Dr Arnaud J Perez

Prof. j.-M Robin Beer

Dr Zifeng Lin

Dr Elodie Salager

Pierre-Louis Ta Berna

Artem M Abakumov

Patrice Simon

Jean-Marie Tarascon
email: jean-marie.tarascon@college-de-france.fr

Prof. j.-M Tarascon

Prof P.-L P Taberna

Prof. j.-M P Simon

Prof A M Abakumov

Proton Ion Exchange Reaction in Li 3 1r0 4 : A Way to New H 3 +x lr0 4 Phases Electrochemically Active in Both Aqueous and Nonaqueous Electrolytes

Keywords: batteries, layered oxides, protons, pseudocapacitors

Progress over the past decade in Li-insertion compounds has led to a new class ofli-rich layered oxide electrodes cumulating both cationic and anionic redox processes. Pertaining to this new class of materials are the Li/Na iridate phases, which present a rich crystal chemistry. This work reports compared to the 200 mA h g-1 of the pres ently used LiNi 0 . 6 Mn 0 . 2 Co 0 . 2 0 2 layered oxide, or NMC 622. Both phases have the same layered structure but solely differ by the presence of Li in the transition metal layers for the Li-rich NMC phases.

on a new protonic iridate phase H 3+x lr0 4 having a layered structure obtained by room temperature acid-leaching ofli 3 1r0 4 • This new phase shows revers ible charge storage properties ofl .5 e-per Ir atom with high rate capabilities

In order to understand the scientific background of the anionic redox process in the complex Li-rich NMC materials containing three competing redox centers, scientists have searched for simplified model compounds. Among them, the Li-based ruthenates and iridates Li 2 M0 3 (M = Ir, Ru), ( 1-3 l which possess a layered structure and can be described as Li-rich oxides Li(Li 1 1 3 M 2 ; 3 )0 2 , show a reversible capacity of 270 mA h g-1 and present a less complex redox chemistry because of a sole redox center M. The synthesis of these phases is well documented as they in both nonaqueous (vs U + /Li) and aqueous (vs capacitive carbon) media. lt is demonstrated that Li-insertion in carbonate LiPF 6 -based electrolyte occurs through a classical reduction process (lr5 + � 1r3 + ), which is accompanied by a well-defined structural transition. ln concentrated H 2 S0 4 electrolyte, this work provides evidence that the overall capacity ofl.7 H + per Ir results from two additive redox processes with the low potential one showing ohmic limitations. Altogether, the room temperature protonation approach, which can be general ized to various Li-rich phases containing either 3d, 4d or Sd metals, offers great opportunities for the judicious design of attractive electrode materials.

Introduction

The field of Li-ion batteries is going through its own paradigm shift with the emergence of the anionic redox process, whereas so far Li-ion batteries were solely relying on cationic redox pro cesses to store energy. The advantages of cumulating cationic and anionic redox processes is exemplified by the numerous studies on the layered Li 1 . 2 Ni 0 .13Mn 0 . 54 Co 0 .130 2 , denoted Li-rich NMC, which exhibits capacity as high as 290 mA h g-capturing of small cations in tetrahedral sites.1 4 l Very recently, we expanded this family of model compounds by reporting on a new member Li 3 IrO 4 , which enables to push the limit of insertion reactions to a new record of 3.5 c per transition metal. Aside the field of batteries, it is worth mentioning that bath Ru/Ir-based oxides have been heavily studied by electro chemists. First, as highly performant water splitting catalysts, showing a low overpotential and high activity for the oxygen evolution reaction (OER).1 5 • 6 l Following the first studies on the formation of an oxide layer at the surface of metallic Ru/ Ir elec trodes, [ 7 , 8 l it was proposed that the reversible redox processes happening in this oxide layer could be used to store energy ,[9, lOJ leading to the development of pseudocapacitors, with IrO 2 or RuO 2 .xH 2 O being among the stellar materials with capaci tances exceeding 800 F g-1,l11l Most of the developments in these fields were done using amorphous, hydrated [ 12 l or high surface area iridium oxides (nanoparticles [ 13 l or nanosheets [ 14 l) in order to maximize the shell contribution while often over looking the bulk contribution to energy storage.

In light of the versatility offered by these Ru(lr)-based com pounds to undergo redox chemical reactions in bath aqueous or organic solvents, it is becoming tempting to further extend the rich crystal chemistry of the Li-based iridate phases to proton-based phases and exploit their electrochemistry. Herein we demonstrate, by focusing on Li 3 IrO 4 , the feasibility to pre pare a new protonated H 3+x lrO 4 phase by room temperature ion exchange of Li for protons in aqueous media. This proto nated phase is shown to present a spectacular reversible electro chemical activity in bath nonaqueous media versus metallic Li and in aqueous media versus activated carbon.

Results

Single phase Li 3 IrO 4 powder was prepared by a previously described ceramic process, which consists in heating a stoichio metric mixture of Ir and Li 2 CO 3 in air at 950 °C for 24 h.1 15 l The resulting powder was stirred in a 0.1 M H 2 SO 4 solution and, after 1 h of stirring, the powder was recovered by centrifugation and washed with distilled water prior to its characterization. Com parative scanning electron microscopy (SEM) pictures of the pristine and recovered powders (Figure 1, inset) indicate the break-up of the initial 10--20 µm aggregates but no impact of the acid treatrnent on the 1-2 µm size primary particles. The powder composition was indirectly obtained via analysis of the reaction supernatant by complementary inductively coupled plasma mass spectrometry (ICP-MS) for the amount of released lithium, and by acid-base titration to determine the amount of remaining protons in solution. By cross-cutting the results of bath meas urements we could deduce the composition H 3 _ 5 Li 0 _ 05 IrO 4 for the recovered sample within the accuracy of the analysis. The completion of the exchange reaction was confirmed by the absence of 7 Li signal in the solid-state nuclear magnetic reso nance (NMR) spectrum (Figure Sla, Supporting Information), indicative of the absence of Li in the exchanged sample.

