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Figure 11 Schematic representation of (a) a sand battery system, (b) operating principle of the same, (c) typical temperature profile of the system during charging, and (d) discharging.

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Figure 1. (a) Comparison of the different battery technologies in terms of volumetric and gravimetric energy density. Adapted from [17] with permission from Springer Nature. (b) Spider chart for LIBs with various anode and cathode materials. Reproduced from [25]. CC BY 4.0.

Figure 2. (a) Various battery technologies’ relative market share. Source [16]. (b) Application areas of LIBs. Adapted from [18], with permission from Springer Nature. (c) Relative global LIB market share by application. Source [19]. (d) Relative global LIB market share by type. Source [28]. (e) Relative global LIB Market by region. Source [29]. (f) Relative global leaders in LIB production by countries. Source [30]. (g) LIB-related relative publications by country. Source [31].

Table 2. Comparison of Li-ion battery technology.

Table 2. (Continued.)

Figure 3. (a) Schematic classification of various sources for heat generation within a Li-ion battery and their impacts on different components. © 2022 IEEE. Reprinted, with permission, from [23]. (b) Schematic overview of the battery safety issues in terms of various abuses. Reprinted from [33], Copyright 2020, with permission from Elsevier.

Figure 4. (a) Comparison of baseline and reduced pack costs (per kWh-usable basis) of LIBs. Reprinted from [42], Copyright 2014, with permission from Elsevier. (b) Previous analyses of lithium-ion cell price versus time and projections assuming exponential growth in cumulative market size. Previously reported single-factor analyses of lithium-ion cells’ price per energy capacity vs. cumulative market si (e.g. production, installation, sales, etc) as measured in energy capacity. The requisite cumulative market size projections assume exponential growth in cumulative market size, as extrapolated from the market size data used in each analysis. Adapted from [41] with permission from the Royal Society of Chemistry.

Figure 5. (a) Volume-weighted average LIB pack and cell price over the last decade. Source [51]. (b) Number of publications within the last 10 years (2012-2022) reported in “Google Scholar’ with the keywords ‘Conventional Battery Materials’ and ‘Lithium-ion Battery’. (c) Energy density ranges of next the generation ‘beyond LIB’ technologies. Adapted from [55]. © The Author(s). Published by IOP Publishin; Ltd. CC BY 4.0. (d) Number of publications within the last 10 years (2012-2022) reported in ‘Google Scholar’ with keywords ‘Na-ion’, ‘K-ion’, ‘Mg-ion’, and ‘Zn-air’ battery, (e) ‘Li-ion capacitor’, ‘Hybrid supercapacitor’, and ‘Redox flow battery’, (f) “Li-S’, ‘Li-air’, and ‘Li-polymer’ battery. (g) The concept of potential applications of ‘Beyond LIB’ technologies. Adapted from [56] with permission from the Royal Society of Chemistry.

