research paper on solid state chemistry

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Themed collection Advances in Solid State Chemistry and its Applications

Themed issue on advances in solid state chemistry and its applications.

Guest Editors Caroline Kirk, Finlay Morrison, Jan Skakle, Derek Sinclair and John Irvine introduce this Journal of Materials Chemistry A themed issue on advances in solid state chemistry and its applications, in celebration of Professor Tony West’s 70th birthday.

Defect chemistry and electrical properties of sodium bismuth titanate perovskite

We review the diversity of the electrical behaviour of NBT induced by various defect mechanisms, including A-site Na or Bi non-stoichiometry, isovalent-substitution, and acceptor- and donor-doping.

Identification and characterisation of high energy density P2-type Na 2/3 [Ni 1/3− y /2 Mn 2/3− y /2 Fe y ]O 2 compounds for Na-ion batteries

The Na x [Ni ( x − y )/2 Mn (2− x − y )/2 Fe y ]O 2 composition space was explored, and two compositions were identified as P2 compounds that can deliver high energy densities.

Pressure-induced chemistry for the 2D to 3D transformation of zeolites

ADOR, an unconventional synthesis strategy based on a four-step mechanism: assembly, disassembly, organization, and reassembly, has opened new possibilities in zeolite chemistry.

Bubble-supported engineering of hierarchical CuCo 2 S 4 hollow spheres for enhanced electrochemical performance

Hierarchical CuCo 2 S 4 hollow spheres are constructed by continual aggregation and growth of CuCo 2 S 4 nanocrystals on the surface of gas bubbles.

Gaudefroyite: a mineral with excellent magnetocaloric effect suitable for liquefying hydrogen

A natural mineral, gaudefroyite, displays excellent low temperature magnetocaloric properties that are suitable for liquefying hydrogen.

Cation, magnetic, and charge ordering in MnFe 3 O 5

The high pressure material MnFe 3 O 5 displays a rich variety of magnetically ordered states on cooling through three separate phase transitions.

Superexchange-mediated negative thermal expansion in Nd-doped BiFeO 3

Bi 0.7 Nd 0.3 FeO 3 is a G z -type antiferromagnet (space group Pn ′ ma ′); competition between geometric effects and magnetic superexchange results negative thermal expansion below 200 K.

Remarkable impact of low BiYbO 3 doping levels on the local structure and phase transitions of BaTiO 3

Bi 3+ with a stereochemically active lone-pair of electrons induces severe lattice strain in BaTiO 3 as revealed by a significant Raman shift of the mode associated with the O–Ti–O bonds.

Crystal structure and compositional effects on the electrical and electrochemical properties of GdBaCo 2− x Mn x O 5+ δ (0 ≤ x ≤ 2) oxides for use as air electrodes in solid oxide fuel cells

GdBaCo 2− x Mn x O 5+ δ is a new system of layered perovskites displaying better electrochemical properties when a layered-type ordering of Gd and Ba cations is adopted.

Interplay between humidity, temperature and electrical response of a conductivity sensor based on a La 2 LiNbO 6 double perovskite

The electrical response to RH% of a new La 2 LiNbO 6 double perovskite as a sensing material in a humidity sensor.

NASICON LiM 2 (PO 4 ) 3 electrolyte (M = Zr) and electrode (M = Ti) materials for all solid-state Li-ion batteries with high total conductivity and low interfacial resistance

All solid-state batteries based on NASICON-type LiM 2 (PO 4 ) 3 electrolyte phases are highly promising owing to their high ionic conductivities and chemical stabilities.

Optimisation of functional properties in lead-free BiFeO 3 –BaTiO 3 ceramics through La 3+ substitution strategy

The structure and key functional properties of a promising lead-free solid solution, BiFeO 3 –BaTiO 3 , have been optimised by controlling chemical homogeneity via La-substitution strategies and thermal treatment.

Local structure and conductivity behaviour in Bi 7 WO 13.5

Total neutron scattering analysis reveals details of cation coordination and vacancy distribution in Bi 7 WO 13.5 .

Electric field effect on the microstructure and properties of Ba 0.9 Ca 0.1 Ti 0.9 Zr 0.1 O 3 (BCTZ) lead-free ceramics

Systematic evaluation of the effect that electric field application has on the structure, microstructure and piezo-ferroelectric properties of barium titanate-based lead-free piezoelectric ceramics reveals a field-induced phase transition underlying its high sensibility.

Nano-scale hydroxyapatite compositions for the utilization of CO 2 recovered using post-combustion carbon capture

A novel approach to carbon sequestering using hydroxyapatite to incorporate significant amounts of CO 2 with potential product applications as fertiliser.