The X-ray powder diffraction pattern of the Li-free sample shows sharp Bragg peaks characteristic of a well crystallized material (Figure lb). All the peaks could be indexed in a hex agonal R3m unit cell, as for the parent phase, with however a main difference in the stacking sequence which is P3 for the H 3+ x1rO 4 phase as opposed to 03 for the precursor Li 3 IrO 4 phase (Figure lc,d). The a lattice parameter slightly increases from 2.96 A for Li 3 IrO 4 to 3.04 A for H 3+x lrO 4 , while the c parameter shows a greater decrease from 14.40 to 14.07 A as expected since H + is smaller than u + . Within the O3-Li 3 IrO 4 structure, or Li(Li 1 1 2 Ir 1 1 2 )O 2 , u + sits in octahedral sites with 1/3 being located in the metal layers and the remaining 2/3 between the layers, but no precise dues can be obtained from the X-ray powder diffraction (XRD) powder pattern regarding the proton positions. To obtain information on the sites accu pied by protons, deuterated D 3 + x lrO 4 samples were prepared for NMR studies. The thermal stability of the H 3+x irO 4 phase was investigated by combined thermogravimetric analysis (TGA) and MS meas urements by heating a sample under Ar to 1000 °C at a rate of 5 K min-1 while analyzing the released gases. The TGA profile for H 3+x irO 4 (Figure 2a) shows a staircase behavior with three consecutive steps at 190, 700, and 900 °C, corresponding to the departure of H 2 O for the first step and of 0 2 for the two remaining ones (Figure 2b), with the products obtained at 500 and 1000 °C being IrO 2 and Ir, respectively, as deduced from XRD of the recovered powders (Figure 2c). From the weight loss, and knowing the final products, we could deduce that the formula of the sample is H 3 .41rO 4 • The H + content exceeding three cannot be explained by a simple ion exchange reaction which does not involve a redox process. Due to the high redox potential of the H 3 IrO 4 phase, as we will see later, the material oxidizes water hence leading to a reduced H 3+x lrO 4 phase with x being slightly pH dependent. To further characterize the pro tons within the sample and their existence as either OH groups or H 2 O, infrared (IR) spectroscopy measurements were done. Note the presence of bands associated to Li carbonate impu rities in Li 3 IrO 4 that disappear after acid-leaching (Figure S2, Supporting Information), but to our surprise no bands appear around 1600 and 3600 cm-1; wavelength domains over which the OH groups are IR-active. The absence of such bands could simply be nested in the metallic character of H 3 .4lrO 4 which prevents, for absorption reasons, the detection of OH group, as previously put forward to explain the inability to detect the OH bands in the metallic Li 1 _ x H x MO 2 phase.11 7 l Having established the structural/physical properties of H 3 _ 4 IrO 4 , we next probe its electrochemical activity versus u + /Li in nonaqueous media and versus capacitive carbon in aqueous electrolyte.

The electrochemical performances of H 3 .4IrO 4 were meas ured in organic electrolyte versus Li in Swagelok cells between 1.5 and 4.2 V at a C/10 rate. Remarkably, the cell can reversibly uptake 1.5 u + with limited polarization (Figure 3a) and shows the feasibility to deliver 75% of its energy density at a rate of 1 C (Figure Je). Moreover, the voltage profile varies smoothly with the removal/uptake of Li but also shows a narrow plateau at nearly 3.2 V, which can nicely be visualized on the derivative curve dQ/dY (Figure 3c) and is indicative of a phase transition.

To better understand Li-driven structural changes in (Li,Hh, 4 lrO 4 , in situ XRD measurements were conducted (Figure 4) and XRD patterns were collected with 0.05 step in the lithium stoichiometry. The collected patterns are shown as 2D contour plots in Figure 4a. As an Li/LixH 3 .41rO 4 cell is dis charged, we observed initially a slight shift of position and then a drastic change in the intensity of the peaks near x = 0.6, with some peaks disappearing at the expense of new ones, which sharpen beyond x = 0.7 to give a well-defined XRD powder pattern that remained till the end of the insertion process at x = 1.5 (Li 1 .5H 3 _ 4 IrO 4 ). Refined XRD patterns demonstrate a Li-driven structural transition, which is accompanied by a change in the stacking sequence from P3 to Tl, with the cor responding variation of lattice parameters shown in Figure 4c. There is nearly a continuous increase of the lattice parameter upon reduction, which is consistent with the increase in the Ir ionic radii associated to its sequential Ir 5+ ➔ Ir 4+ ➔ Ir 3+ reduction. By contrast, the interlayer distance (d) remains nearly constant till the P3-Tl transition where it severely drops from 4.68 to 4.52 A due to the migration of the u + ions from prismatic to tetrahedral sites. Further lithiation up to x = 1.5 compensates this contraction with an increase of the interlayer distance d back to 4.71 A. Such a Li-driven prismatic-tetrahedral ., .

,:-•-■ -.

,,,,>, , ..__ transition, which is fully reversed upon the removal of one u + from the Tl phase, is indicative of a reversible Li insertion deinsertion process. This is fully confirmed by the remark able similarity between the XRD patterns of the pristine and discharged/charged electrode (Figure S3, Supporting Informa tion). Lastly, bath 7 Li and 2 H NMR signal evolutions were mon itored during the Li-insertion into D 3 .4IrO 4 • Surprisingly, the 2 H signal disappears for Li 1 .sD 3 .41rO 4 , but can be explained by the strong interaction with the Ir4+ unpaired electrons. Similarly, this should cause the disappearance of the 7 Li NMR signal. This is not the case since Li 1 . 5 D 3 . 4 IrO 4 shows an intense peak near 0 ppm (Figure Sl, Supporting Information), quite more intense than in the pristine material, which is characteristic of a diamagnetic material (i.e., without Ir). Altogether, these two observations indirectly suggest that upon reduction of D 3 .41rO 4 , there is in parallel to the insertion process the growth of a lithi ated amorphous phase containing little Ir and no deuterium.