INID/INID WOU be SMahver an that OF LIDS due tO We 1oOWer (more negative) redox potential of Li (—3.05 V vs. SHE) against Ni (—2.71 V vs. SHE) and K (—2.93 V vs. SHE). However, this argument is too simplistic as the redox poten- tial depends on the type of solvent used (large deviation may occur between aqueous and non-aqueous electrolytes), and the properties of the applied electrodes. Even though the electrode potential depends on the half-cell configuration, to obtain a high full-cell voltage, suitable intercalation electrodes need to be selected for which the negative one releases very little energy during interaction with Na/K ions (redox potential close to Na/Nat or K/K* = 0 V) while the positive elec- trode releases a large amount of energy during interaction with Na/K ions (redox potential much positive than Na/Na* or K/K* = 0 V). This indicates that the cell voltage (E..1)) is dependent on the Gibbs energy change of the cell reaction (AG®), according to the following well-known relation [70] V.2.9. YWaAUIUUS IHIaleridalo. LU AUIOUe CUOMIOMEHL Plays PiVOtdalL role on the performance of NIBs/KIBs, and it accounts for 1/3rd of the total expense of the battery pack [79, 80]. Intensive R&D activities are going on around the globe to explore appro- priate cathode materials having distinct structures. Amongst three types of cathode materials (such as LTMO, polyanionic compound, and PBA), LTMOs are used extensively, as they can accommodate the higher ionic radii of Nat/K* (against Lit) within the interlayer spacings during intercalation, to withstand the volume expansion [72], leading to higher capa- city than the others. But the aforementioned volume expan- sion sometimes leads to poor stability of the cathode. However, polyanion-based and PBA cathodes show longer stability, and higher working voltage due to the inductive effect and strong covalent bonds to form stable framework [74]. Especially, the PBA systems show higher volumetric as well as gravimetric energy density against LTMOs and polyanion-based cathodes with increasing alkali-ion size [38]. This implies that, com- paratively, for KIBs, PBAs work best, while LTMOs perform- ance are relatively better for LIBs, whereas polyanionic cath- odes perform well in Na-systems. Obviously, this is a general notion, and with proper modulations, these electrodes can be optimized for best performance in NIB/KIB systems too. Few types of NIB/KIB cathodes are shown in table 4. Rest can be found in the following references [56, 66, 67, 71, 73, 75, 76, 80-90].

Figure 6. Spider chart about the performance, cost, safety and sustainability of (a) LIBs (Red: LFP, Purple: NMC), (b) NIBs, (c) KIBs (Blue: experimental values, Green line: theoretical values). Adapted from [64]. CC BY 4.0. (d) Schematic structure of NIB/KIB. [70] John Wiley & Sons. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (e) Crystal structures of NIB/KIB cathodes: (1) LTMO — P2-Ax3MOy, (ii) LTMO-O03-AMOsg, (iii) polyanion AMXOg, and (iv) PBA-AMM/’(CN)¢ [A: Na, K; M/M’: transition metal; X: P, Si, S etc.]. [77] John Wiley & Sons. © 2023 Wiley-VCH GmbH. Adapted with permission from [77]. (f) Tabular comparison of the performance of LTMOs, polyanions, and PBAs. Source [73]. (g) Schematic diagram of MXene. From [78]. Reprinted with permission from AAAS.

Table 4. Various type of cathode materials used in NIBs/KIBs.

Figure 7. (a) Technical issues related to ASSB optimization. Reprinted (adapted) with permission from [199]. Copyright 2020 Americ Chemical Society. (b) Schematic diagram of a single-phase Na-ASSB. [201] John Wiley & Sons. © 2016 WILEY-VCH Verlag GmbH Co. KGaA, Weinheim. (c) Schematic representation of various issues related to Na/K-S batteries. [202] John Wiley & Sons. © 2020 Wiley-VCH GmbH.

Figure 8. Comparison of the electrochemical characteristics of (a) LiCs, Li and polyvalent metal anodes, (b) M-K batteries, consisting of M (=LiCg, Li, Mg, Ca, Zn, Al) anodes and K (=Mn2Ozu, S) cathodes. (c) Typical plating morphologies of polyvalent metal-ion metallic anodes having compact crystals, (d) tree-like dendrites, (e) connected platelets, (f) random fibers, (g) connected spheres. Adapted from [229], with permission from Springer Nature. (h) Schematic diagram of a RFB system. (i) Comparison of the cost of flow batteries with some other high-performance batteries. Source: Saudi Aramco [230]. (j) Electrodes with (a)‘flow-through’ and (b) ‘flow-by’ design. Adapted from [231], Copyright 2016, with permission from Elsevier. (k) Membrane-less flow-cell with (a) single-phase co-laminar design, (b) flow-separating electrolyte cell designs for RFBs. Adapted from [232], Copyright 2016, with permission from Elsevier.