Phase-pure BiFeO 3 produced by reaction flash-sintering of Bi 2 O 3 and Fe 2 O 3

Nanostructured, highly-insulating, single-phase BiFeO 3 is obtained by applying a small DC voltage to a mixture of Bi 2 O 3 and Fe 2 O 3 at 625 °C in seconds.

Microstructure dependence of performance degradation for intermediate temperature solid oxide fuel cells based on the metallic catalyst infiltrated La- and Ca-doped SrTiO 3 anode support

High peak power density and slow performance degradation for Ni–Fe infiltrated LSCT A− anode resulted from a favourable interaction between NiFe and the perovskite backbone due to the formation of a Fe-rich oxide interface layer.

Biotemplating: a sustainable synthetic methodology for Na-ion battery materials

Dextran biotemplating offers a novel, sustainable and fast reduced-temperature synthetic route for energy storage materials ( e.g. P3-Na 2/3 Ni 1/3 Mn 2/3 O 2 ) with fine control over particle size and morphology that offers a new route to optimizing electrochemical properties.

First transparent oxide ion conducting ceramics synthesized by full crystallization from glass

New transparent Ln 1+ x Sr 1− x Ga 3 O 7+ δ (Eu/Gd/Tb) melilite ceramics, elaborated by full crystallization from glass, show anionic conductivity (>0.01 S cm −1 at 700 °C).

Crystal structure and surface characteristics of Sr-doped GdBaCo 2 O 6− δ double perovskites: oxygen evolution reaction and conductivity

Upon Sr-doping in GdBa 1− x Sr x Co 2 O 6− δ , a shift of the valence band maximum VB max towards the Fermi energy E F was observed leading to better OER activity.

The crystal structure and electrical properties of the oxide ion conductor Ba 3 WNbO 8.5

The crystal structure of the novel oxide ion conductor Ba 3 WNbO 8.5 .

Thermal evolution of structures and conductivity of Pr-substituted BaZr 0.7 Ce 0.2 Y 0.1 O 3− δ : potential cathode components for protonic ceramic fuel cells

Pr doping in BZCY72 induces symmetry changes and enhances mixed-conductivity for electrochemical applications, with Pr concentration influencing the charge-compensation mechanism.

A structural study of Ruddlesden–Popper phases Sr 3− x Y x (Fe 1.25 Ni 0.75 )O 7− δ with x ≤ 0.75 by neutron powder diffraction and EXAFS/XANES spectroscopy

Ruddlesden–Popper phases Sr 3− x Y x (Fe 1.25 Ni 0.75 )O 7− δ with x ≤ 0.75 have been characterised by neutron powder diffraction and EXAFS/XANES spectroscopy.

Oxygen transport phenomena in (La,Sr) 2 (Ni,Fe)O 4 materials

Oxygen conductivity of La 1.5 Sr 0.5 Ni 1− y Fe y O 4+ δ membranes.

About this collection

Professor Tony West was the founding Editor of Journal of Materials Chemistry . In celebration of Professor West’s 70 th birthday, this issue honours his contributions to the field and includes those people who have worked with him over the course of his career. 

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Advances in solid-state transformations of coordination bonds: from the ball mill to the aging chamber.

1. Introduction

2. the role of solvent-free synthesis in coordination chemistry, 3. mechanochemical synthesis of coordination polymers, 3.1. mechanochemistry, history, scope and benefits, 3.2. mechanochemical synthesis of coordination polymers by neat grinding, 3.3. mechanochemical synthesis of coordination polymers by liquid-assisted grinding (lag), 3.4. mechanochemical screening for metal-based derivatives of active pharmaceutical ingredients (apis), 3.5. mechanochemical synthesis of mofs by neat grinding, 3.6. mechanochemical amorphization of mofs, 3.7. mechanochemical synthesis of mofs using lag and ilag methodology, 4. recent mechanistic studies, 4.1. ex situ (stepwise) monitoring of mechanochemical reactions, 4.2. in situ and real-time monitoring of mof synthesis, 5. synthesis assisted by solvent vapour, 5.1. vapour digestion, 5.2. accelerated aging: synthesis of mofs inspired by mineral neogenesis, 5.3. geological significance, 5.4. accelerated aging as a materials testing procedure, 6. thermochemical solid-state synthesis, 7. conclusions, acknowledgments, author contributions, conflicts of interest.