One reasonable explanation for this signal is the deposition of nondeuterated electrolyte decomposition products at the sur face of the positive electrode.

In a separate experiment, we tested the electrochemical behavior of H 3 .4IrO 4 in aqueous media using three-electrode PFA Swagelok cells with glassy carbon plungers as current collectors. The same polytetrafluoroethylene (PTFE) laminated electrodes, as described before, were used and assembled against negative electrodes containing capacitive carbon (YPS0) in excess with an Hg/Hg 2 SO 4 reference electrode, all of which was immersed in 1 M H 2 SO 4 water solution. The electrodes were cycled either in galvanostatic mode or by cyclic voltammetry.

Figure 3b shows the variation of the potential as a fonction of x. Upon reduction (discharge) from the open circuit voltage (OCV) (0.5 V vs Hg/Hg 2 SO 4 ) to -0.2 V, the material can uptake one H + (H 4 .4lrO 4 ) while, on the following oxidation (charge) up to 0.8 V, 1.7 H + are removed ("H 2 .7lrO/). 2 H NMR performed

�«è' Q) - 2! '° 4.6
]! C:

.El .!:: Once the first cycle is achieved, the electrode can reversibly uptake 1.7 protons with minor polarization between oxidation and reduction curves, suggesting a rapid and reversible H + release/uptake. Worth mentioning is that by starting the elec trode on oxidation we can nearly remove 0.7 H + as well. As an indication, from simple charge counting, this implies that on reduction H 3 _ 4 Ir 0 _ 6 5+ Ir 0 _/+O 4 will transform to H 4 _ 4 Ir 0 _/ + Ir 0 } + O 4 which will be oxidized to H 2 .7Ir 0 _l + Ir 0 }+O 4 upon full oxidation.

CVs collected at 1 mV s-1 between -0.1 and 0.8 V versus Hg/Hg 2 SO 4 (Figure 3d) show several redox peaks confirming a large electrochemical activity which can be estimated to a reversible uptake of 1.7 protons as determined by galvano static cycling. Strikingly, the CV obtained after 5000 cycles at 20 mV ç 1 neatly superimposes with the first one, indicative of an amazingly reversible redox process not too common at such level for battery materials (Figure S4, Supporting Informa tion). Finally, the rate capability of the material was measured from 1 to 1000 C. It reveals the high-power performances of the electrode, which can sustain a capacity of 130 mA h g-1 up to 100 mV ç 1 ("'400 C) when the electrode thickness is decreased from 150 to 30 µm (Figure 3f). This value competes favorably with pseudocapacitive performances of transition metal car bides (also known as MXene), which can uphold "'92 mA h g-1 up to 100-200 mV ç 1 for electrodes of comparable thickness and loading.11 8 1 However, alike the MXene or other pseudoca pacitive materials, the rate capability ofH 3 .4IrO 4 is, as expected, largely depending on the electrode design. An even more drastic consequence of the electrode design was observed by testing Swagelok cells containing "'1 mg of active material powder with and without carbon additive. In the presence of carbon, both the low and the high potential processes appear, whereas in the absence of car bon we can solely trigger the capacity of the high potential domain (Figure SS, Supporting Information).

To understand the kinetic differences between the low and the high potential processes, Swagelok cells using thin films as positive electrodes were further assembled. Cyclic voltammo grams were collected up to scan rates of 50 mV ç 1 at first over the full potential range (Figure Sa) and then independently over the low and the high potential range (Figure Sb,c). Both the low and the high potential regions show kinetic limitations as can be seen from the increasing polarization of anodic and cathodic processes (peaks moving to the right or the left in oxidation and reduction, respectively) whatever these potential ranges are swept independently or together. However, noticeable dif ferences can be observed by focusing on the slope of the oxida tion and the reduction curves at various rates (Figure 5, bottom) with namely greater rate polarization dependence for the lower potential domain compared to the high potential one. This observation, combined with the disappearance of the low poten tial domain without carbon, strongly suggests that the kinetic of the low potential process is under ohmic control. Interesting to note is the symmetry of the polarization for the high potential domain as opposed to an asymmetric one for the low potential domain, with the kinetic being more sluggish on oxidation than on reduction. This is indicative of a different ohmic limitation on charge and discharge, which is most likely linked to changes in the electrode conductivity, as will be discussed later.

To get rid of the ohmic limitations at high scan rates and better assess the kinetics of the material itself, we repeated the aforementioned experiments using a cavity microelectrode (CME), which presents several advantages compared to con ventional Swagelok set-ups. First, neat active material powders can be used free from any binder. Besides, the feasibility to use only a few micrograms of active material helps to achieve high cycling rates since ohmic drop is negligible for the low current flowing in the electrode. As shown in Figure S6 (Supporting Information), ohmic limitation are effectively negligible from 1 to 200 mV ç 1 for all processes, except for the anodic process of the low potential region, whose kinetic seems limited by the (poor) electrical percolation inside the active material.

