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Solid-state inorganic electrolytes for next generation potassium batteries

Grill, Jonas; Steensen, Simon K.; Castro, Diana Lucia Quintero; Castelli, Ivano E.; Popovic-Neuber,
Jelena

Published in:
Communications Materials

Link to article, DOI:

10.1038/s43246-024-00568-3

Publication date:
2024

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Citation (APA):
Grill, J., Steensen, S. K., Castro, D. L. Q., Castelli, I. E., & Popovic-Neuber, J. (2024). Solid-state inorganic
electrolytes for next generation potassium batteries. Communications Materials, 5(1), Article 127.
https://doi.org/10.1038/s43246-024-00568-3

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 communications materials Review article

https://doi.org/10.1038/s43246-024-00568-3

Solid-state inorganic electrolytes for next

generation potassium batteries
Check for updates

Jonas Grill1, Simon K. Steensen 2

, Diana Lucia Quintero Castro3, Ivano E. Castelli 2
&
Jelena Popovic-Neuber 1

Necessary diversification of battery chemistry and related cell design call for investigation of more
exotic materials and configurations, such as solid-state potassium batteries. In the core of their
development lies the necessity of discovering new and electrochemically more efficient inorganic
solid-state electrolytes. This review focuses on suitable chemical structures, their fundamental
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properties and status of the materials synthesis, related electrochemical performance, contemporary
characterization techniques and modeling efforts for inorganic solid-state potassium electrolytes.

Solid-state batteries (SSB) have been in the focus of the academic scientific high pressure (4 GPa)14. On the other hand, theoretical calculations suggest
community and companies dealing with battery technology, related mate- high K+ diffusion in amorphous Si due to weak electrostatic K-single bond-
rials, and their electrochemistry due to promise of higher energy and power Si attraction, high carrier ion concentration, and the formation of isolated
density, higher device safety and stability, as well as potentially fast charging Sin (n = 3–5) clusters during the potassiation process15. In addition to all
capabilities1–5. The key challenges for development of SSB technologies are previously mentioned possibilities, new solid-state electrolytes offering high
(i) design of solid-state electrolytes (SSEs) requiring a minimum stack ionic conductivity should be developed, with sulfides, halides, polymers and
pressure (few MPa) for long term operation, (ii) development of stable high- oxides being at the forefront16. Ionic conductivity of SSEs should be high and
rate and high-capacity anodes such as alkali metals and silicon, (iii) design of even higher than in the liquid electrolyte case (ca. 10 mS cm−1), since they
low-cost SSEs with high ionic conductivities in thick and optimized cath- are, in most configurations, mixed with cathode materials8. Often, it is
odes, (iv) optimization of SSE interfaces, (v) sustainability improvement6–8. pointed out that SSBs should offer higher materials stability compared to
Thus, development of SSEs and related interfaces lies in the core of the cells containing liquid electrolyte since the electrode cross-talk is
current efforts. Ragone plots comparing specific energy and power of dif- circumvented17. Non-uniform alkali metal flux is however a fingerprint of
ferent materials suggest that much is to be done to improve room tem- such cross-talk and should not be neglected in real systems18. Electro-
perature performance of cells with inorganic SSEs, while the cells containing chemical high-throughput screenings of crystal structures have been gen-
inorganic/polymer composite SSEs behave well at elevated temperatures erally employed in recent years to accelerate material search for structures
(50–100 °C), at least in the lithium case1. with desired properties within battery research. Utilizing availability of
To achieve the necessary energy densities, the issues related to the computational resources allows for integration of ab-initio methods, geo-
reactivity of K anode resulting in continuous solid electrolyte interphase metrical characteristics structures, machine learning and other techniques
(SEI), dendrite, and porous and ‘dead’ electrode growth need to be solved9. used for screenings of electrode and solid electrolyte materials by filtering
Regarding the SEI improvement, in the case of K metal, Pilling-Bedworth the key aspects such as electrochemical stability, activation barriers, volume
ratios (Supplementary Information, Table S1) suggest that only KHCO3 as expansion and open-circuit-voltage insight in the case of electrodes
well as some polysulfides and pyrosulfates (K2S, K2S5 and K2S2O7) may throughout the process19–24.
form a stable non-porous artificial SEI layer. One of the approaches to In terms of technological feasibility, lithium-based SSBs seem to be
circumvent the “dead” metal formation is the so-called anode-free or anode- techno-economically comparable with the commercial lithium-ion
less SSB, where the alkali metal is electrodeposited at the beginning of technology25. Sodium and potassium ion batteries show comparable
operation10–12. However, the SEI evolution is expected to be even more environmental performances and lower supply risks26. The techno-
amplified in this case, since freshly deposited alkali metals are expected to be economical predictions of K-SSBs are difficult, as high uncertainties are
more reactive as they are not covered by native films. Another option for expected in terms of solid state electrolyte price, K metal price and required
improving the energy density is employment of a silicon anode13. Even metal excess27. In general, SSBs are slightly more expensive than conven-
though it is expected that potassium may react with silicon, it has been tional liquid-electrolyte based batteries due to higher price of manufacturing
shown that the reactions occur at either high temperature (above 550 °C) or and processing of solid-state electrolytes, as well as full cells, and are still far

