The concept, structure, and progress of seawater metal-air batteries

Abstract

Seawater metal-air batteries (SMABs) are promising energy storage technologies for their advantages of high energy density, intrinsic safety, and low cost. However, the presence of such chloride ions complex components in seawater inevitably has complex effects on the air electrode process, including oxygen reduction and oxygen evolution reactions (ORR and OER), which requires the development of highly-active chloride-resistant electrocatalysts. In this review, we first summarized the developing status of various types of SMABs, explaining their working principle and comparing the battery performance. Then, the reported chlorine-resistant electrocatalysts were classified. The composition and structural design strategies of high-efficient chlorine-resistant ORR/OER electrocatalysts in seawater electrolytes were comprehensively summarized. Finally, the main challenges to be overcome in the commercialization of SMABs were discussed.

Keywords

Seawater metal-air batteries / oxygen reduction reactions / oxygen evolution reactions / chloride-resistant

References

[1] Helveston JP,Davidson MR.Quantifying the cost savings of global solar photovoltaic supply chains.Nature2022;612:83-7

[2] Russo G.Renewable energy: wind power tests the waters.Nature2014;513:478-80

[3] Aziz MJ,Johnson K.A co-design framework for wind energy integrated with storage.Joule2022;6:1995-2015

[4] Almora O,Bazan GC.Device performance of emerging photovoltaic materials (version 1).Adv Energy Mater2021;11:2002774

[5] Zhang C,Yu H.Single-atom catalysts for hydrogen generation: rational design, recent advances, and perspectives.Adv Energy Mater2022;12:e2200875

[6] van Cresce A.Aqueous lithium-ion batteries.Carbon Energy2021;3:721-51

[7] Lopes PP.Past, present, and future of lead-acid batteries.Science2020;369:923-4

[8] Kim J,Kim H,Cho J.Rechargeable seawater battery and its electrochemical mechanism.ChemElectroChem2015;2:328-32

[9] Kim Y.Secondary seawater batteries. In: Seawater batteries. Green Energy and Technology. Singapore: Springer; 2022. pp. 91-293.

[10] Mozaffari S.Recent advances in solar rechargeable seawater batteries based on semiconductor photoelectrodes.Top Curr Chem2022;380:28

[11] Khan Z,Yang J.Binary N,S-doped carbon nanospheres from bio-inspired artificial melanosomes: a route to efficient air electrodes for seawater batteries.J Mater Chem A2018;6:24459-67

[12] Sun Q,Luo T,Liang F.Recent advances in solid-state metal-air batteries.Carbon Energy2023;5:e276

[13] Li Y.Metal-air batteries: will they be the future electrochemical energy storage device of choice?.ACS Energy Lett2017;2:1370-7

[14] Rahman MA,Wen C.High energy density metal-air batteries: a review.J Electrochem Soc2013;160:A1759-71

[15] Zhang J,He F.Defect and doping co-engineered non-metal nanocarbon ORR electrocatalyst.Nanomicro Lett2021;13:65 PMCID:PMC8187682

[16] Chen Y,He P.Metal-air batteries: progress and perspective.Sci Bull2022;67:2449-86

[17] Galili N,Yam R.The geologic history of seawater oxygen isotopes from marine iron oxides.Science2019;365:469-73

[18] Gayen P,Ramani V.Pyrochlores for advanced oxygen electrocatalysis.ACC Chem Res2022;55:2191-200

[19] Lv X,Wang H,Dai Y.Multifunctional electrocatalyst PtM with low Pt loading and high activity towards hydrogen and oxygen electrode reactions: a computational study.Appl Catal B2019;255:117743

[20] Cui X,Ma C.Robust interface Ru Centers for high-performance acidic oxygen evolution.Adv Mater2020;32:e1908126

[21] Kwon J,Choi S.Tailored electronic structure of Ir in high entropy alloy for highly active and durable bifunctional electrocatalyst for water splitting under an acidic environment.Adv Mater2023;35:e2300091

[22] Cai J,Zhang L,Ouyang T.Hetero-anionic structure activated Co-S bonds promote oxygen electrocatalytic activity for high-efficiency zinc-air batteries.Adv Mater2023;35:e2303488