To fully sort out the origin of the kinetic limitation in the low potential domain, we decided to run step potentio static intermittent transient technique (PITT) potentiostatic experiments i 19 l using conventional Swagelok cells in the -0.4 to +0.8 V versus Hg/Hg 2 SO 4 range. During each potentiostatic step, the current was recorded versus time and then integrated to calculate the electrode capacity at different equivalent poten tial scan rates (see the Experimental Section). As a result, we could recalculate and replot cyclic voltammetry curves at dif ferent potential scan rate. Those CVs calculated from potentio static experiments (Figure 6) differ from real CV experiments shown in Figure 5 in the way that ohmic contribution is mini mized using a potentiostatic technique. We considered the cur rent at each potential from the recalculated CVs as the sum of a nondiffusion-limited (surface) and a diffusion-limited (bulk) processesl 2 0-- 22 l (1)

where the nondiffusion-limited redox contribution is defined by the k 1 coefficient, associated with electrochemical processes occurring onto accessible surface sites, and the k 2 coefficient represents bulk diffusion-limited redox processes. Finding the values of k 1 and k 2 at each potential allows for the separation of the nondiffusion and diffusion currents (orange and blue in Figure 6, respectively). The area under the CV is the sum of the blue and orange areas. First, the CV envelop is consistent with the experimental CVs plotted in Figure 5 under conventional dynamic conditions, validating the experiments. Furthermore, Figure 6 shows that the electrochemical kinetics of the low and the high potential processes are equivalent since the ratio of their respective area are roughly similar at each scan rates, for both the diffusion limited and the nondiffusion limited contri butions. These results unambiguously support the existence of an ohmic limitation in the low potential domain in Figure 6 rather than an electrochemical kinetic limitation.

At this stage a legitimate question regards the mechanistic of such low and high potential processes which, in light of the aforementioned results, are most likely not capacitive. To grasp further insights into this issue, in situ XRD measurements were done using a similar cell as before with the exception that the Be window, which cannot chemically resist acidic electro lyte, was replaced by a Kapton film, hence we reconfigured the positive electrode compartment (see the Experimental Section). We follow a similar experimental protocol as before (XRD pat tern taken for every step in �x of 0.05). The 2D contour plot representation of the collected data (Figure 3b) shows a smooth and continuous displacement of the Bragg peaks toward lower angles upon reduction to -0.2 V, indicative of a proton-driven solid solution insertion process. This process is perfectly revers ible as the Bragg peaks move back toward their initial position by switching the current. Refinement of the collected patterns indicates that the P3 stacking is preserved through the process, with however a decrease in both a and c lattice parameters when the potential is increased to 0.4 V and a flattening toward the end. Altogether, these results prove that the electrochemical activity at low potential is simply due to a classical insertion deinsertion reaction.

The upper potential domain turns out to be more difficult to explore as we could not reach oxidation potentials greater than 0.5 V with our cell hardware because of copious water decom position. To circumvent these difficulties, we returned to ex situ measurements where an electrode was polarized to 0.8 V in Teflon Swagelok cells, the glassy carbon current collector was recovered with the working electrode and directly measured by XRD without further processing (Figure S7, Supporting Infor mation). No change in lattice parameters was detected, sug gesting that the high potential storage process does not imply structural changes. To comfort the robustness of such a daim and ensure absence of experimental artefacts, the potential of the sample was measured again in an electrochemical cell after XRD and nearly the same potential was measured at OCV. Lastly, and for sake of completion, it is worth mentioning that identical results were obtained using HCl rather than H 2 SO 4 as electrolyte. andc) the high potential regions. The beginning of cathodic and anodic processes for both regions is highlighted and show little polariza tion, except for the anodic process in the low potential region (left) which starts to polarize even at low scan rates.

Discussion

We have reported a new chemical aspect of the Li-based iridates that is their great aptitude to form protonic phases as dem onstrated with the formation of H Li 3 lr0 4 (A) H3_4lr04 (B) The metal cations and oxygens are shown as gray and red spheres, respectively. The "out-of-plane" and "in-plane" proton positions are colored with dark blue and cyan, respectively. Thick and thin bonds denote short covalent 0-H and long hydrogen bonds, respectively.

1 1 1 1 F B 1 1 1 • A 0 0 Acid A C 8 leaching C A 1 1 t 1 1 : • C • B 0 0 0 1 1 1 1 t 1 1 1 F B . .J .... J A O3stacking
insertion of Li + or H + , respectively. Therefore, getting insights into the local positioning of the different guest ions, namely H + , is quite complex, owing to their transparency to XRD, as well as to the large incoherent neutron scattering of H + , which can be overcome by using deuterated samples. In absence of such measurements, a valuable alternative consists in looking for possible proton location among the known structures of layered hydroxides such as CrOOH, which adopts a P3 struc ture (Figure Sa). T yp ically, protons form strong covalent bond to one oxygen atom, with a typical length of se0.85-1.0 A, and one weaker "hydrogen'' bond to another oxygen atom, which has more electrostatic nature and a length that can vary between 1.5-2.5 A. In CrOOH, protons occupy "out-of-plane" position between two successive (CrO 2 ) octahedral layers being doser to one O atom (d(O-H) = 1.05 À) and more distant from the 0 atom from the neighboring layer (d(O-H) = 1.53 A)J2 3 l Thus a linear 0-H-O fragment is formed. Tuming to the protons within the metal layers, their position at the Li octahedral sites is quite unlikely. A more likely location could be deduced from the known hydroxide Al(OHh, which surprisingly has a very similar structure to Li-rich layered oxides with honeycomb orderingJ 24 l In this structure, the hon eycomb ordering of the Al-filled and vacant oxygen octahedra within the (AlO 3 ) layers provides extra "in-plane" proton posi tions, sitting almost within the oxygen close packed layers, with one short 0-H bond of O. 94-1.0 A and another longer one of 2.11-2.43 A to the oxygen atoms of the same layer (Figure 8b). To gether, the "out-of-plane" and "in-plane" proton positions can account for the hydrogen atoms in H 3 . 4 IrO 4 .

Now moving to the inserted compound, we should recall that the insertion of Li in Li 3 IrO 4 has led to a phase change through which the Li-ions move from octahedral to tetrahedral sites. Along that line it does not corne as a surprise that the insertion of 1.5 Li + in H 3 .4IrO 4 triggers a P3 to Tl structural transition with the extra Li + occupying the tetrahedral sites. As we suspect that 7 Li and 2 H NMR signals from the materiafs bulk are not visible due to the vicinity of paramagnetic Ir4+ cations, neutron diffraction on deuterated samples is being planned to support most of our hypothesis relying on well-known compounds.