1
Department of Energy and Petroleum Engineering, University of Stavanger, Stavanger, Norway. 2Department of Energy Conversion and Storage, Technical
University of Denmark, Kongens, Lyngby, Denmark. 3Department of Mathematics and Physics, University of Stavanger, Stavanger, Norway.
e-mail: jelena.popovic-neuber@uis.no

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https://doi.org/10.1038/s43246-024-00568-3 Review article

away from necessary 100 $ kWh−1 28. For example, densification is very AIMD descriptors, yielding low mean-absolute-percentage-error (MAPE)
important for all components of SSBs, which results in potentially different on the test set of 0.061 for Cv, and 0.3 for <ω> predictions. While the more
production conditions necessary29. Also, the difference in pressure needed interesting diffusion coefficient prediction is improved by including all
for successful operation is still considerable (1 vs. several MPa)30. Recently, it descriptors going from test MAPE: 2.8, train MAPE: 1.4 to test MAPE: 2.6,
has been shown that it is not sufficient to focus solely on increasing materials train MAPE: 0.79, though unfortunately with the MAPE score remaining
supply or on enhancing cell capacity of SSB, since these two parameters are extremely high. While potassium ionic conductors are not included, the
coupled31. Another problem in terms of commercialization of SSBs is their universality of the study and inclusion of anharmonic descriptors remain
scalability, where high throughput processes might be beneficial but are relevant.
challenging for already existing battery industry32. From a production point While considerable amount of research has been done on oxide-based
of view, additional processes involving compaction of materials through transition-metal doped K+ ionic conductors such as doped and undoped
isostatic pressing are necessary33. In terms of design, bipolar design is seen as KFeO2, most oxides offer reasonable conductivities in the 10−4 to
a potentially successful technique for improvement34. 10−2 S cm−1 range only at high temperatures around 300–400 °C, making
In the first part of this review, we give insight into bulk performance them unsuitable for the use in all solid-state batteries (ASSBs)38. Ionic
parameters, promising chemical structures and related ion transport conductivity of potassium ions in oxides has also been the subject of high-
mechanisms in currently known inorganic K-conductors of interest as SSEs. throughput screening. 374 ternary and quaternary ionic conducting can-
Secondly, we focus on the efforts to understand and solve the issues related didates were reported in ref. 39, where a Voronoi partition method was
to the anode (predominantly K metal)/K SSE interphase instability. For applied to 1957 crystal structures. The approach computes infinite migra-
more information on cathode/SSE interface, we suggest consulting refs. 6,7. tion maps for the K+ cation in the one-, two- and three-periodic case, if they
Finally, we give a contemporary overview of characterization techniques exist in the computed Voronoi partition of the structure. A total of
targeting structural and morphological evolution on several scales, as well as 18 structures are investigated further using the nudged elastic band (NEB)
electrochemical and operando/in situ techniques. DFT method to compute the migration energies with 4 structures already
having been reported to be ionic conductors, although predominantly
Bulk performance parameters, chemical structures, mixed conductors suitable to be used as electrodes. The four known
and ion transport mechanisms structures and their minimal path migration energy in each periodic type are
Key parameters governing the electrochemical performance of SSEs include proposed based on comparable migration barriers to the known conductors
high room temperature ionic conductivity linked with very low electronic analyzed as can be seen in Table 1.
conductivity (e.g., electronic transference number, tel, close to zero), low In another study, high-throughput screening of potassium containing
activation energy for ion transport, EA, and high alkali metal diffusion oxides has been performed using bond valence calculations in which K+ ions
coefficient, DK. The complexity of the bulk performance is amplified by the are assumed to move within stationary anions and cations40. A bond valence
fact that migration of ions in SSB is a multiscale process, encompassing both computed migration energy of 0.96 eV is set as a screening criterion, only
atomic and device scale35. The macroscopic diffusivity and its Arrhenius allowing for 22 structures with lower migration energy to proceed. A sub-
expression is obtained from the barrier of the single diffusion event by sequent ab initio molecular dynamics computation shows both a low