[23] Kim C,Kim J.Boosting electrochemical methane conversion by oxygen evolution reactions on Fe-N-C single atom catalysts.Energy Environ Sci2023;16:3158-65

[24] Gao FY.Nickel-based anode catalysts for efficient and affordable anion-exchange membrane fuel cells.ACC Chem Res2023;56:1445-57

[25] Wang L,Deng M.Sustainable aqueous metal-air batteries: an insight into electrolyte system.Energy Stor Mater2022;52:573-97

[26] Zhang W,Wang G.Surface oxygenation induced strong interaction between Pd catalyst and functional support for zinc-air batteries.Energy Environ Sci2022;15:1573-84

[27] Kim S,Yang H.Near surface electric field enhancement: pyridinic-N rich few-layer graphene encapsulating cobalt catalysts as highly active and stable bifunctional ORR/OER catalyst for seawater batteries.Appl Catal B2022;310:121361

[28] Zhu J,Cui T.F doping and P vacancy engineered FeCoP nanosheets for efficient and stable seawater electrolysis at large current density.Appl Catal B2023;328:122487

[29] Stamenkovic V.Markovic N, Ross P. Structure-relationships in electrocatalysis: oxygen reduction and hydrogen oxidation reactions on Pt(111) and Pt(100) in solutions containing chloride ions.J Electroanal Chem2001;500:44-51

[30] Liu K,Lin Y.Insights into the activity of single-atom Fe-N-C catalysts for oxygen reduction reaction.Nat Commun2022;13:2075 PMCID:PMC9018836

[31] An L,Li J.Tailoring oxygen reduction reaction pathway on spinel oxides via surficial geometrical-site occupation modification driven by the oxygen evolution reaction.Adv Mater2022;34:e2202874

[32] Wang N,Hung SF.Strong-proton-adsorption Co-based electrocatalysts achieve active and stable neutral seawater splitting.Adv Mater2023;35:e2210057

[33] Hwang SM,Kim Y.Rechargeable seawater batteries-from concept to applications.Adv Mater2019;31:e1804936

[34] Blake IC.Fiftieth anniversary: the anniversary issue on primary cell: silver chloride-magnesium reserve battery.J Electrochem Soc1952;99:202C

[35] Huang Q,Yang S,Dai Y.Effects of Al and Sn on electrochemical properties of Mg-6%Al-1%Sn (mass fraction) magnesium alloy as anode in 3.5%NaCl solution.J Cent South Univ2014;21:4409-14

[36] Wang N,Peng C,Feng Y.Discharge behaviour of Mg-Al-Pb and Mg-Al-Pb-In alloys as anodes for Mg-air battery.Electrochim Acta2014;149:193-205

[37] Abdulrehman T,Al-ameri S,Abdulla A.Enhancing the performance of Mg-Al brine water batteries using conductive polymer-PEDOT:PSS.Renew Energ2015;82:125-30

[38] Yu K,Wen L.Discharge behavior and electrochemical properties of Mg-Al-Sn alloy anode for seawater activated battery.T Nonferr Metal Soc2015;25:1234-40

[39] Yuasa M,Suzuki K,Chino Y.Discharge properties of Mg-Al-Mn-Ca and Mg-Al-Mn alloys as anode materials for primary magnesium-air batteries.J Power Sources2015;297:449-56

[40] Shi Y,Feng Y,Wang N.Microstructure and electrochemical corrosion behavior of extruded Mg-Al-Pb-La alloy as anode for seawater-activated battery.Mater Des2017;124:24-33

[41] Shi Y,Feng Y,Wang N.Enhancement of discharge properties of an extruded Mg-Al-Pb anode for seawater-activated battery by lanthanum addition.J Alloys Compd2017;721:392-404

[42] Wang L,Feng Y,Wang N.Effect of heat treatment on electrochemical properties of Mg-9 wt.%Al-2.5 wt.%Pb alloy in sodium chloride solution.JOM2017;69:2467-70