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Mottillo, C.; Friščić, T. Advances in Solid-State Transformations of Coordination Bonds: From the Ball Mill to the Aging Chamber. Molecules 2017 , 22 , 144. https://doi.org/10.3390/molecules22010144

Mottillo C, Friščić T. Advances in Solid-State Transformations of Coordination Bonds: From the Ball Mill to the Aging Chamber. Molecules . 2017; 22(1):144. https://doi.org/10.3390/molecules22010144

Mottillo, Cristina, and Tomislav Friščić. 2017. "Advances in Solid-State Transformations of Coordination Bonds: From the Ball Mill to the Aging Chamber" Molecules 22, no. 1: 144. https://doi.org/10.3390/molecules22010144

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Solid-state batteries: from ‘all-solid’ to ‘almost-solid’

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Hanyu Huo, Jürgen Janek, Solid-state batteries: from ‘all-solid’ to ‘almost-solid’, National Science Review , Volume 10, Issue 6, June 2023, nwad098, https://doi.org/10.1093/nsr/nwad098

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Lithium-ion batteries (LIBs) have been the undisputed leading technology in electrochemical energy storage since they were commercialized in 1991. Since then, the mass manufacturing of LIBs has reached maturity, and we have also seen the realization of high energy density, long cycling stability and low cost. LIB technology enabled the huge success of mobile consumer electronics, with its usage in electric vehicles and other advanced devices. Due to the use of organic solvents for the electrolytes, LIBs are sensitive to high temperatures, lose performance at low temperatures and show inherent safety risks with increasing energy density (Fig. 1a ). As the performance of current LIBs is also limited, next-generation battery technologies are being intensively investigated, especially given the ever-increasing demand for high energy density as well as high power density.

Comparison of various cell concepts with different fractions of liquid components.

All-solid-state batteries (all-SSBs) have emerged in the last decade as an alternative battery strategy, with higher safety and energy density expected [ 1 ]. The substitution of flammable liquid electrolytes (LEs) with solid electrolytes (SEs) promises improved safety. Moreover, the possibility of bipolar stacking, and the use of high-voltage cathodes and a lithium metal anode can potentially improve the energy density of SSBs compared to LIBs. The work reported by Kanno and other Japanese scientists, in which an SE (i.e. Li 10 GeP 2 S 12 ) showed a lithium ion conductivity higher than LEs [ 2 ] for the first time, further fueled interest and confidence in the practical applications of SSBs.

Although many companies announced their all-SSB layout based on different SEs a long time ago, most companies experienced difficulties when it came to launching any all-SSB products. The critical bottleneck comes from the SEs and their properties, especially their interface issues (Fig. 1d ) [ 3 ]. Oxide SEs made of authentic ceramics not only require high temperature/pressure sintering for densification but also show slow interface kinetics, mainly due to

poor interface contact. The use of sulfide/halide SEs is inevitably affected by moisture and requires dry-room operation, although cold-press densification is feasible for relatively soft sulfide/halide SEs. All-SSBs based on inorganic SEs in general suffer from chemo-mechanical issues (either contact loss, interphase formation, or both) during operation, even if the SE/electrode contact is sufficient after assembly. Polymer-based all-SSBs have the advantage of apparently good SE/electrode contact but require an elevated operation temperature due to the insufficient ionic conductivity of polymers at room temperature. Interface degradation occurs at high potentials considering the narrow electrochemical window of typical polymer SEs. Current all-SSBs are therefore still less competitive than LIBs with regard to cycling stability, rate performance and energy density. Moreover, the high price of SEs, unmatured production lines and additional devices for stack pressure create barriers for the scaling up of all-SSBs.

Recently, hybrid battery concepts have emerged as an intermediate route, where both SEs and LEs are involved in pursuing higher safety and energy density than LIBs while mitigating the chemo-mechanical problems in SSBs (Fig. 1b ). These hybrid solid-liquid concepts have been advanced by various scientists and companies, and are often referred to as ‘semi-’, ‘quasi-’ or ‘pseudo-’ SSB concepts—but also often simply considered as SSBs in public, which may be misleading [ 4 ]. In the case of polymer-based cells, adding a (substantial amount of) LE leads to the formation of gel polymer electrolytes with improved ionic conductivity; this method is widely used. In the case of inorganic SEs, the LE ideally fills voids and gaps, increases the electrochemically active interface areas, and thus lowers the electrode tortuosity and impedance.