transition state theory, while on the macroscopic scale, the diffusion coef- migration energy barrier and a large mean square displacement for K2CdO2.
ficient can be described by Fick’s laws36. Favorable migration pathways are a Subsequent NEB calculations yield a migration energy barrier of 0.40 meV
function of availability and interconnectivity of different sites, defined by the for vacancy-assisted movement, while energy of interstitial-assisted
crystal structure of the framework, with most observed vacancy diffusion, mechanism was reported to be 0.13 meV. However, a formation energy of
direct interstitial, and correlated (knock-on) ion transport mechanisms35. 0.29 eV for one charged interstitial site limits the realization of the above-
On the other hand, ionic conductivity of SSEs is proportional to con- mentioned mechanism.
centration of mobile ions, their charge and mobility. Thus, doping, or ele- Most of the known ionic conductors with viable room temperature
mental substitution can affect both mobility and concentration, but also conductivities and lowest EA can be classified as derivatives of known Li+ or
structural distribution of ions, remaining a powerful tool to optimize elec- Na+ ionic conductors (for example K3SbS4 and K-β”−Al2O3). Though their
trochemical performance of SSEs. At the nanometer to micrometer scale, EA is comparable, their ionic conductivity is still significantly lower than
microstructural features such as grain boundaries, pores and other higher some of the best-known Li and Na-based electrolytes (Li7Si2S7I,
order defects can affect the ion transport significantly, in many cases 1.0 × 10−2 S cm−1, Li9.54Si1.74P1.44S11.7Cl0.3, 2.5 × 10−2 S cm−1,41 and
detrimentally. Na2.88Sb0.88W0.12S4, 3.2 × 10−2 S cm−1, 42). Figure 1 lists the K+-ion con-
Modern data-driven perspective approaches the problem of ionic ductivities of known materials and the respective EA of solid electrolytes with
diffusivity by using ion descriptors to model and understand which prop- highest ionic conductivity σion at RT (for detailed data and references see
erties affect ionic diffusion37. Such an investigation enabled the construction table S2 (SI)). While materials like K0.4Cd0.3FeO2 and K07Sr0.15GaO2 offer
of a database for the analyses of 61 materials with different mobile ions excellent σion at elevated temperatures (3.4 × 10−2 S cm−1 and
consisting of 46% Li-, 23% halides-, 15% Na-, 8% O- and 8% Ag/Cu- 2.1 × 10−2 S cm−1 at 400 °C), this review will focus on electrolytes with rea-
containing structures. A total of 54 computed descriptors were divided into sonable (near) RT σion. Prospective electrode materials, for example layered
the categories of mechanical-elastic (based on Density Functional Theory, oxides43, have been excluded as they typically show both ionic and electronic
DFT, data), diffusive-vibrational (DFT), and structural-compositional (Ab- conductivity, the latter of which is undesirable for electrolytes which should
initio molecular dynamics, AIMD), with the inclusion of anharmonic effects be purely ionic conductors. The highest room temperature ionic con-
from AIMD simulations being highlighted as the most crucial novelty in the ductivity (3.5 × 102 S cm−1) and lowest EA (0.08 eV) has been reported for
work. A statistical correlation analysis does not reveal a single feature to single crystalline K2Fe4O7, however this material is expected to be a mixed
determine diffusion and fully account for the ionic behavior, rather a col- conductor, as its bandgap is predicted to be 1.32 eV44. Albrecht et. al.
lection of 19 out of 53 features (diffusion coefficient discarded) with an reported the formation of a K1.7Fe4O6.7(OH)0.3 hydroxide of the same space
absolute Spearman correlation of over 20%. The correlation study indicates group and with near identical lattice parameters under similar synthesis
that insulators with small average phonon frequencies, large heat capacity conditions45,46. A substantial hydrogen content was observed via carrier gas
and large vibrational entropy are promising ionic conducting candidates. hot extraction as well as a recorded loss of water during heating at 200 °C via
Several neural networks are trained using only DFT descriptors and a thermogravimetry mass spectroscopy (TG-MS), while no mass loss during
scheme including AIMD descriptors to predict the ionic diffusion coeffi- heating to 800 °C was reported for K2Fe4O7. The presence of hydroxide ions
cient, volume heat capacity Cv and mean vibrational frequency <ω > . The and residual crystal water from the hydrothermal synthesis could explain
predictions of <ω> and Cv can be significantly improved when including the both the reported high ionic conductivity as well as the low EA of K2Fe4O7.