From a materiafs prospective we should recall that the iridate family is rich and still largely unexplored, hence the numerous opportunities presented by this simple room temperature one step acid leaching technique. For proof concept generalization, we have already prepared several other members, among which are the a and ,6-Li 2 IrO 3 phases with either Li or Na, and we could equally confirm the feasibility to obtain the corresponding protonic phases with a reaction kinetics slightly depending upon the pristine material structure. For broader generaliza tion, we could also demonstrate that the ruthenates share sim ilar chemistry versus the leaching technique approaches which, however, compete in some cases with decomposition reactions. So, a multitude of new protonic phases remain to be discovered and studied for their electrochemical properties.

Tu ming to the fondamental (de)insertion mechanisms of these protonic phases, they fall in line with the classical cati onic insertion mechanism involving the reversible Ir 5+ ➔ Ir 3+ redox for the storage capacity of Li/H 3 .4IrO 4 cells. Charging the material above 4.2 V versus Li + /Li results in limited capacity retention indicative of some electrolyte degradation at high potential. Thus, the need to develop a proper electrolyte formu lation that resists to hydrolysis to properly evaluate the depro tonation of the material and its long-term cycling stability. In aqueous media there is, besides a low potential process govemed by cationic insertion, a high potential process associated to a reversible uptake/release of 0.7 e-for which, based on charge counting, one could invoke some anionic redox process: "H 2 _ 7 Ir 5+ o 3 . 4 (O 2 ) 3 -0 _ 3 ." This is quite unlikely as anionic redox affects the structure and usually leads to sluggish kinetic as compared to cationic redox; which is not what we found. Moreover, the participation of lattice oxygen can lead, as discussed by Gri maud et al. to an OER activityl 25 • 26 1 which could jeopardize the stability of our electrode, but this is not the case either. Thus, we are left with a small amount of Ir 6+ , which is not frequent, or, more likely, we underestimated the amount of H + in the material owing to the experimental uncertainty. The kinetic of each process is dictated by the slowest contribution to the electrochemical reaction and we have shown from PITT meas urements that the two processes observed at low and high potential have similar electrochemical kinetics (charge transfer and diffusion). They only differ by the existence of a greater ohmic polarization for the low potential domain process which cannot be triggered in absence of carbon additive. Its origin is most likely linked to the increasing amount of Ir 3+ during the reduction of the H x irO 4 phase, bearing in mind that Ir 3+ adopts a d 6 configuration so that all the t 2 g levels are filled, thus lim iting the conductivity of the material. It is the same explanation given by Conway in the 1980s to explain why there is no cur rent in IrO 2 below 0.8 V versus SHE (0.15 V vs Hg/Hg 2 SO 4 )) 8 1 Otherwise, besides such a difference, the capacity of each pro cess was shown to be the cumulative contribution of a diffusion limited (bulk) and a nondiffusion limited (surface, or more gen erally highly accessible sites) components, bath being related to charge transfer (faradaic) reactions. The surface charge contri bution was found greater than the diffusion contribution, while the diffusion versus nondiffusion charge ratio was similar for bath low and high potential domains. We believe that the pro nounced surface charge transfer contribution is nested in a spe cific modification of the Li 3 IrO 4 particles morphology during the acid leaching treatment. Nevertheless, a question still remains regarding the absence of structural changes detectable by XRD for the high potential process. We thus could envision, in light of previous studies on V 2 O 5 powders showing extra capacities not associated to structural changes, the emergence of a core-shell like process within a single particle, during the uptake-removal of proton, with the shell operating via a pseu docapacitive behavior enabling changes in the Ir oxidation state without affecting the structure. Obviously, further experiments, namely, operando X-ray absorption spectroscopy at Ir-Lm edge to track changes in the Ir oxidation states, have to be done to test our h yp othesis and fully elucidate the high potential mech anism observed for the aqueous H + /H 3+x lrO 4 system.

In summary, we have successfully synthesized a new pro tonie iridate phase that shows large capacity storage (1.5 c per transition metal), while presenting attractive rate capabilities in aqueous systems. Such a storage process was shown to mainly rely on cationic redox reactions with the eventual connivance of a pseudocapacitive behavior to account for the total redox process in aqueous media. Besides the synthesis and fonda mental aspects, this work also bears importance application wise provided that we can implement our protonation strategy to other Li-rich phases, hence deviating from the use of poorly abundant and costly Ir. Lastly, this proton chemistry opens new opportunities within the field of energy bearing in mind that Ir based materials also present a great interest for water splitting applications.

Experimental Section

Materials Synthesis and Characterization: Li 3 1r0 4 was prepared by mixing stoichiometric amounts of metallic Ir and Li 2 C0 3 and heating at 950 °C for 24 h in air. The prepared sample was then acid-leached in 0.1 M H 2 S0 4 during l h with a fivefold excess of H + over exchangeable u + in the material. The powder and the supernatant were separated by centrifugation and the sample washed three times with distilled water prior to being dried overnight at 55 °C under vacuum. D 2 S0 4 solution and D 2 0 were alternatively used to prepare deuterated samples. The u + and H + contents in the supernatant after reaction were measured by ICP-MS and acid-base titration, respectively. TGA-MS was done under high purity Ar gas (5.0) with 15-20 mg of samples, using a heating ramp of 5 K min-1 from room temperature to 1000 °C. X-ray diffraction was performed at each step to confirm the success of the synthesis using a BRUl<ER D8 Advance diffractometer with Cu l<a radiation (ÂKal = l.54056 A, ÂKa 2 = l.54439 A). NMR experiments were performed on a Bruker 4.7 T Avance Ill spectrometer, using a 1.3 mm doube-resonance probehead. The spinning rate was 62.5 kHz except for the D4.41r04 sample that could not be spun above 59 kHz. 7 Li NMR experiments were performed using a Hahn-echo with a repetition time chosen to ensure full relaxation, and referenced against an aqueous LiCI solution (l mol L-1 ) at a chemical shift of O ppm. 2 H NMR experiments were performed using a quadrupolar echo and a repetition time ofO.l s, and referenced against liquid D 2 0 at 4.8 ppm.