maintained without the negative and positive active materials coming into direct contact with each other. During charging, electrons released at the positive electrode (through oxidation of the electroactive species in that half-cell) are pushed round the external circuit to the negative electrode (where reduction of electroactive species in that half-cell takes place). The pro- cesses are reversed on discharge, and the cell voltage is con- stituted through the voltage difference between the negative and positive electrode reactions [289-291]. The electroactive materials are redox pairs, i.e. chemical compounds that can reversibly undergo reduction and oxidation, such as V/V (four different vacancy states of V, cf figure 8(h)), Fe/Cr, Zn/Br etc. On the other hand, most RFBs use carbon electrodes, which do not participate in the energy conversion reactions. Generally, in RFBs, glassy carbon, pristine graphite, non- activated graphite felt etc. are used, which exhibit expectedly low electric double layer capacitor (EDLC) behavior, due to the absence of defects and primary exposure of basal planes, and hence negligibly affect the overall electrochemical per- formance. However, chemical, and thermal activation of these electrodes to incorporate functional groups to improve redox activity sometimes increase the EDLC behavior due to the introduction of greater number of defects. But its influence is also marginal as these double layers do not provide relevant active sites for increase in the redox reactions to the same extent, and hence, does not affect the overall electrochemical performance significantly [292]. Also, these electrodes do not cause any side reactions (like undesirable byproducts, and gas formation) to deteriorate the battery performance [230, 293-300]. The generalized electrochemical process in RFBs can be summarized using A/A™~ as the negative, and B/B™ as the positive redox pairs {with E°(A/A~) < E°(B/B~)}, con- tained within the respective electrolytes (called anolyte and catholyte), where the reactions take place on the electrode- electrolyte interface as follows [295]: where, V°+/V** oxidation states are composed of the pair VO/VO"*, respectively. As described in figure 8(h), during charging, V*+ is oxidized to V**, losing one electron which is driven to the other half cell where it reacts with V**, reducing it to V+. State-of-charge (SoC) for the battery is defined as the percentage of charged species (V°+ and V*+) in respect to the discharged species (V*+ and V7+). Cations X+ (e.g. H*) pass through the membrane to maintain the charge neutrality. Opposite process occurs during discharge, creating a discharge potential [295]: RFBs are electrochemical storage systems that consists of two separate liquids (anolyte and catholyte in separate tanks) flowing (through pumps) on either side of an ion-selective/ion- exchange membrane within a flow cell (cf figure 8(h)), where the chemical energy contained within the system converts to electrical energy via ion exchange through the membrane, accompanied by current flow through an external circuit/load. Fundamentally, the flow cells on either side of the porous membrane act as half cells and the redox reactions during charge and discharge take place at the electrodes of the half cells. The ion-permeable membrane or separator ensures that the liquids of the half cells mix as little as possible and a charge balance between positive and negative half cells is

Figure 9. (a) Schematic comparison of LIB (A) vs. FIB (B). Adapted from [365], Copyright 2021, with permission from Elsevier. (b) Schematic structure of an FIB. (c) Crystal structures of various binary fluorides. Adapted from [365], Copyright 2021, with permission from Elsevier. (d) Schematic structure of Ruddlesden—Popper [(AMO3),AO] crystal, for n = 1 (left), fully fluorinated [(AMO3),AO] crystal, for n = 2 (middle), and same for n = 3 (right). Adapted from [364] with permission from the Royal Society of Chemistry. (e) Schematic structure of Schafarzikite-type (MSb2Ox) crystal (left) and fluorinated MSb2O4F, crystal (right). Not to scale. [369] John Wiley & Sons. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Figure 10. (a) Schematic structure of an AIB. (b) Schematic view of various host materials used in AIBs. [409] John Wiley & Sons. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. (c) The NH? ion extraction/insertion mechanism in an MnAI-LDH cathode is illustrated schematically. [410] John Wiley & Sons. © 2022 Wiley-VCH GmbH.