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Table 1 | Minimal 1,2 and 3-dimensional path migration are shown to be synthetically obtainable, but their ionic conductivities have
energies of known and potential K+ ion conductors, based on not yet been tested. In the K3OI anti-perovskite, which is structurally
nudged elastic band density functional theory calculations39 identical to conventional perovskites but with inverted cation and anion
sites, ab initio methods were employed to understand the diffusion and an
Structure Minimal path migration energy [eV]
experimentally observed phase-change. Modelling conductivity for the
1D 2D 3D
K3OI structure reveals that the existence of vacancies is crucial for the ion-
KFeO2 0.106 0.155 0.227 diffusion observed. By computing probability distribution function of the
KAlO2 0.094 0.135 0.257 ionic species, the study shows a high-temperature disorder in the I-O
K2Cu3Ge5O14 0.261 0.883 sublattice with a low activation energy (0.76 eV through NEB) compared to
that of the K-ion. This is believed to be the observed phase-change, which
K2SbPO6 0.292 0.359 0.668
causes the ions to diffuse through the local gaps of I-O disorder and
K5As3O10 0.279 0.300 0.425 vacancies.
K4V2O7 0.218 0.341 0.388 Generally, body-centered cubic (bcc) anion sublattices seem to be
K2Zn3O4 0.064 - - beneficial for fast ion conduction as cations can hop between energetically
K2Sb4O11 0.096 - -
equivalent adjacent tetrahedral sites, while in face-centered cubic (fcc) and
hexagonal close-packed (hcp) sublattices ion migration occurs through
K3NbAs2O9 0.130 - 0.611
higher energy octahedral sites56. This rationale has been demonstrated to be
K3NbP2O9 0.195 - 0.774 favorable for fast Li+ and Na+ migration in, for example, Li10GeP2S12 and
K2Al2Sb2O7 - 0.141 - Li7P3S11 and can also be applied for potassium. Na3PS4 and W-doped
K6CuSi2O8 0.240 0.463 0.512 Na3SbS4 display similarly high σion > 10−4 S cm−1 at RT compared to
W-doped K2.92Sb0.92W0.08S4 σion = 7.7 × 10−5 S cm−1, 42,57. Newly reported
Cl-doped K3SbS4 shows a record RT conductivity σion = 3.2 × 10−4 S cm−1
linked with low EA = 0.26 eV58. This class of materials consists of a bcc anion
framework of the PS43− or SbS43− tetrahedra, which is slightly distorted for
K3SbS4.
Depending on the crystal structure, K+ migration can predominantly
occur through 2D or 3D pathways. The K- β”-Al2O3 structure consists of
alternatively stacked non-conducting Al2O3 spinel blocks, separated by
loosely packed layers of potassium oxide which form conduction planes and
allow for K+ transport. It has been experimentally observed that the room-
temperature σion of K-beta”-Al2O3 is higher compared to Li and Na coun-
terparts. Recently, a DFT study showed that in these materials, vacancy
mechanisms dominate, meaning that the occupation of the conduction
plane sites determines the σion59. In the orthorhombic K3SbS4, K+ migration
is through void sides, resulting in a two-dimensional diffusion network,
while the open 3D framework of K2Fe4O7 consists of 2D 6-ring channels
parallel to the a and b axis, filled with highly disordered K+ cations
(Fig. 2b, c). The σion of single crystals along the a axis was reported to be up to
5 × 102 S cm−1 at 500 °C (5 S cm−1 along the c axis at the same temperature),
demonstrating the highly anisotropic σion, a consequence of sufficiently
open channels of optimal size along the a axis and smaller openings between
two FeO6 octahedra and one FeO4 tetrahedra along the c axis.
Another interesting electrolyte is T5 KSi2P3 as it also has a good room
Fig. 1 | Temperature-dependent conductivity of various K+ solid electrolytes temperature σion = 2.6 × 10−4 S cm−1 and an interesting structure consisting
together with EA of selected compounds. The data for K2Fe4O7 is obtained from of a network of interconnected five SiP4 tetrahedra long supertetrahedra
single-crystal measurements. K-BASE denotes a sample consisting of 91 wt% K-β”- (Fig. 2d)60. The voids of this network are filled by a second crystal-
Al2O3, 8.4 wt% K-β-Al2O3, and 0.6 wt% ZrO2. K2Fe4O7 is included as the electrolyte lographically identical network, with the K+ residing in the big cavities
with the currently best reported RT σion and EA, but those might be partially from H+ between the two networks. The eleven K+ positions have an average occu-
conduction as well as crystal water. The ionic conductivities are summarized pancy of 0.4 and are thus disordered, leading to a high mobility of the K+
from42,49,58,60,65,90–104. Detailed references can be found in Table S2 (SI). ions at room temperature through isotropic 3D channels along the
supertetrahedra.
This structure has not been reported experimentally for the Li and Na case, It should be noted that for oxide and sulfide-based solid-state ionic
possibly as due to a tendency to decompose into Li- or NaFeO2 and conductors, doping has been shown as beneficial for transport performance
Fe2O347,48.For some of the ionic conductors like K-BASE, which consists of as it creates additional vacancies which boost σion. This can either be done by
K-β”−Al2O3 with minor amounts of K-β-Al2O3 and ZrO2, existence of such modifying the anion lattice, for example by partially replacing Sb5+ with W6+
additional poorly conductive phases is necessary in the material entering for K3SbS4 or by introducing aliovalent cations of a similar size to K+. For
battery cell as the mechanical integrity of pure K-β”−Al2O3 is too low for example, Ba2+−doped K2.9Ba0.05OI has a reported σion = 3.5 × 10−3 S cm−1 at
practical applications49. 270 °C and crystallizes in the antiperovskite structure. The Li compound
K+ electrolytes derived from Li+ or Na+ conductors usually need a Li3-2xBaxOCl (x = 0.005) is also an excellent ionic conductor
volumetric adaptation of the lattice to accommodate the larger K+ cation. (σion = 2.5 × 10−2 S cm−1 at RT). Similarly, to mitigate the energy necessary
Examples are K3SbS4, derived from Na3PS4, as well as K3OI, derived from for carrier creation an Al-doping is proposed at Cd sites in K2CdO2 for
Li3OCl. This is done via partial substitution with bigger ions, for example which they report a migration energy barrier of 0.42 ± 0.03 eV with
Sb5+ instead of P5+, I− instead of Cl−, or K+ instead of Na+ in K-β”-alumina. σion = 2.2 × 10−5 S cm−1 at 27 °C40. A computational study was conducted on
In some case, structures such as K3OCl50 and K6PS5Cl51, which are similar to the doping effect of Ti in structurally similar KFeO261. Here all inequivalent
the known solid electrolytes Li3OCl52, Na3OCl53, Li6PS5Cl54 and Na6PS5Cl55 atomic arrangements with minimal Ti doping (x = 0.03, x = 0.06, x = 0.09)