[43] Xiong H,Zhang Y.Microstructure and discharge behavior of Mg-Al-Sn-in anode alloys.J Electrochem Soc2017;164:A1745-54

[44] Wu J,Feng Y.Effect of hot rolling on the microstructure and discharge properties of Mg-1.6 wt%Hg-2 wt%Ga alloy anodes.J Alloys Compd2018;765:736-46

[45] Li J,Jing J.Electrochemical behavior of Mg-Al-Zn-Ga-In alloy as the anode for seawater-activated battery.J Mater Sci Technol2020;41:33-42

[46] Wu Z,Zou J.Effect of microstructure on discharge performance of Al-0.8Sn-0.05Ga-0.9Mg-1.0Zn (wt%) alloy as anode for seawater-activated battery.Mater Corros2020;71:1680-90

[47] Xie Q,Jiang J,Saleh B.Discharge properties of ECAP processed AZ31-Ca alloys as anodes for seawater-activated battery.J Mater Res Technol2021;11:1031-44

[48] Huang J,Fang H.Effects of intermetallic phases on electrochemical properties of powder metallurgy Mg-6%Al-5%Pb anode alloy used for seawater activated battery.Mater Res Express2022;9:066504

[49] Zhao C,Yao N.Low-temperature working feasibility of zinc-air batteries with noble metal-free electrocatalysts.Renewa2023;1:73-80

[50] Renuka R.Influence of allotropic modifications of sulphur on the cell voltage in Mg-CuI(S) seawater activated battery.Mater Chem Phys1999;59:42-8

[51] Senthilkumar ST,Han J.Emergence of rechargeable seawater batteries.J Mater Chem A2019;7:22803-25

[52] Prasad K,Mathur P.Preliminary report on the performance characteristics of the magnesium-mercurous chloride battery system.J Power Sources1977;1:371-5

[53] Yu J,Zhao C.Seawater electrolyte-based metal-air batteries: from strategies to applications.Energy Environ Sci2020;13:3253-68

[54] Shinohara M,Mochizuki M,Suyehiro K.Practical application of a sea-water battery in deep-sea basin and its performance.J Power Sources2009;187:253-60

[55] Liu Q,Wang E,Sun G.A high-specific-energy magnesium/water battery for full-depth ocean application.Int J Hydrog Energy2017;42:23045-53

[56] Al-eggiely AH,Gvozdenović MM,Grgur BN.Seawater zinc/polypyrrole-air cell possessing multifunctional charge-discharge characteristics.J Solid State Electrochem2017;21:2769-77

[57] Jiao W,Huang C.Effect of modified polyacrylonitrile-based carbon fiber on the oxygen reduction reactions in seawater batteries.Ionics2018;24:285-96

[58] Zhang Q,Dai W.Chloride ion as redox mediator in reducing charge overpotential of aprotic lithium-oxygen batteries.Batteries Supercaps2021;4:232-9

[59] Kim Y,Jeong S.Large-scale stationary energy storage: seawater batteries with high rate and reversible performance.Energy Stor Mater2019;16:56-64

[60] Kim Y,Park S,Kim Y.Na ion-conducting ceramic as solid electrolyte for rechargeable seawater batteries.Electrochim Acta2016;191:1-7

[61] Kim Y,Jung Y,Kim Y.Development of prismatic cells for rechargeable seawater batteries.Adv Sustain Syst2022;6:2100484

[62] Son M,Kim N,Kim Y.Simultaneous energy storage and seawater desalination using rechargeable seawater battery: feasibility and future directions.Adv Sci2021;8:e2101289 PMCID:PMC8456281

[63] Kim Y,Yu H.Sodium biphenyl as anolyte for sodium-seawater batteries.Adv Funct Mater2020;30:2001249

[64] Han J,Go W,Jeon D.Development of coin-type cell and engineering of its compartments for rechargeable seawater batteries.J Power Sources2018;374:24-30

[65] Xu Y,Lu H.Mg/seawater batteries driven self-powered direct seawater electrolysis systems for hydrogen production.Nano Energy2022;98:107295

[66] Yu J,Liu J,Tang C.Seawater-based electrolyte for zinc-air batteries.Green Chem Eng2020;1:117-23

