Interface-Engineered Atomic Layer Deposition of 3D Li4Ti5O12 for High-Capacity Lithium-Ion 3D Thin-Film Batteries.

Upcoming energy-autonomous mm-scale Internet-of-things devices require high-energy and high-power microbatteries. On-chip 3D thin-film batteries (TFBs) are the most promising option but lack high-rate anode materials. Here, Li4Ti5O12 thin films fabricated by atomic layer deposition (ALD) are electrochemically evaluated on 3D substrates for the first time. The 3D Li4Ti5O12 reveals an excellent footprint capacity of 20.23 µAh cm-2 at 1 C. The outstanding high-rate capability is demonstrated with 7.75 µAh cm-2 at 5 mA cm-2 (250 C) while preserving a remarkable capacity retention of 97.4% after 500 cycles. Planar films with various thicknesses exhibit electrochemical nanoscale effects and are tuned to maximize performance. The developed ALD process enables conformal high-quality spinel (111)-textured Li4Ti5O12 films on Si substrates with an area enhancement of 9. Interface engineering by employing ultrathin AlOx on the current collector facilitates a required crystallization time reduction which ensures high film and interface quality and prospective on-chip integration. This work demonstrates that 3D Li4Ti5O12 by ALD can be an attractive solution for the microelectronics-compatible fabrication of scalable high-energy and high-power Li-ion 3D TFBs.

One-Pot Synthesis of High-Capacity Sulfur Cathodes via In-Situ Polymerization of a Porous Imine-Based Polymer.

Lithium-ion batteries, essential for electronics and electric vehicles, predominantly use cathodes made from critical materials like cobalt. Sulfur-based cathodes, offering a high theoretical capacity of 1675 mAh g-1 and environmental advantages due to sulfur's abundance and lower toxicity, present a more sustainable alternative. However, state-of-the-art sulfur-based electrodes do not reach the theoretical capacities, mainly because conventional electrode production relies on mixing of components into weakly coordinated slurries. Consequently, sulfur's mobility leads to battery degradation-an effect known as the "sulfur-shuttle". This study introduces a solution by developing a microporous, covalently-bonded, imine-based polymer network grown in situ around sulfur particles on the current collector. The polymer network (i) enables selective transport of electrolyte and Li-ions through pores of defined size, and (ii) acts as a robust host to retain the active component of the electrode (sulfur species). The resulting cathode has superior rate performance from 0.1 C (1360 mAh g-1) to 3 C (807 mAh g-1). Demonstrating a high-performance, sustainable sulfur cathode produced via a simple one-pot process, our research underlines the potential of microporous polymers in addressing sulfur diffusion issues, paving the way for sulfur electrodes as viable alternatives to traditional metal-based cathodes.

Halide and Sulfide Electrolytes in Cathode Composites for Sodium All-Solid-State Batteries and their Stability.

Sodium all-solid-state batteries may become a novel storage technology overcoming the safety and energy density issues of (liquid-based) sodium ion batteries at low cost and good resource availability. However, compared to liquid electrolyte cells, contact issues and capacity losses due to interface reactions leading to high cell resistance are still a problem in solid-state batteries. In particular, sulfide-based electrolytes, which show very high ionic conductivity and good malleability, exhibit degradation reactions at the interface with electrode materials and carbon additives. A new group of solid electrolytes, i.e., sodium halides, shows wider potential windows and better stability at typical cathode potentials. A detailed investigation of the interface reactions of Na3SbS4 and Na2.4Er0.4Zr0.6Cl6 as catholytes in cathodes and their cycling performance in full cells is performed. X-ray spectroscopy, time-of-flight spectrometry, and impedance spectroscopy are used to study the interface of each catholyte with a transition metal oxide cathode active material. In addition, impedance measurements were used to study the separator electrolyte Na3SbS4 with the catholyte Na2.4Er0.4Zr0.6Cl6. In conclusion, cathodes with Na2.4Er0.4Zr0.6Cl6 show a higher stability at low C-rates, resulting in lower interfacial resistance and improved cycling performance.

Competing Mechanisms Determine Oxygen Redox in Doped Ni-Mn Based Layered Oxides for Na-Ion Batteries.

Cation doping is an effective strategy for improving the cyclability of layered oxide cathode materials through suppression of phase transitions in the high voltage region. In this study, Mg and Sc are chosen as dopants in P2-Na0.67Ni0.33Mn0.67O2, and both have found to positively impact the cycling stability, but influence the high voltage regime in different ways. Through a combination of synchrotron-based methods and theoretical calculations it is shown that it is more than just suppression of the P2 to O2 phase transition that is critical for promoting the favorable properties, and that the interplay between Ni and O activity is also a critical aspect that dictates the performance. With Mg doping, the Ni activity can be enhanced while simultaneously suppressing the O activity. This is surprising because it is in contrast to what has been reported in other Mn-based layered oxides where Mg is known to trigger oxygen redox. This contradiction is addressed by proposing a competing mechanism between Ni and Mg that impacts differences in O activity in Na0.67MgxNi0.33- xMn0.67O2 (x < 0 < 0.33). These findings provide a new direction in understanding the effects of cation doping on the electrochemical behavior of layered oxides.

Protective NaSICON Interlayer between a Sodium-Tin Alloy Anode and Sulfide-Based Solid Electrolytes for All-Solid-State Sodium Batteries.