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Fig. 2 | Crystal structures of promising solid-state

potassium electrolytes. a K-β”-Al2O3, b K2Fe4O7, a) b) c)
c K3SbS4, d KSi2P3 with K+ diffusion along the ab-
plane for K-β”-Al2O3, along channels for K2Fe4O7
(along the b-axis) and K3SbS4 (along the c-axis) and
the 3D ionic conductor KSi2P3. This figure was
drawn using the program Diamond Version 5.0.0.

/ AlO4/AlO6
d)
/ FeO4/FeO6

SbS4

/ SiP4

K+

in K1-xFe1-xTixO2 are generated along with all migration pathways for the Critical currents for dendrite penetration and voiding in potassium
three dopant cases. For the x = 0.03 case, all K+ migration energy barriers metal anode SSBs are usually higher than those in similar Li- and Na-
were computed using the NEB method, properties such as pathway dopant systems due to lower yield strengths and therefore more pronounced creep
distance and angles were used as descriptors for a machine learning model of potassium64. For K-β”−Al2O3, the critical current for dendrite formation
using ridge regression and ensemble-based (gradient boosting and random of 4.8 mA cm−2 is among the highest reported for a metal anode/SSE
forest) regression aiming to predict the maximum energy of the pathways. interface. However, it should be noted that the critical current density for
In the study, the pathway dopant angle is concluded to have a large effect on voiding in this system is reported to be as low as 2 mA cm−2, as can be seen in
the K+ ion diffusion perhaps due to the doping effect on the crystal struc- Fig. 3d, e. This leads to a decreased contact area between the metal anode and
tures’ lability. The pathway dopant distance did not have a large impact on solid electrolyte (SE), localized higher current densities, and dendrite for-
the migration, therefore no indication of a decisive electrostatic role of the mation at those positions.
dopant on the K+ migration. Interfacial stability between the SE and electrodes is another challenge,
Metal borates have been getting an increased amount of attention as a especially for K metal electrodes. Zheng et al. demonstrated that Ba2+ doped
possible SSE candidate, however only at elevated temperatures. The special antiperovskite K3OI shows excellent stability against K metal as its anions
cases of closo-dodecaborates M2B12H12 (M = Li, Na, K), are also analyzed by cannot be further reduced by K metal or K+ containing anodes, but its high
ab initio methods62. The aim is to model the electronic, ionic, vibrational, phase transition temperature of 240 °C is needed for good σion65. In addition,
and thermodynamic properties of the materials, of which ionic conductivity the observed high charge transfer resistance is expected to limit its appli-
for the LiB12H12, NaB12H12, and even LiNaB12H12 cases have been reported. cations in real systems. The interfacial stability of borohydride complexes
Furthermore, the high-temperature superionic phase of Na2B12H12 has such as KB3H8·NH3B3H7, which incorporate a neutral NH3B3H7 molecule
been shown to exhibit rapid reorientation dynamics of the B12H122− anion to achieve higher σion of 1.3 × 10−4 S cm−1 and cationic transference number,
aiding the cation motion. However, the reported computed EA in the tK+ = 0.93 has also been investigated. This material exhibits good initial
potassium case is 1.25 eV, compared to 0.7 eV and 1.16 eV for Li and Na interfacial stability against K metal, however, the formation of unknown
respectively. A large insulator bandgap of 5.59 eV is reported in the case of decomposition products was visible after 166 cycles.
K2B12H12. Additionally, MD simulations demonstrated the material to be The interfacial stability of oxide based Na-BASE against Na metal was
stable at 300 K and 600 K, with thermal stability being a general necessary confirmed via X-ray photoelectron spectroscopy (XPS)66. Comparable sta-
property needed for potential SSEs. bility of K-BASE against K is expected as a K-S cell with a K-BASE electrolyte
showed excellent cycle stability over 1000 cycles49. For solid electrolytes with
Anode/electrolyte interfaces in K-based solid-state sulfides, such as K3SbS4, formation of a potassium-sulfide based SEI is
batteries expected, since continuous formation of a Na2S and Na3P based interphase
One of the main issues to be addressed in high energy K-based solid-state has been reported for Na3PS466. While sulfides are electronic isolators, the
batteries is the adhesion of K metal and the solid-state electrolyte as well as higher electronic conductivity of phosphides can lead to a reduction of the
related interfacial reactivity. Electrochemical impedance spectroscopy (EIS) is electrolyte and constant growth of the SEI67. As the volume fraction of
possibly the most relevant in situ diagnostic tool to track the (electro)chemical phosphides in K3PS4 is supposed to be lower than sulfides, an encasement of
degradation pathways and state-of-health (SOH) via voids formation, isolated K3P clusters in a sulfide-based matrix is possible. The formation of
interfacial contact area decreases, creep through the impedance increase or electronically conducting interphases may be a problem for K3SbS4 and
decrease, respectively, combined with an informed mechanistic model63. especially KSi2P3 as potassium-antimony compounds may show a higher
To achieve high critical currents, the interfacial resistance needs to be electronic conductivity than their phosphide analogues. In addition, the
minimized to reduce its detrimental effect on K+ ion transport. For K- formation of potassium-silicon compounds has only been reported at ele-
β”−Al2O3, it could be demonstrated that polishing and heat-treatment vated temperatures and pressures.
could reduce the interfacial resistance between K-β”−Al2O3 and the
potassium electrodes. Figure 3a shows the Nyquist plot of a K/K-β”−Al2O3/ Contemporary characterization techniques
K cell after heat-treatment at different temperatures under Ar. Depending X-ray powder diffraction
on the heat-treatment temperature, the interfacial resistance could be X-ray powder diffraction is widely used for compound identification when
decreased by an order of magnitude (Fig. 3c) which could be attributed to a new materials are synthesized. In addition, Rietveld refinement (such as in
loss of surficial hydroxide and carbonates. Fig. 4a) can be used for quantitative analysis of crystalline phases and