[67] Wang C,Niu J.Recent progress of metal-air batteries - a mini review.App Sci2019;9:2787

[68] Zhang T,Chen J.Magnesium-air batteries: from principle to application.Mater Horiz2014;1:196-206

[69] Park S,Kim Y,Son M.Investigating the influence of catholyte salinity on seawater battery desalination.Desalination2021;506:115018

[70] Mamtani K,Co AC.Investigation of chloride poisoning resistance for nitrogen-doped carbon nanostructures as oxygen depolarized cathode catalysts in acidic media.Catal Lett2017;147:2903-9

[71] Kim Y,Vaalma C.Optimized hard carbon derived from starch for rechargeable seawater batteries.Carbon2018;129:564-71

[72] Jin Z,Meng Y,Xiao D.Understanding the inter-site distance effect in single-atom catalysts for oxygen electroreduction.Nat Catal2021;4:615-22

[73] Millero FJ,Wright DG.The composition of standard seawater and the definition of the reference-composition salinity scale.Deep Sea Res Part I Oceanogr Res Pap2008;55:50-72

[74] Kim DH,Hwang DY.Reliable seawater battery anode: controlled sodium nucleation via deactivation of the current collector surface.J Mater Chem A2018;6:19672-80

[75] Liu Q,Wang E,Sun G.Aqueous metal-air batteries: fundamentals and applications.Energy Stor Mater2020;27:478-505

[76] Kim D,Lee W,Kim Y.Development of rechargeable seawater battery module.J Electrochem Soc2022;169:040508

[77] Arnold S,Presser V.Dual-Use of seawater batteries for energy storage and water desalination.Small2022;18:e2107913

[78] Kim K,Park J,Kim J.Highly improved voltage efficiency of seawater battery by use of chloride ion capturing electrode.J Power Sources2016;313:46-50

[79] Jung J,Kristanto I,Kang SJ.Deterministic growth of a sodium metal anode on a pre-patterned current collector for highly rechargeable seawater batteries.J Mater Chem A2019;7:9773-81

[80] Lee C,Park J.Tetraruthenium polyoxometalate as an atom-efficient bifunctional oxygen evolution reaction/oxygen reduction reaction catalyst and its application in seawater batteries.ACS Appl Mater Interfaces2020;12:32689-97

[81] Kim J,Lee J,Jo C.Biomass-derived P, N self-doped hard carbon as bifunctional oxygen electrocatalyst and anode material for seawater batteries.Adv Funct Mater2021;31:2010882

[82] Kim J,Kim H.Rechargeable-hybrid-seawater fuel cell.NPG Asia Mater2014;6:e144

[83] Manikandan P,Han J.Advanced perspective on the synchronized bifunctional activities of P2-type materials to implement an interconnected voltage profile for seawater batteries.J Mater Chem A2018;6:11012-21

[84] Kim S,Jeong S.Negative surface charge-mediated Fe Quantum dots with N-doped graphene/Ti₃C₂T_x MXene as chlorine-resistance electrocatalysts for high performance seawater-based Al-air batteries.J Power Sources2023;566:232923

[85] Le Z,Dang Q.A high-power seawater battery working in a wide temperature range enabled by an ultra-stable Prussian blue analogue cathode.J Mater Chem A2021;9:8685-91

[86] Guo Y,Xie RC.The oxygen reduction reaction at silver electrodes in high chloride media and the implications for silver nanoparticle toxicity.Chem Sci2020;12:397-406 PMCID:PMC8178706

[87] Hasvold Ø,Melv˦r E.Sea-water battery for subsea control systems.J Power Sources1997;65:253-61

[88] Li J,Liu K,Hou B.Efficient electrocatalytic H₂O₂ production in simulated seawater on ZnO/reduced graphene oxide nanocomposite.Colloids Surf A Physicochem Eng Asp2023;668:131446

[89] Shao M,Dodelet JP.Recent advances in electrocatalysts for oxygen reduction reaction.Chem Rev2016;116:3594-657

[90] Nie Y,Wei Z.Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction.Chem Soc Rev2015;44:2168-201