Semi-SSBs share major materials, similar manufacturing processes and similar production lines with current LIBs, thus are easier to scale up compared to all-SSBs. Many companies demonstrated their semi-SSB products successively. Energy densities have been announced to be ∼350 Wh kg –1 , with claims of up to 400 Wh kg –1 achieved by optimized pack structures and alternative electrodes with higher specific capacities. For example, NIO launched a 150 kWh semi-SSB consisting of a hybrid electrolyte, Si-C composite anode and ultra-high nickel cathode, with an energy density of 360 Wh kg –1 , enabling a 1000 km driving range on a single charge [ 5 ]. The fraction of liquids in these semi-SSBs was never revealed, yet it is speculated to be 10 wt% to 15 wt% based on typical gel polymer electrolytes. However, the targeted increase in safety will probably only be achieved if the fraction of added liquid gets much smaller. The liquid fraction should probably be <5 wt% for almost-SSBs (Fig. 1c ) [ 6 ]. However, even all-SSBs exclusively containing solid components may still have a risk of thermal runaway [ 7 ]. Clearly, the safety issues of SSBs will be different from LIBs, yet clear-cut proof still requires in-depth evaluation.

Current semi-SSBs, often considered SSBs for simplicity, are based on the modification of LIBs, where the ion transport in both electrolyte and electrode is mainly governed by an LE. We assume that this modification may be a marketing strategy, rather than a real advantage of SSBs over LIBs, especially if only a small amount of SE is added to what is otherwise an LE. From our point of view, the liquid component should only serve as an interface agent to keep the liquid fraction low, for safety reasons, and the solid/liquid interfaces need to be chemically stable. Otherwise, degradation and interphase formation may occur, leading to a performance decrease in the long term and compromising the whole concept. Since both oxide SEs and sulfide SEs show a strong tendency toward interaction with organic solvents, small-molecular-weight polymers are applied to substitute conventional LEs to stabilize the interfaces [ 8 ]. Super-concentrated (or solvent-in-salt) electrolytes or solvate ionic liquids are also suggested, where the strong interaction between Li + ions and electronegative elements in the polar solvents can alleviate the reactivity of solvents, thus stabilizing the liquid/solid interfaces [ 9 , 10 ]. In addition, adding a liquid improves the electrochemical properties of electrodes only if ion transport through the composite is improved and electron transport is not compromised. This requires that ion transfer across the solid/liquid interfaces shows a sufficiently low resistance—which has rarely been proven. Recently, in situ polymerization has been used to solidify an originally liquid component in semi-SSBs, thus lowering the liquid content [ 11 ]. The liquid acts as a ‘self-healing’ additive at the beginning. Once it polymerizes, it still helps to keep sufficient contact even in the case of volume changes of electrodes.

Thin separators (<60 μm) and thick cathodes (>4 mAh cm –2 ) are required to boost the energy density (>350 Wh kg –1 ) of almost-SSBs [ 6 ]. This not only needs advanced fabrication processes with optimized microstructures, but also requires solid/liquid electrolytes with good ionic conductivity to ensure fast ion transport. Organic-inorganic composite SEs, which combine the advantages of both organic and inorganic SEs, show good ductility and mechanical strength, good processability, and sufficient ionic conductivity for mass production. The porosity of cathode composites should be decreased to meet the target of <5 wt% (pore-filling) LE for almost-SSBs. Techniques, such as microstructure optimization and calendering in a dry process with different shear forces, need to be explored to minimize porosity without compromising the structural integrity of cathodes. In addition, we highlight the need for a high yield strength of SEs instead of a high Young's modulus to mitigate the interface stress by the volume change of electrodes [ 12 ]. The quantitative study of the role of a liquid component on chemo-mechanical properties deserves further investigation as we transition from all-SSBs to almost-SSBs. Not least, lithium dendrite suppression should be considered once lithium metal is used as the anode.

The ‘all-solid’ concept is not necessarily the most rewarding target; rather, ‘almost-solid’ may be the most feasible strategy. A small fraction of liquid interface additive may lower the electrode impedance, help to mitigate contact loss when there are local cracks and keep long-term stability under the influence of cyclic volume changes of active materials—provided that LE and SE do not react and cause chemical degradation. To move from current semi-SSBs to almost-SSBs, a smaller liquid fraction (probably <5 wt%) is required to achieve safety targets. Both highly conductive SEs and LEs (i.e. >10 mS cm –1 at room temperature) and corresponding solid/liquid interface stability need to be achieved and further explored en route. The cost of mass production should be decreased via optimized manufacturing processes and innovative material recycling routes. In any case, we are confident that we will see the commercial success of almost-SSBs in the near future.