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Fig. 3 | Interfacial properties of K-β”-Al2O3 as measured from symmetric K cells microscopy (SEM) images and energy dispersive X-ray spectroscopy (EDX) map-
cycled at 20 °C. a Nyquist plot of symmetric K/K-β”-Al2O3/K cell after heat- ping of K (turquoise) of the K/K-β”-Al2O3 interface after 25 cycles. Reproduced with
treatment at different temperatures under Ar, b equivalent circuit model used for the permission from105.
determination of the interfacial resistance, c plot showing the modelled interfacial
resistance against heat treatment temperature and d, e showing scanning electron

amorphous content as well as refinement of crystal structures. Due to its most commonly used, offering in-operando and in-situ experiments with
non-destructive nature, low sample demand (in the mg range) and ability to outstandingly flexible sample environments (see ref. 68 for a review). The
do fast in situ measurements in special cells, it has become a standard application of these methods allows for the determination of atomic
method in the lab. While it is an excellent method for structure refinement structure, atomic positions, and diffusion pathways using diffraction tech-
and in situ studies (for example the change in lattice parameters due to Li/K niques similar to those performed with X-rays69–71. INS and QENS methods
intercalation or doping) due to its high 2θ resolution and therefore accurate allow the determination of re-orientational dynamics and the under-
determination of lattice parameters, an unambiguous structure solution is standing of the physical mechanisms of diffusion dynamics72.To the day,
often difficult or factually impossible as symmetry-equivalent reflections most reported investigations using neutron methods in K-solid-state battery
have the same d spacing. As the scattering intensity depends on the atomic materials are focused on electrodes. This could be due to multiple electrolyte
number Z, K+ occupancy should be easier to determine compared to Li+ due compounds (such as the ones listed in Fig. 1) containing boron, gadolinium,
to the higher scattering intensity. While a plethora of information like the cadmium, and antimony, which show large neutron absorption cross sec-
weight fraction of crystalline compounds (and amorphous phases), their tions, making the experiments more difficult. Besides, the hydrogen content
lattice parameters, occupancy, crystallite size and strain can be extracted, with a remarkably high incoherent cross-section, can hinder the observation
accurate Rietveld refinements, especially in multi-component systems still of coherent potassium signal. Dimitrievska et. al. report on QENS and INS
require a fair bit of experience and can hardly be automatized. Data results on KCB11H1273 specifying the use of an ultra-thin sample geometry to
representation of Rietveld refinements should clearly state which para- avoid these issues. From the neutron data, it could be concluded that the
meters were refined (e.g., atomic positions, structural, microstructural, and anion diffusive jump frequencies are very small in comparison to over-
thermal displacement parameters) and according to which order. The damped vibrational frequencies with a motion of 0.41(3) Å. The comparison
observed pattern, fit profile, difference curve and reflection positions should of these results for K with those for Li and Na, show a consistent correlation
be clearly visible. In addition, chemical compositions calculated from between cation size and anion reorientation jump rates. Another example
occupancy should be cross-checked using other characterization methods, on the use of QENS and INS is presented by Andersson et. al. for KB3H872,
such as inductively coupled plasma mass spectrometry (ICP-MS) of solu- where a clear connection can be made between the local structure (deter-
tions. For structure solution, single crystal X-ray diffraction (SXRD) is mined by X-rays) and the reorientation dynamics. In this study, use of
usually required as it measures the intensity as a function of the Miller ultrathin samples for QENS experiments and reflection geometry for the
indices hkl compared to d spacing for powder XRD and enables an INS experiments has also been mentioned.
unambiguous space group determination. Neutron powder diffraction can
serve as a complementary method as its scattering intensities rely on the Electrochemical impedance spectroscopy
scattering length and not on the Z of ions. Electrochemical impedance spectroscopy (EIS) is an invaluable in situ tool
for studying electrochemical systems as it can deconvolute electrochemical
Neutron techniques processes in the cells by their different relaxation time. In batteries, those
Multiple neutron absorption and scattering methods are increasing in processes (e.g., electron transfer from the current collector to the electrode,
popularity in the investigation of solid-state battery materials. Neutron electron conduction across the electrode, ion migration across the electrode,
powder diffraction (NPD), neutron tomography, quasielastic neutron insertion of ions and electrons into active particles, double layer charging at
scattering (QENS) and inelastic neutron scattering (INS) are among the solid/liquid interfaces, coupled ion diffusion in the active particle and

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Fig. 4 | Contemporary characterization techniques. a Rietveld refinement of SXRD dependence of the interface impedance of a symmetric Li|Li7La3Zr2O12(LLZO)|Li
data and crystal structure for orthorhombic b-K3SbS4. Reproduced with permission cell. Reproduced with permission from77 d Demonstration of the working principle
from b elastic incoherent structure factor vs the neutron momentum transfer Q of of the operando plating of Na on the solid electrolyte Na3.4Zr2Si2.4P0.6O12 by using
KCB11H12 at different temperatures, derived from quasielastic neutron scattering the flood gun as an electron source inside a XPS to study the interphase formation
(QENS) measurements with model curves for various anion reoriental mechanisms between the SE and a Na electrode. Reproduced with permission from ref. 106.
for comparison. Reproduced with permission from73. c EIS data on the pressure