Figure 12. (a) Schematic diagram of a hydrogen fuel cell. (b) Membrane-electrode-assembly schematic. (c) Various water movements within a PEMFC.

Figure 13. (a) Various aspects of Hydrogen Economy. (b) Number of publications within the last 10 years (2012-2022) reported in ‘Google Scholar’ with the keywords ‘Hydrogen Fuel Cell’, and ‘Hydrogen Economy’ (a dip is 2022 is probably due to the post-pandemic effect), (c) ‘Hydrogen production by electrolysis’ and ‘Hydrogen production by photoelectrochemical’ processes.

Table 5. Hydrogen production via different pathways. solar and wind power generation makes hydrogen production via renewables cheaper. All these lead to an increment in the production of green hydrogen, and projected to a market value of $108.64 billion by 2031. Also, the number of publications on the production of green hydrogen (via electrolysis and pho- toelectrochemical methods) has increased steadily over the last decade, as shown in figure 13(c), indicating its great potential for the development of a sustainable future [495-500]. Chemical method of hydrogen storage is a materials-based hydrogen storage system, where the hydrogen gas interacts with the storage media. This interaction can be weak van der Waals force or moderate Kubus interaction or strong ionic/covalent bond formation. Chemical method recently gained considerable attention due to the fact that hydrogen storage capacity of certain materials is considerably higher than that of compressed, cryo-compressed and/or liquified hydrogen storage methods. Typically, chemical method can be categorized into (1) solid-state storage, and (2) chem- ical storage (cf figure 14). The solid-state storage techno- logy involves on-board regenerable materials, which means the storage material can be re-charged by hydrogen on-board a vehicle, whereas in chemical storage, this hydrogen rechar- ging should be done off-board, in a centralized facility, due to unfavorable kinetics and/or thermodynamics of the gas- solid system. Apparently, on-board regeneration is conveni- ent, simple, and cost-effective than that of off-board regenera- tion, and hence, solid-state storage materials are preferred over chemical storage materials. The solid-state hydrogen storage materials (on-board regenerable) can further be divided into (i) reversible hydrides, and (ii) physisorption materials. The reversible hydrides are based on strong interactions between the hydrogen and the host, where the host can be a metal or bimetallic alloy, like MgH2, ZrMn2H,2 (AB>-type alloy), Mg 2NiHy (A2B-type alloy), FeTiH2 (AB-type alloy), LaNisHe (ABs-type alloy), etc. In this type of materials, the chem- ical bonds are having both covalent and ionic characters and the hydrogen atoms are located at the interstitial positions of the crystal lattice sites of the metal hydride. The major issues with this type of reversible hydrides are low gravi- metric capacity, high temperature synthesis, high operating temperature, high cost of rare-earth metals, among others. To overcome these shortcomings, some complex hydrides are investigated which are mainly doped versions of lighter metal

Figure 15. (A) Number of publications over the last 10 years (2012—2022) reported in ‘Google Scholar’ with the keywords ‘Hydrogen Physisorption Materials’, ‘Physical Storage of Hydrogen’ and ‘Chemical Storage of Hydrogen’; (B) ‘Hydrogen Economy & Nanotechnology, and ‘Hydrogen Economy & Graphene’. (C) Schematic representation of the hydrogen storage mechanism of metal-incorporated graphitic microporous network. Hydrogen storage and electron hopping mechanism in the micropores of activated carbon (a), and within the inter-layer spacing of graphene walls (b); hydrogen spill-over mechanism on metal nanoparticles and corresponding hydrogen diffusion within the graphene layers (c), and breaking of 7t-bonds in graphene during hydrogen uptake to conver into hydrogenated graphene (d). Adapted from [505], Copyright 2013, with permission from Elsevier.

Figure 16. Periodic table of elements with approximate price and charge capacity of each element at the indicated oxidation state. Adapted from [366], with permission from Springer Nature.