This work was supported by the Federal Ministry of Education and Research (BMBF, Bundesministerium für Bildung und Forschung) within the FESTBATT consortium (03XP0430A).

Conflict of interest statement . None declared.

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• Published: 23 February 2023

Challenges in speeding up solid-state battery development

• Jürgen Janek   ORCID: orcid.org/0000-0002-9221-4756 1 , 2 &
• Wolfgang G. Zeier   ORCID: orcid.org/0000-0001-7749-5089 3 , 4  

Nature Energy volume  8 ,  pages 230–240 ( 2023 ) Cite this article

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• Materials for energy and catalysis

Recent worldwide efforts to establish solid-state batteries as a potentially safe and stable high-energy and high-rate electrochemical storage technology still face issues with long-term performance, specific power and economic viability. Here, we review key challenges that still involve the need for fast-conducting solid electrolytes to provide sufficient transport in composite cathodes. In addition, we show that high-performance anodes together with protection concepts are paramount to establish dense high-energy solid-state batteries and that lithium-based solid-state batteries as well as metal anodes may not be the ultimate solution. We further discuss that diversity in terms of materials, research teams and approaches is key to establish long-term solid-state batteries. About ten years after the first ground-breaking publication of lithium solid electrolytes with an ionic conductivity higher than that of liquid electrolytes, it is time to realistically address the remaining key challenges for full-scale commercialization, cell performance and implementation.

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Acknowledgements

We acknowledge financial support within the cluster of competence FESTBATT funded by Bundesministerium für Bildung und Forschung (BMBF; projects 03XP0431, 03XP0430A and 03XP0430F). We thank P. Till for support in data analyses.

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Janek, J., Zeier, W.G. Challenges in speeding up solid-state battery development. Nat Energy 8 , 230–240 (2023). https://doi.org/10.1038/s41560-023-01208-9

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Solid State ChemiStry and itS appliCationS Anthony R. West

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In Lecture 2 we went through the three cubic 1:1 structures possible: CsCl(8,8 coordinate , i.e. the coordination number of both the cation and the anion is 8) NaCl(6,6 coordinate) and ZnS (4,4 coordinate). In this lecture, we will look in more quantitative detail at some of the concepts already outlined i.e. lattice energies, packing radius ratios, a detailed look at structure selection (first: stoichiometry, then either extent of covalency, or radius ratio, or both). And finally, we will cover some stoichiometries other than 1:1. By taking the electronegativities on page 3 of handout one and plotting points on a Van Arkel-Ketelaar Triangle, with colour coding according to the type of structure adopted, for a wide range of binary XY solids, the following pattern emerges: Using this method, there is a remarkably clear distinction between the 6,6-coordinate , more ionic NaCl-type structures (dark grey diamonds), and the more covalent 4,4 zincblende structures (pale grey squares). To define the triangle, Cs metal and F 2 are shown along the bottom as black diamonds, and also along the bottom (zero electronegativity difference) Si, C, Ge and Sn are shown as zincblende structures because of the identical 4,4 tetrahedral coordination , though the fact that both types of position " cation " and " anion " are identical in those cases means that they are not strictly describable as zincblende structures. This diagram is persuasive of the notion that electronegativity difference, directly correlated with extent of covalency, is a powerful director and predictor of structural preference: More covalent: lower coordination number. You will not find this point discussed in Chem 3 nor in any other text in existence, though there is some discussion of bonding triangles on page 295-296. However, there is one 1:1 structure yet to be included: CsCl structure is surprisingly rare, being more rarely observed than would be predicted on the basis of radius ratio (see below). Though it is the ideal way for ionic 1:1 solids to pack in terms of maximizing the electrostatic attractive terms, it is only adopted by CsCl, CsBr, and CsI amongs all the alkali halides. All others are Rocksalt, NaCl lattice. In so doing these three define the outer edge of the Van Arkel Triangle. There are other compounds which fit less-well, but there are questions over the accuracy of the assumptions on bonding: TlCl, TlBr and TlI also adopt CsCl structures, despite TlI being predicted NaCl.

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Previous studies of kieserite analogues and also other systems (Tutton’s salts, alums and -K2SO4 isomorphs) have shown that in a series of isostructural/isomorphous compounds the unit-cell parameters and volumes vary linearly with the effective ionic radii (the &#39;size&#39;) of the structural units. This is in line with the results of Shannon (Acta Cryst. A32 (1976) 751–767). Somewhat unexpectedly, other important parameters of the crystal structure, such as fractional atomic co-ordinates, exhibit systematic variations as well. An attempt is made to reveal the reasons that are at the origin of this finding.

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