Electrochemical Characterization: For electrochemical characterization, self-standing PTFE electrodes were prepared. H 3 _ 4 1r0 4 was mixed with l O wt% Csp and 5 wt% PTFE, and laminated several times to obtain films of different thickness (l 0-150 µm) and density of material (4-30 mg cm-2 ). Li half cells were prepared with the thicker films with typical loadings of l O mg. Metallic lithium was used as the anode material, LPl 00 (l M LiPF 6 in ethylene carbonate/propylene carbonate/dimethylcarbonate with l :l :3 weight ratio) as the electrolyte and Wh atm an GF /D borosilicate glass fiber membrane as the separator. Swagelok or coin cells were assembled in an Ar-filled glovebox and cycled in galvanostatic mode between 1.5 and 4.2 V versus u + /Li. Characterization in aqueous media (l M H 2 S0 4 / D 2 S0 4 in H 2 0/D 2 0) was done using three-electrode PFA Swagelok cells with two glassy carbon current collectors and Hg/Hg 2 S0 4 reference electrode. 6.5 mm diameter electrodes (0.322 cm 2 ) were punched from the laminated H 3 .4I r0 4 /Csp/PTFE film for the working electrode, and from PTFE electrodes of overcapacitive carbon (YP50) for the counter electrode. The proton release/uptake value was obtained from coulombic titration assuming the formula H 3 ) r0 4 for the starting material and that only protons participate to the charge storage mechanism. The cavity microelectrode used here consists in a thin platinum wire (0 100 µm) sealed into a low melting glass; a laser beam was then focused on the Pt wire to dig a cavity of 80 µm in diameter and 70 µm in depth. The active mate rial was mixed with l O wt% Csp and dipped the CM E in the powder to fill the cavity. For the in situ XRD experiment, a Swagelok-derived electrochemical cell equipped from a Be window was used in organic electrolyte.1 27 1 The same measurements were done in acidic media by replacing the Be window with a Kapton film and a flexible graphite film as current collector, the latter being punched with a hale slightly smaller than the working electrode size, in order to ensure a good electronic conductivity without masking the diffraction signal of the material. Prior and after the measurement with the in situ cell, the working and counter electrodes used in the experiment where measured in the three-electrode set up in order to establish the relationship between the cell voltage and the working electrode potential.

PITT Experiments and Kinetic Study: PITT experiments were done in PFA Swagelok cells using thin electrodes. During the experiment, the potential was increased by steps of 25 mV, and hold du ring 60 s. For each potentiostatic step, the current was recorded � ersus time. The current was integrated versus time according to Q = J 1 /dt to calculate the electrode capacity at different equivalent potential 0 scan rates. For instance, the integration of the current during the first 11t = 5 s for a potential step of 25 mV gives an equivalent scan rate of 5 mV ç 1 and the integration during the first 25 s gives an equivalent scan rate of l mV ç 1 . The mean current during each potential step was calculated J'idt according to / = 1 t . As a result, for each potential step, the current and replat cyclic voltammetry curves could be recalculated at different potential scan rates. CVs calculated from potentiostatic experiments minimize the ohmic drop contribution. To estimate the contribution of the diffusion limited and nondiffusion limited processes to the total current, the current at each potential as the sum of the nondiffusion limited and diffusion limited processes was considered as follows:

i(v)=k 1 v+k 2 .Jv, where the nondiffusion limited redox contribution is defined by the k 1 coefficient, associated with electrochemical processes occurring onto accessible sites, and the k 2 coefficient representing diffusion limited (bulk) processes. Consequently, it becomes possible to determine the phenomenon governing the reaction kinetics by calculating the ratio k i fk 2 and to accurately observe the changes in the kinetic behavior of the material. Considering Equation (1) and plotting i/v 1 1 2 versus v 1 i 2 , k 1 was calculated as the slope of the plot, and k 2 its y-intercept. Calculation of k 1 and k 2 at each potential allows for the separation ofthe nondiffusion and diffusion currents.

Figure 1 .

 1 Figure 1. Refinement ofX-ray diffraction data and SEM picture of a) the parent Li 3 1r0 4 and b) acid-leached H 3 +xlr0 4 phases, with c,d) the corresponding structural models.

20 :Figure 2 .

 202 Figure2. a) TGA analysis under Ar of the acid-leached sample shows three consecutive weight lasses, whereas the parent Li 3 1r0 4 is stable up to 1000 °C. b) Mass spectrometry reveals that the first loss up to 500 °C is due to water, followed by lasses of0 2 at 700 and 900 °C. c) X-ray powder dif fraction of the samples taken at 500 and 1000 °C shows diffraction patterns oflr0 2 and metallic Ir, respectively.

6 V

 6 vs. Hg/Hg 2 SO 4

Figure 3 .

 3 Figure 3.Electrochemical properties of H 34 1 rO 4 in Li half cells (left) and in acidic electrolyte versus capacitive carbon (right). Up to 1.5 u + can be revers ibly inserted in the structure between a) 1.5 and 4.2 V versus u + /Li, c) with a phase transition around 3.2 V and e) fair rate capability. A larger capacity can be achieved in aqueous electrolyte, b) with up to 1.7 e-exchanged d) through two well-defined redox regions between -0. l /0.4 and 0.4/0.8 V versus Hg/Hg 2 SO 4 • f) This process shows excellent rate capability even when thick electrodes and large loadings are used.

a

  T1 -Li, 4 H,I rO, . ----------,• L ! '

  �� 'f<H=l-1 t-- -,----,vs. Hg/Hg 2 SO,

Figure 4 .