[91] Ryu JH,Park J.Carbothermal shock-induced bifunctional Pt-Co alloy electrocatalysts for high-performance seawater batteries.Energy Stor Mater2022;45:281-90

[92] Jin C,Xia W,Schuhmann W.Polythiophene-assisted vapor phase synthesis of carbon nanotube-supported rhodium sulfide as oxygen reduction catalyst for HCl electrolysis.ChemSusChem2011;4:927-30

[93] Chen Y,Weiler E,Artyushkova K.Mechanism of oxygen reduction reaction on transition metal-nitrogen-carbon catalysts: establishing the role of nitrogen-containing active sites.ACS Appl Energy Mater2018;1:5948-53

[94] Gu W,Li J.Recent advancements in transition metal-nitrogen-carbon catalysts for oxygen reduction reaction.Electroanalysis2018;30:1217-28

[95] Zhao C,Wang J.Regeneration of single-atom catalysts deactivated under acid oxygen reduction reaction conditions.J Energy Chem2022;73:478-84

[96] Liu M,Cao S.A “pre-constrained metal twins” strategy to prepare efficient dual-metal-atom catalysts for cooperative oxygen electrocatalysis.Adv Mater2022;34:e2107421

[97] Suh DH,Nakhanivej P,Hwang SM.Hierarchically structured graphene-carbon nanotube-cobalt hybrid electrocatalyst for seawater battery.J Power Sources2017;372:31-7

[98] Wu S,Mao H.Realizing high-efficient oxygen reduction reaction in alkaline seawater by tailoring defect-rich hierarchical heterogeneous assemblies.Appl Catal B2023;330:122634

[99] Gao Z,Qiu P.p-type plastic inorganic thermoelectric materials.Adv Energy Mater2021;11:2100883

[100] Zhan Y,He F.Active site switching of Fe-N-C as a chloride-poisoning resistant catalyst for efficient oxygen reduction in seawater-based electrolyte.Chem Eng J2022;443:136456

[101] Li H,Guevarra D.Analysis of the limitations in the oxygen reduction activity of transition metal oxide surfaces.Nat Catal2021;4:463-8

[102] Son M,Im E.Sacrificial catalyst of carbothermal-shock-synthesized 1T-MoS₂ layers for ultralong-lifespan seawater battery.Nano Lett2023;23:344-52

[103] Zhang Y,Senthilkumar ST.A novel rechargeable hybrid Na-seawater flow battery using bifunctional electrocatalytic carbon sponge as cathode current collector.J Power Sources2018;400:478-84

[104] Tu NDK,Park J,Kwak SK.Pyridinic-nitrogen-containing carbon cathode: efficient electrocatalyst for seawater batteries.ACS Appl Energy Mater2020;3:1602-8

[105] Zhang F,Wu L,Ren Z.Rational design of oxygen evolution reaction catalysts for seawater electrolysis.Trends Chem2021;3:485-98

[106] Dresp S,Klingenhof M.Direct electrolytic splitting of seawater: opportunities and challenges.ACS Energy Lett2019;4:933-42

[107] Vos JG,Jeremiasse AW.MnO_x/IrO_x as selective oxygen evolution electrocatalyst in acidic chloride solution.J Am Chem Soc2018;140:10270-81 PMCID:PMC6099550

[108] Kim S,Han S,Kim C.Ir_0.11Fe_0.25O_0.64 as a highly efficient electrode for electrochlorination in dilute chloride solutions.J Ind Eng Chem2021;102:155-62

[109] Kim Y,Lee J,Kim Y.Design of large-scale rectangular cells for rechargeable seawater batteries.Adv Sustain Syst2021;5:2000106

[110] Hansen HA,Studt F,Bligaard T.Electrochemical chlorine evolution at rutile oxide (110) surfaces.Phys Chem Chem Phys2010;12:283-90

[111] Komiya H,Takanabe K.Electrolyte engineering for oxygen evolution reaction over non-noble metal electrodes achieving high current density in the presence of chloride ion.ChemSusChem2022;15:e202201088 PMCID:PMC9804667

