⁺ ion batteries based on a sodium-vanadium-phosphate-fluoride cathode material Na₃V₂(PO₄)₂F₃, which undergoes two reversible 0.5 e-/V transitions: at 3.2V and at 4.0 V.^[48] A startup from Singapore,SgNaPlus is developing and commercialising Na₃V₂(PO₄)₂F₃ cathode material, which shows very good cycling stability, utilising the non-flammable glyme-based electrolyte.^[49]

Numerous research groups investigated the use ofPrussian blue and various Prussian blue analogues (PBAs) as cathodes for Na⁺-ion batteries. The ideal formula for a discharged material isNa₂M[Fe(CN)₆], and it corresponds to the theoretical capacity of ca. 170 mAh/g, which is equally split between two one-electron voltage plateaus. Such high specific charges are rarely observed only in PBA samples with a low number of structural defects.

For example, the patented rhombohedral Na₂MnFe(CN)₆ displaying 150–160 mAh/g in capacity and a 3.4 V average discharge voltage^[50][51][52] and rhombohedral Prussian white Na_1.88(5)Fe[Fe(CN)₆]·0.18(9)H₂O displaying initial capacity of 158 mAh/g and retaining 90% capacity after 50 cycles.^[53]

While Ti, Mn, Fe and Co PBAs show a two-electron electrochemistry, the Ni PBA shows only one-electron (Ni is not electrochemically active in the accessible voltage range). Iron-free PBA Na₂Mn^II[Mn^II(CN)₆] is also known. It has a fairly large reversible capacity of 209 mAh/g at C/5, but its voltage is unfortunately low (1.8 V versus Na⁺/Na).^[4]

Bis-tetraaminobenzoquinone, a low-bandgap, conductive, and highly insoluble layered metal-free material was used as a cathode. It exhibited a theoretical capacity of 355 mAh g–1. Researchers used a four-electron redox process, and achieved an electrode-level energy density of 606 Wh kg–1electrode (90 wt % active material) with excellent cycling stability. Forming the material in the presence of as little as 2 wt % carboxyl-functionalizedcarbon nanotubes improved charge transport and kinetics. Cathode energy density reached 472 Wh kg–1 when charging/discharging in 90 s with specific power of 31.6 kW kg–1.^[54]

Sodium-ion batteries can useaqueous and non-aqueous electrolytes. The limitedelectrochemical stability window of water results in lower voltages and limited energy densities. Non-aqueouscarbonate ester polar aprotic solvents extend the voltage range. These includeethylene carbonate,dimethyl carbonate,diethyl carbonate, andpropylene carbonate. The most widely used salts in non-aqueous electrolytes are NaClO₄ andsodium hexafluorophosphate (NaPF₆) dissolved in a mixture of these solvents. It is a well-established fact that these carbonate-based electrolytes are flammable, which pose safety concerns in large-scale applications. A type of glyme-based electrolyte, withsodium tetrafluoroborate as the salt is demonstrated to be non-flammable.^[55] In addition, NaTFSI (TFSI = bis(trifluoromethane)sulfonimide) and NaFSI (FSI = bis(fluorosulfonyl)imide, NaDFOB (DFOB = difluoro(oxalato)borate) and NaBOB (bis(oxalato)borate) anions have emerged lately as new interesting salts. Of course, electrolyte additives can be used as well to improve the performance metrics.^[56]

Sodium-ion batteries have several advantages over competing battery technologies. Compared to lithium-ion batteries, sodium-ion batteries have somewhat lower cost, better safety characteristics (for the aqueous versions), and similar power delivery characteristics, but also a lower energy density (especially the aqueous versions).^[57]

The table below compares how NIBs in general fare against the two established rechargeable battery technologies in the market currently: the lithium-ion battery and the rechargeablelead–acid battery.^[41][58]

Companies around the world have been working to develop commercially viable sodium-ion batteries. A 2-hour 5MW/10MWhgrid battery was installed in China in 2023.^[73]

Farasis Energy'sJMEV EV3 (Youth Edition) sets a new standard as the world's first serial-production A00-classelectric vehicle equipped with sodium batteries (sodium-ion batteries), offering a range of 251 kilometres (156 mi).^[74]