 4 Figure 4. ln situ XRD study in a,c) nonaqueous (left) and b,d) aqueous (right) electrolytes. Insertion of Li proceeds with a phase transition from P3 to Tl stacking a round x = 0.7 and large changes in a parameter (3.04-3.13 À) and interlayer distance (d = 4.5-4.7 À), whereas the process in aqueous electrolyte shows limited changes in cell parameters (a = 3.04-3.06 A, d = 4.7-4.8 À) that correspond to the low potential region (below 0.4 V vs Hg/Hg 2 S0 4 ). The high potential region cannot be reached at low current because of the concurrent water splitting reaction.

Figure S .

 S Figure S. Kinetic analysis of the electrochemical processes in three-electrode Swagelok cells. a) CVs measured on the full potential range are compared to b) the low and c) the high potential regions. The beginning of cathodic and anodic processes for both regions is highlighted and show little polariza tion, except for the anodic process in the low potential region (left) which starts to polarize even at low scan rates.

F i gure 6 .

 6 3 .41r0 4 • Such a new phase demonstrates an exciting, but not yet fully understood, elec trochemistry with namely an electrochemical activity of 1.5 c per Ir metal in both aqueous and nonaqueous media with fast kinetics.From the structural point of view, this work off ers very rich crystal chemistry, summarized in Figure7, as we start with 03 stacking in the parent Li 3 Ir0 4 phase, that changes to P3 stacking in H 3 .4lr0 4 by acid leaching and eventually transforms to a Tl staking or maintain the P3 stacking upon additional Calculated CVs from PITT experiments. The contributions of the diffusion limited and nondiffusion limited electrochemical reaction kinetics are shown in blue and orange colors, respectively, for PITT measurements collected at l mV ç 1 (top) and 5 mV ç 1 (bottom). These contributions were calculated from the deconvolution of the total current (see text).

F i gure 7 .Figure 8 .

 78 Figure 8. Proton positions in a) layered CrOOH and b) Al(OH) J bayerite structures. ln the CrOOH structure, protons form a strong covalent bond with oxygen atoms from one (Cr0 2 ) octahedral layer and a weaker hydrogen bond with the facing oxygen in the adjacent layer. Al(OH) J shows a honeycomb ordering of the AI0 6 octahedra and vacant oxygen octahedra that creates free space to accommodate protons almost in the oxygen close packed planes.The metal cations and oxygens are shown as gray and red spheres, respectively. The "out-of-plane" and "in-plane" proton positions are colored with dark blue and cyan, respectively. Thick and thin bonds denote short covalent 0-H and long hydrogen bonds, respectively.

  2 H NMR measurements detect a single peak near 15 ppm with a width at half height of 200 ppm (Figure Sl, Supporting Information), but this 2 H peak is broad and without spinning sidebands compared to previous work by Paik et al. on deuterated Li 2 MnO 3 _[ 16 l The 2 H environments are probably disordered with various distances and geometries relative to the paramagnetic Ir 5+ centers, resulting in a distribution of Fermi contact shift. If some 2 H atoms are close to Ir4 + centers, they are probably not detected due to the strong paramagnetic inter action with Ir 4 + .

Acknowledgements

The authors thank M. Courty for TGA-MS measurements, D. Giaume for ICPMS measurements, C. Yang, A. Grimaud, and G. Rousse for useful discussions. J.-M.T. acknowledges funding from the European Research Council (ERC) (FP/2014)/ERC Grant-Project 670116-ARPEMA.

Supporting Information

Supporting Information is available from the Wiley Online Library or from the author.

Conflict of I nterest

The authors declare no conflict of interest.


Analytical methods for dynamic modelers By Hazhir Rahmandad, Rogelio Oliva and Nathanael D. Osgood (eds.)