electrode and migration/diffusion of ions in the separator and others) often contributions of the individual electrodes can be determined. The same
overlap, making an unambiguous assignment of features of the impedance method should also be applicable for other alkali metals and enables the
spectrum challenging74,75. Methods for reducing the number of observed convenient use of a RE with minimal changes to the cell geometry.
processes, like the use of symmetric cells with two identical electrodes
(where the interfacial processes are expected to be symmetric), change of Nuclear magnetic resonance
temperature, and the use of ion-blocking electrodes especially for the Solid-state nuclear magnetic resonance (ssNMR) can probe both local
separation of the bulk and grain boundary are some of the possible structure and ionic motion, which was implemented in many battery
solutions76. Eckhardt et al. demonstrated that geometric current constriction materials, including oxide-type solid state electrolytes80. However, in the
due to poor contact between electrode and solid electrolyte resistance can case of 39K ssNMR, the quadrupolar coupling constants are high, leading to
even dominate the interfacial properties, especially in the case of an interface central transitions, thus studying materials at high magnetic fields (above
with a rigid electrolyte such as Li-LLZO system and proposed a strategy for 21 T) is necessary81. Another way to reduce the central transition line width
the identification of interfacial processes via EIS in chemically stable systems is by magic angle spinning82. The sensitivity can be increased by quadrupolar
(no considerable SEI evolution). By measuring impedance at different stack echo NMR during a Carr-Purcell-Meiboom-Gill train, as shown on
pressures and performance of a distribution of relaxation times (DRT) K[BPh4]83. The complexity of such experiments results in the fact that
analysis, the influence of the bulk, grain-boundary resistance, geometric chemical shift anisotropy (CSA) parameters have been reported rarely, for
current constriction and charge-transfer resistance can be separated, and the any K-containing samples83,84. Relative chemical shifts are known for some
rate-limiting process identified(see Fig. 4c)77. In full cells, separating the borate glasses85. Most recently, when investigating K2SnCl6 compound,
contributions from anode and cathode can be difficult and while the use of DFT analysis helped predict the CSA parameters86. Simulation of 39K
reference electrodes (RE) has been common for liquid cells, they have not ssNMR spectra of pristine and Cl-doped K3SbS4 shows subtle changes in
been widespread in solid-state batteries. Sedlmeier et. al. and Hertle et. al. ratios of mobile K1 and immobile K2 sites58.
showed that 64 μm thick gold-wires and 10 μm thick gold-plated tungsten
wires can be embedded in Li6PS5Cl and used as reference electrodes in solid In situ/operando techniques
state batteries78,79. By applying a small current (and with negligible charges in As most processes in batteries which limit their performance happen at the
the μAh range) against a Li or In/Li anode, a gold wire can be in situ lithiated electrode/electrolyte interface like the formation of SEIs, voids, dendrites,
to form a reference electrode (RE). By measuring the impedance of the in situ and operando measurements are crucial for understanding interfacial
individual electrodes against RE as well as by comparison of the full cell evolution and reaction mechanisms in working batteries. One of the pro-
impedance with the sum of the two measurements against RE the mising ones would, for example, be in situ87 or operando XPS (Fig. 4d) where