Dongfeng revealed theNammi 01 electric vehicle, which Dongfeng claimed features a sodium solid state battery at a launch event.^{[75][better source needed]}

Altris AB was founded by Associate Professor Reza Younesi, his former PhD student, Ronnie Mogensen, and Associate Professor William Brant as a spin-off fromUppsala University, Sweden,^[76] launched in 2017 as part of research efforts from the team on sodium-ion batteries. The research was conducted at the Ångström Advanced Battery Centre led by Prof.Kristina Edström atUppsala University. The company offers a proprietary iron-based Prussian blue analogue for the positive electrode in non-aqueous sodium-ion batteries that use hard carbon as the anode.^[77] Altris holds patents on non-flammable fluorine-free electrolytes consisting of NaBOB in alkyl-phosphate solvents, Prussian white cathode, and cell production. Clarios is partnering to produce batteries using Altris technology.^[78]

TheBYD Company is a Chinese electric vehicle manufacturer and battery manufacturer. In 2023, they invested $1.4B USD into the construction of a sodium-ion battery plant in Xuzhou with an annual output of 30 GWh.^[79]

Chinese battery manufacturerCATL announced in 2021 that it would bring a sodium-ion based battery to market by 2023.^[80] It uses Prussian blue analogue for the positive electrode and porous carbon for the negative electrode. They claimed a specific energy density of 160 Wh/kg in their first generation battery.^[64]

In 2024, CATL unveiled the Freevoy hybrid chemistry battery pack for use inhybrid vehicles with a mix of sodium ion and lithium ion cells. This battery pack features an expected range of over 400 kilometres (250 mi), 4C fast charging capability, the ability to be discharged at −40 °C (−40 °F), and no difference to the driving experience at −20 °C (−4 °F). By 2025, around 30 different hybrid vehicle models are expected to be equipped with this pack.^[81]

On November 18th 2024, CATL announced its second generation sodium-ion battery to be released in 2025 and reach mass market by 2027. The battery is expected to be able to be discharged normally at temperatures of −40 °C (−40 °F).^[82]

Faradion Limited is a subsidiary of India'sReliance Industries.^[83] Its cell design uses oxide cathodes with hard carbon anode and a liquid electrolyte. Theirpouch cells have energy densities comparable to commercial Li-ion batteries (160 Wh/kg at cell-level), with good rate performance up to3C, and cycle lives of 300 (100%depth of discharge) to over 1,000 cycles (80% depth of discharge). Its battery packs have demonstrated use for e-bike and e-scooter applications.^[41] They demonstrated transporting sodium-ion cells in the shorted state (at 0 V), eliminating risks from commercial transport of such cells.^[84] It is partnering with AMTE Power plc^[85] (formerly known as AGM Batteries Limited).^{[86][87][88][89]}

In November 2019, Faradion co-authored a report with Bridge India^[90] titled 'The Future of Clean Transportation: Sodium-ion Batteries'^[91] looking at the growing role India can play in manufacturing sodium-ion batteries.

On December 5, 2022, Faradion installed its first sodium-ion battery for Nation in New South Wales Australia.^[92]

HiNa Battery Technology Co., Ltd is, a spin-off from theChinese Academy of Sciences (CAS). It leverages research conducted by Prof. Hu Yong-sheng's group at the Institute of Physics at CAS. HiNa's batteries are based on Na-Fe-Mn-Cu based oxide cathodes andanthracite-based carbon anode. In 2023, HiNa partnered with JAC as the first company to put a sodium-ion battery in an electric car, the Sehol E10X. HiNa also revealed three sodium-ion products, the NaCR32140-ME12 cylindrical cell, the NaCP50160118-ME80 square cell and the NaCP73174207-ME240 square cell, with gravimetric energy densities of 140 Wh/kg, 145 Wh/kg and 155 Wh/kg respectively.^[93] The cycle life of Hina's Battery was reported to by 4,500 cycles in 2022. The company's goals were increasing specific energy to 180-200 Wh/kg and the cycle life to 8,000-10,000 cycles.CATL andBYD also made similar statements around the same time.^[94]

In 2019, it was reported that HiNa installed a 100 kWh sodium-ion battery energy storage system in East China.^[95]