[112] Zhao X,Shi Y.Exploiting interfacial Cl^-/Cl⁰ redox for a 1.8-V voltage plateau aqueous electrochemical capacitor.ACS Energy Lett2021;6:1134-40

[113] Vos JG,Speck FD.Selectivity trends between oxygen evolution and chlorine evolution on iridium-based double perovskites in acidic media.ACS Catal2019;9:8561-74

[114] Dionigi F,Pawolek Z,Strasser P.Design criteria, operating conditions, and nickel-iron hydroxide catalyst materials for selective seawater electrolysis.ChemSusChem2016;9:962-72

[115] You H,Si D.Monolayer NiIr-layered double hydroxide as a long-lived efficient oxygen evolution catalyst for seawater splitting.J Am Chem Soc2022;144:9254-63

[116] Enkhtuvshin E,Kim Y.Stabilizing oxygen intermediates on redox-flexible active sites in multimetallic Ni-Fe-Al-Co layered double hydroxide anodes for excellent alkaline and seawater electrolysis.J Mater Chem A2021;9:27332-46

[117] Zhang K.Advanced transition metal-based OER electrocatalysts: current status, opportunities, and challenges.Small2021;17:e2100129

[118] Ibrahim KB,Chala SA.A review of transition metal-based bifunctional oxygen electrocatalysts.J Chin Chem Soc2019;66:829-65

[119] Wang J,Liu J.Composing atomic transition metal sites for high-performance bifunctional oxygen electrocatalysis in rechargeable zinc-air batteries.Particuology2023;77:146-52

[120] Yu L,Song S.Non-noble metal-nitride based electrocatalysts for high-performance alkaline seawater electrolysis.Nat Commun2019;10:5106 PMCID:PMC6841982

[121] Kuang Y,Meng Y.Solar-driven, highly sustained splitting of seawater into hydrogen and oxygen fuels.Proc Natl Acad Sci USA2019;116:6624-9 PMCID:PMC6452679

[122] Zhao Y,Zheng Y,Jiao Y.Charge state manipulation of cobalt selenide catalyst for overall seawater electrolysis.Adv Energy Mater2018;8:1801926

[123] Liu J,Shi H.Breaking the scaling relations of oxygen evolution reaction on amorphous NiFeP nanostructures with enhanced activity for overall seawater splitting.Appl Catal B2022;302:120862

[124] Song Y,Liao T,Wu Y.Electronic structure tuning of 2D metal (Hydr)oxides nanosheets for electrocatalysis.Small2021;17:e2002240

[125] Joo J,Lee J,Lee K.Morphology-controlled metal sulfides and phosphides for electrochemical water splitting.Adv Mater2019;31:e1806682

[126] Dutta A.Developments of metal phosphides as efficient OER precatalysts.J Phys Chem Lett2017;8:144-52

[127] Tan L,Wang C.Partial sulfidation strategy to NiFe-LDH@FeNi₂S₄ heterostructure enable high-performance water/seawater oxidation.Adv Funct Mater2022;32:2200951

[128] Zhang H,Ouyang M,Xie F.A self-reconstructed bifunctional electrocatalyst of pseudo-amorphous nickel carbide@iron oxide network for seawater splitting.Adv Sci2022;9:e2200146 PMCID:PMC9131433

[129] Song HJ,Ju B,Kim D.Electrocatalytic selective oxygen evolution of carbon-coated Na₂Co_1-xFe_xP₂O₇ nanoparticles for alkaline seawater electrolysis.ACS Catal2020;10:702-9

[130] Guo J,Hu Z.Direct seawater electrolysis by adjusting the local reaction environment of a catalyst.Nat Energy2023;8:264-72

[131] Kim J,Jeong J.Designing fluorine-free electrolytes for stable sodium metal anodes and high-power seawater batteries via SEI reconstruction.Energy Environ Sci2022;15:4109-18

[132] Bae H,Senthilkumar S,Kim Y.Hybrid seawater desalination-carbon capture using modified seawater battery system.J Power Sources2019;410-11:99-105

[133] Budde-meiwes H,Lunz B.A review of current automotive battery technology and future prospects.J Aut Eng2013;227:761-76