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chemical aspects can be determined precisely. Ex situ/post-mortem tech- negative formation energies for K1+xAlxTi2−x(PO4)3 and KTa2PO8, but it
niques like XPS or time-of-flight secondary ion mass spectrometry (TOF- would no doubt be beneficial for the community since the continuous
SIMS) and atom probe tomography require disassembly of the cell and symmetry measure (CSM) of crystal structures, which quantifies how dis-
exposition of the buried interface to an atmosphere, which is experimentally torted polyhedrons are from their perfect counterpart (CSM = 0), have been
difficult in the solid-state and may change the composition (to the kineti- shown to be an important parameter determining the structural capability
cally stabilized phases) or morphology of it in the process. for superionic conductance.
Few studies of potassium solid-state batteries employ XPS such as the In terms of interfacial characterization, this field is in its infancy, and
one by Shao et al. where SO2 and polysulfide species were characterized at much is yet to be understood on how the specificities of structure, pressure
the cathode of a K | K2.92Sb0.92W0.08S4 | S battery. It has furthermore been dependence of electrochemical properties of K-SSEs, and their behavior in
demonstrated that due to a higher ionization potential of potassium and a contact with K metal may be further tuned to allow for high-energy density
more pronounced screening effect than for Li and Na the observed binding cells with long enough lifetime. Here, new and revived spectroscopic and
energy may change significantly. For instance, the binding energy value of diffraction techniques, preferably applied in situ and operando, play a crucial
the C 1 s peak of K2CO3 is typical of the C 1 s peak of RCO2Li, potentially role in elucidating ion transport mechanisms at different time scales, as well
leading to misidentification88. Most in situ techniques like optical, electron as chemical changes at different length scales, from atomic to battery cell
or scanning probe microscopy require specially designed electrochemical level. For example, three-electrode cells can be used to separately study the
cells where care must be taken that the conditions in those cells resemble real processes of stripping and plating of alkali metals. Optical microscopy can
battery cells. potentially be used to study deposition/dissolution and the growth of
dendrites on the μm scale but requires a cell design where one side of the cell
Conclusions and outlook is open to the visible light. In situ electron microscopy techniques have been
Development of inorganic SSEs remains one of the most important mate- used to study the morphology, plating and evolution of lithium dendrites in
rials challenges for enabling commercialization of solid-state batteries. In solid electrolytes during cycling, but operando measurements of potassium
K-based chemistries, several classes of electrolytes (sulfide, oxide, and remain challenging due to the required thin films for transmission setups
phosphidosilicates) show promising bulk (low activation energy and rela- and the low electron beam damage threshold of potassium, necessitating the
tively high RT ionic conductivity) and interfacial electrochemical perfor- use of cryo-stages. Electrochemical atomic force microscopy may be used to
mance (stable cycling for up to 1000 of cycles). study the morphology of the cathode electrolyte interface in potassium solid
For the new synthesis routes of new K-electrolytes with high σion, state batteries on the nm scale, but its temporal resolution due to the time
inspiration can be drawn from their Li/Na analogues where change of the required for a single scan limits its use as an operando method.
synthesis conditions and thus cdefects significantly improved room tem- Computational studies dedicated to electrolyte/electrode all-solid-state
perature σion. In addition, traditional high temperature synthesis leads to interfaces for potassium ion batteries are currently close to non-existent.
relatively low σion, while a harsh mechanochemical synthesis via ball-milling Due to the complexity of interphases compared to the bulk properties,
is known to introduce defects, leading to around an order of magnitude computational studies will usually limit the work to a single ionic type. Ab-
higher σion. It should, therefore, be noted that for the search for new initio assessment on the electrochemical stability window and thermo-
potassium ionic conductors, the structure of electrolyte, doping/vacancy dynamic phase equilibria of proposed K+ ionic conductors, similarly to the
concentration as well as the synthesis methods play an important role, in work on Na+ conductors, is necessary to further the potential of potassium
particular when other phases or water might be present in the structure. SSB. The existence, and relevance of space charge layers for SSBs has been
Reproducibility of synthesis routes as well as detailed description of mate- discussed as it can potentially affect the SSE interfaces with cathode and
rials’ handling outside of inert gas environments prior to electrochemical anode. If relevant, the effects are to be similarly present in the Na and K-case
measurements remains non-addressed in many cases. Similarly, as effect of with the easiest indicator being increase/decrease of measured activation
internal strain and dislocations due to applied pressure have also been energy of ion transport compared to the bulk.
shown to be beneficial to Li+ conduction, these should also merit con- Modeling studies of superionic conductance tend to assume a static
sideration for the potassium case. framework of anions in which the cations move, recent findings however
The effects of nanoconfinement on the ionic conductivity of potassium suggest that there is much to learn about the influence of the effect anion
borohydrides might be worth exploring, as pure KBH4 is unsuitable as a SSE rotational dynamics has on the diffusivity of the cations. Structures that
due to its low RT ionic conductivity in the 10−11 S cm−1 range. In the lithium exhibit the rotor phase, however, rarely do so at the low temperatures
case, the nanoconfinement of LiBH4 into various oxides yielded a σion necessary for SSE, and even predicting which materials might have this
increase of four orders of magnitude due to the introduction of space charge property is currently not possible. Rotor phases in inorganic salts such as
effects. Those effects are expected to be even more pronounced for the anti-perovskite [BH4]−, closo-borates and carba-closo-borates ([B10H10]2−,
potassium case due to its lower ionic conductivity, making it a potentially [CB9H10]−, [B12H12]2−, [CB11H12]−), phosphates ([PO4]3−), sulfates
viable electrolyte. ([SO4]2−) and thiophosphates ([SiS4]4−, [PS4]3−, [PSe4]3−) have been shown
Anti-perovskites have been the subject of many computational studies to contribute to Li+ and Na+ diffusion via the paddle-wheel effect as well as
for SSEs for various charge carriers. However, there seems to be a gap in the in K3−2xMxPO4 (M = Mg, Ca, Sr, Ba Zn, Cd, Pb) and K3−xP1−xExO4 (E = S,
literature, when it specifically comes to computational studies focusing on Cr, Mo, W) in data analysis due to orientation disorder of the PO4 tetra-
potassium. An example of a more recent accelerated workflow investigating hedra. Further exploration into the paddle-wheel effect can potentially lead
Li, Na and Mg containing anti-perovskites combined ab initio methods with to insights in potassium ionic conductors and might already be a con-
machine learning (ML) to obtain thermodynamic and electrochemical tributing factor in several known conductors.
stability, ionic diffusivity, and semiconductance. To accelerate the compu- The conductivity of crystalline material at the mesoscale can be
tationally heavy NEB calculations, a surrogate model was employed to modeled through kinetic Monte Carlo (kMC). In this method, a stochastic
predict transition states during diffusion. The Li, Na, and Mg candidates ensemble of ionic migration enables the evaluation of the transition rate of
identified in the study as potential SSE have all already been discovered to be different events, which allows for extraction of the conductivity through the
ionic conductors, which highlights why an inclusion of K in the future would Einstein relation in a kMC simulation. This method is however yet to be
be interesting. applied to SSEs for potassium batteries.
Recent advances in superionic conductivity have shown that a corner- The modeling and computational research conducted for electrode-
sharing framework can promote ionic conduction effectively. Computa- electrolyte interfaces for solid-state potassium batteries is limited. The
tional screenings investigating this trend have not been pursued for challenges for potassium are expected to be similar, but the subject is not as
potassium-containing oxides yet, although Materials Project does report mature as lithium-based systems. Currently, most necessary is to screen

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electrolyte materials with a large electrochemical window allowing for uti- 10. Heubner, C. et al. From lithium-metal toward anode-free solid-state
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window can be investigated by subjecting the electrolytes to the chemical Funct. Mater. 31, 2106608 (2021).
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