Chinese automaker Yiwei debuted the first sodium-ion battery-powered car in 2023. It uses JAC Group's UE module technology, which is similar to CATL's cell-to-pack design.^[96] The car has a 23.2 kWh battery pack with a CLTC range of 230 kilometres (140 mi).^[97]

KPIT Technologies introduced India's first sodium-ion battery technology, marking a significant breakthrough in the country. This newly developed technology is predicted to reduce the cost of batteries for electric vehicles by 25-30%. It has been developed in cooperation with Pune's Indian Institute of Science Education and Research over the course of almost a decade and claims several notable benefits over existing alternatives such as lead-acid and lithium-ion. Among its standout features are a longer lifespan of 3,000–6,000 cycles, faster charging than traditional batteries, greater resistance to below-freezing temperatures and with varied energy densities between 100 and 170 Wh/Kg.^{[98][99][100]}

Natron Energy, a spin-off fromStanford University, uses Prussian blue analogues for both cathode and anode with an aqueous electrolyte.^[101] Clarios is partnering to produce a battery using Natron technology.^[102]

Northvolt, Europe's only large homegrown electric battery maker, has said it has made a "breakthrough" sodium-ion battery. Northvolt said its new battery, which has an energy density of more than 160 watt-hours per kilogram, has been designed for electricity storage plants but could in future be used in electric vehicles, such as two wheeled scooters.^[5] The company filed for bankruptcy in November 2024.^[103]

TIAMAT spun off from theCNRS/CEA and aH2020 EU-project called NAIADES.^[104] Its technology focuses on the development of18650-format cylindrical cells based on polyanionic materials. It achieved energy density between 100 Wh/kg to 120 Wh/kg. The technology targets applications in the fast charge and discharge markets. Power density is between 2 and 5 kW/kg, allowing for a 5 min charging time. Lifetime is 5000+ cycles to 80% of capacity.^{[105][106][107][108]}

They are responsible for one of the first commercialized product powered by Sodium-Ion battery technology, as of October 2023, through the commercialization of an electric screw-driver.^[109]

SgNaPlus is a spin off fromNational University of Singapore, that uses a propeitary electrode and electrolyte.[1] It is based in Singapore and leverages on research conducted by Alternative Energy Systems Laboratory (AESL) from Energy and Bio-Thermal Systems Division in the Department of Mechanical Engineering, National University of Singapore (NUS). The division is founded by Prof Palani Balaya. SgNaPlus also has rights for the patent for a non-flammable sodium-ion batteries.^{[citation needed]}

Aquion Energy was (between 2008 and 2017) aspin-off fromCarnegie Mellon University. Their batteries (salt water battery) were based on sodium titanium phosphate anode,manganese dioxide cathode, and aqueoussodium perchlorate electrolyte. After receiving government and private loans, the company filed for bankruptcy in 2017. Its assets were sold to a Chinese manufacturer Juline-Titans, who abandoned most of Aquion's patents.^{[110][111][109]}

Types are:^[112]

• Molten-sodium battery:
  • Sodium-sulfur battery (NaS).
  • Sodium-metal halide or Sodium-nickel chloride battery (${\displaystyle \text{Na}-{\text{NiCl}}_2^{}}$ orZebra battery).
• Sodium-ion battery (NaIBs).

• List of battery types
• Comparison of commercial battery types
• Alkali metal-ion batteries:
  • Lithium-ion battery
  • Sodium-ion battery
  • Potassium-ion battery
• Alkaline earth metal-ion batteries:
  • Calcium-ion battery
• Rechargeable battery
• Solid state battery

• Ma, Bingyuan; Lee, Youngju; Bai, Peng (2021)."Dynamic Interfacial Stability Confirmed by Microscopic Optical Operando Experiments Enables High-Retention-Rate Anode-Free Na Metal Full Cells".Advanced Science.8 (12): 2005006.doi:10.1002/advs.202005006.PMC 8224441.PMID 34194939.
• Wunderlich-Pfeiffer, Frank (April 19, 2023)."Na-ion: A battery worth its salt?".intercalationstation.substack.com. Retrieved2023-04-28.
• Wu, Billy (January 3, 2024).Sodium ion batteries - The low-cost future of energy storage? (Podcast). Retrieved2024-01-05.

• Rechargeable batteries
• Metal-ion batteries
• Battery types

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