Review by Mehdi Saqalli & Melio Saenz

The book edited by Rahmandad and colleagues is intended to be a complete textbook destined for students but mostly fellow researchers. It presents a full set of tools for analyzing modeled systems, each one settled and described with the main issue in introduction, principles and methods as the methodological background and then the theory, related practices and examples and finally some exercises. Organized into three general sections (i. Estimation of model parameters; ii. Model analysis; iii. Decision support and optimization), this book is mainly a strong support for teaching the various tools the editors would like to enhance as very useful and even unavoidable methods designed for dissecting simulation models structures outputs and behaviors. From a general point of view, they succeed in their bet, for the reading of these chapters one after the other naturally urges the reader to absolutely consider the related tools for future works, thanks to a tutorial-like writing style and the tentative for a simple and not-too-technical vocabulary and writing expression. Chapter 1: the method of estimation of maximum likelihood is presented which offers a unified approach towards the estimation of the values sought. The basic concept is to develop a likelihood function as the joint probability density function of observable random variables. The method has some properties: sufficiency providing as much information about the true value of the unknown parameters, consistency to the unknown values, asymptotic efficiency and parameter invariance. Some difficulties arise when it could be applied in complex systems. This method provides two major approaches to building confidence intervals: the asymptotic method and the likelihood ratio method. Chapter 2: The purpose of this chapter is to formulate generic models for a category of objects by quantifying the similarities and differences between their different types. These models are useful when numerical data are available with which parameters can be evaluated in a formal framework. To do this, appropriate moments are defined in the available data and the uncertain parameters are adjusted until solutions in tolerable ranges are reached. The MSM is useful when the errors do not fulfill well-established distribution functions, when the models include stochastic processes and MSM can be applied with various types of data. Chapter 3 deals with modeling by applying the structural equation . It is based on an analysis of the covariance of the data, which facilitates the inclusion of the variables observed directly and serves to simultaneously evaluate parameters and measurement errors by controlling the correlations between variables and errors. Its purpose is to feedback, to strengthen dynamic modeling. This model allows testing causal relationships that include intangible or latent variables. Its basis is found in structural equations that specify causal relationships between variables. In general, SEM allows a flow of innovation and extension that includes multi-level modeling. However, conceptual difficulties exist to formulate causal hypotheses that operate under specific forms of a covariance matrix. Chapter 4 focuses from an idea from Forrester on noise existence in modeling results: it invalidates prediction potential capacity of a model. Some systems simulate prototype behavior under particular conditions or by coincidence. Other ones generate behavior that can be replicated but with some errors. What will be the role of the replication in the model validation process? Using time-series data may be very hard for answering this issue. Applying filtering or other state resetting forms depends on the nature of system's behavior. Techniques may be conditioned by interpretation of parameter estimates. Chapter 5: Decision-making processes cannot always provide all the desired data. Model calibration may then serve as a tool to reach estimates of model parameters despite the constraints it may impose to build a useful overview explaining the variability of model results or political negotiations. The main focus here is that it refers to the use of emerging evidence combining and synergizing the benefits associated with traditional calibration and sensitivity analysis that such distributional assumptions deeply misses. Modeling allows for sampling empirical data, the probabilistic model and the subsequent distribution of the data on the parameters and on the simulation model state and the state outputs of the model. Chapter 6: An important system behavior analysis tool is here presented: automatic pattern recognition. The chapter develops its basic principles regarding the system nature and behavior, allowing point-to-point or global applications to be made. the chapter develops illustrative examples that can serve as a guide for the reader and complements with topics in which care must be taken when interpreting. It highlights the value of automatic interpretation versus the current visualization used as a qualitative evaluation method, which is a subject rarely seen in classical literature. Chapter 7 presents the usefulness of two non-equivalent analysis methods of the eigenvalues of mathematicallydefined linear and even non-linear models: the EEA (Eigenvalue Elasticity Analysis) and the Dynamic Decomposition Weight Analysis (DDWA), both designed to identify the most prominent dynamics of a system. However, synthetizing the insights of the gains of using such methods would have been useful, i.e. not describing loop effects of the example but better what a newbie would have to look after, as well as providing the loop descriptions without having to consult the electronic model and the related textbook sections in the shown examples. In Figure 7.5., we suppose an error in the graph Y which maybe ought to be K graph (thereby in agreement with Figure 7.13 b. The conclusion is a great summary of advantages, limitations and perspectives of the methods, of which the analysis easiness, the linearity obligations and the adaptability are the most important respectively. Chapter 8 deals with optimization in policy space and its stakes and practices, providing the counterintuitive (for a profane point of view) idea that optimization can be used for evaluating non-optimal policies, errors and uncertainties. The chapter is hopefully strongly positioned in the assumption of the impossibility of a perfect optimization and assumes the various postulates one has to integrate in a model optimization/analysis approach. The SOPS method (Stochastic Optimization in Policy Space) is here presented and used: thanks to examples, and especially a fishery one, the chapter goes from closed deterministic systems to nonlinear stochastic bypassing impacts of errors regarding measuring information and tested policy itself, including uncertainty impacts on policy effects. Chapter 9 focuses on incremental adaptive decision processes facing uncertainties. Authors use decision trees to establish the exponentially-growing number of scenarios according to decision and event steps and, by "backwards induction", eliminate major portions of these trees to simplify the analysis. The Hybrid framework combining decision & event scenario interface coupled with a simulation model is a way to explore the various existing paths based on the memory of past events to establish which decision & event path is the most relevant thereby providing clues on decision efficiency but as far as no unknown events occur. Chapter 10 pursue the preceding chapter by presenting two procedures: first, a 7-steps sequential procedure called decision tree approach combining system dynamics (SD) deterministic modeling, uncertainty model building, Monte-Carlo based explorations, approximation estimations and finally backward inductions. Once real managerial choices are determined, this procedure explores the various sequences of decisions/model outputs, including uncertainties until providing the most efficient path according to the one chosen criterion. The second method is the diffusion approximation approach that can integrate fluctuant risks in a more "continuous" way along the simulation steps but is restricted to continuous and less complex scenario options. However, the method is referenced but unfortunately not presented here. : Chapter 11 deals again with optimization through prescriptive models, again both linear and non-linear ones (p. 338: note: Pure optimization does exist in engineering! And modeling is always an approximation of reality whatever the approach). After an example for a non-linear but deterministic model, the article presents the equivalent optimization process on non-linear stochastic models, with or without perfect data. Finally, chapter 12 is dedicated to multiple stakeholders' problems where non-cooperative dynamic games rule the set. However, it focuses on games where all actors are fully rational and knows all about the system including the fact that other actors are rational too, leading to a Nash equilibrium. Again, solving such differential games is assessed through optimization tools for reaching at least one of the equilibrium points, each one being a balanced point between competing actors. One may here definitely question the rationality assumption and even more the full knowledge of actors. Although the great benefit of the book is that it covers a wide range of useful analytical tools, stating that such tools have great potentialities because of their real-world applications faces the fact that real-world problems to model do face more information uncertainty issues than uncertainty optimization issues: roughly, the main issue is to get access to the very model this book tend to analyze and optimize. However, the whole useful presentation of the various cases in which dynamic system analysis can be assessed would have been more convincing without the promotion of a commercial modelling software (apart from initial free elements), i.e. the Vensim product which is apparently systematically used in all chapters. This book brings together, in an organized and systematic way, available and proven techniques around the modeling of dynamic systems. Its reading requires previous knowledge on various topics, which does not prevent it from serving as a basis to contribute to the training of students interested in modeling, especially techno-social systems. As a conclusion, given the consistency of its content and its specific orientation towards analytical modelling students, not all them will want to read this book from the beginning to the end, but many will profit from consulting individual chapters.