This paper presents a suitable combination of different sodium solid electrolytes to surpass the challenge of highly reactive cell components in sodium batteries. The focus is laid on the introduction of ceramic Na3.4Zr2Si2.4P0.6O12 serving as a protective layer for sulfide-based separator electrolytes to avoid the high reactivity with the sodium metal anode. The chemical instability of the anode|sulfide solid electrolyte interface is demonstrated by impedance spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. The Na3.4Zr2Si2.4P0.6O12 disk shows chemical stability with the sodium metal anode as well as the sulfide solid electrolyte. Impedance analysis suggests an electrochemically stable interface. Electron microscopy points to a reaction at the Na3.4Zr2Si2.4P0.6O12 surface toward the sulfide solid electrolyte, which does not seem to affect the performance negatively. The results presented prove the chemical stabilization of the anode-separator interface using a Na3.4Zr2Si2.4P0.6O12 interlayer, which is an important step toward a sodium all-solid-state battery. Due to the applied pressure that is mandatory for battery cells with sulfide-based cathode composite, the use of a brittle ceramic in such cells remains challenging.

Recent Progress for Concurrent Realization of Shuttle-Inhibition and Dendrite-Free Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have become one of the most promising new-generation energy storage systems owing to their ultrahigh energy density (2600 Wh kg-1 ), cost-effectiveness, and environmental friendliness. Nevertheless, their practical applications are seriously impeded by the shuttle effect of soluble lithium polysulfides (LiPSs), and the uncontrolled dendrite growth of metallic Li, which result in rapid capacity fading and battery safety problems. A systematic and comprehensive review of the cooperative combination effect and tackling the fundamental problems in terms of cathode and anode synchronously is still lacking. Herein, for the first time, the strategies for inhibiting shuttle behavior and dendrite-free Li-S batteries simultaneously are summarized and classified into three parts, including "two-in-one" S-cathode and Li-anode host materials toward Li-S full cell, "two birds with one stone" modified functional separators, and tailoring electrolyte for stabilizing sulfur and lithium electrodes. This review also emphasizes the fundamental Li-S chemistry mechanism and catalyst principles for improving electrochemical performance; advanced characterization technologies to monitor real-time LiPS evolution are also discussed in detail. The problems, perspectives, and challenges with respect to inhibiting the shuttle effect and dendrite growth issues as well as the practical application of Li-S batteries are also proposed.

A Practical Guide for Using Electrochemical Dilatometry as Operando Tool in Battery and Supercapacitor Research.

Lithium-ion batteries and related battery concepts show an expansion and shrinkage ("breathing") of the electrodes during cell cycling. The dimensional changes of an individual electrode or a complete cell can be continuously measured by electrochemical dilatometry (ECD). The obtained data provides information on the electrode/cell reaction itself but can be also used to study side reactions or other relevant aspects, e.g., how the breathing is influenced by the electrode binder and porosity. The method spans over a wide measurement range and allows the determination of macroscopic as well as nanoscopic changes. It has also been applied to supercapacitors. The method has been developed already in the 1970s but recent advancements and the availability of commercial setups have led to an increasing interest in ECD. At the same time, there is no "best practice" on how to evaluate the data and several pitfalls exist that can complicate the comparison of literature data. This review highlights the recent development and future trends of ECD and its use in battery and supercapacitor research. A practical guide on how to evaluate the data is provided along with a discussion on various factors that influence the measurement results.

Atomic Layer Deposition of Textured Li4 Ti5 O12 : A High-Power and Long-Cycle Life Anode for Lithium-Ion Thin-Film Batteries.

The "zero-strain" Li4 Ti5 O12 is an attractive anode material for 3D solid-state thin-film batteries (TFB) to power upcoming autonomous sensor systems. Herein, Li4 Ti5 O12 thin films fabricated by atomic layer deposition (ALD) are electrochemically evaluated for the first time. The developed ALD process with a growth per cycle of 0.6 Å cycle-1 at 300 °C enables high-quality and dense spinel films with superior adhesion after annealing. The short lithium-ion diffusion pathways of the nanostructured 30 nm films result in excellent electrochemical properties. Planar films reveal 98% of the theoretical capacity with 588 mAh cm-3 at 1 C. Substrate-dependent film texture is identified as a key tuning parameter for exceptional C-rate performance. The highly parallel grains of a strong out-of-plane (111)-texture allow capacities of 278 mAh cm-3 at extreme rates of 200 C. Outstanding cycle performance is demonstrated, resulting in 97.9% capacity retention of the initial 366 mAh cm-3 after 1000 cycles at 100 C. Compared to other deposition techniques, the superior performance of ALD Li4 Ti5 O12 is a breakthrough towards scalable high-power 3D TFBs.

Strategies for Alleviating Electrode Expansion of Graphite Electrodes in Sodium-Ion Batteries Followed by In Situ Electrochemical Dilatometry.

The electrochemical intercalation/deintercalation of solvated sodium ions into graphite is a highly reversible process, but leads to large, undesired electrode expansion/shrinkage ("breathing"). Herein, two strategies to mitigate the electrode expansion are studied. Starting with the standard configuration (-) sodium | diglyme (2G) electrolyte | graphite (poly(vinylidene difluoride) (PVDF) binder) (+), the PVDF binder is first replaced with a binder made of the sodium salt of carboxymethyl cellulose (CMC). Second, ethylenediamine (EN) is added to the electrolyte solution as a co-solvent. The electrode breathing is followed in situ (operando) through electrochemical dilatometry (ECD). It is found that replacing PVDF with CMC is only effective in reducing the electrode expansion during initial sodiation. During cycling, the electrode breathing for both binders is comparable. Much more effective is the addition of EN. The addition of 10 v/v EN to the diglyme electrolyte strongly reduces the electrode expansion during the initial sodiation (+100% with EN versus +175% without EN) as well as the breathing during cycling. A more detailed analysis of the ECD signals reveals that solvent co-intercalation temporarily leads to pillaring of the graphite lattice and that the addition of EN to 2G leads to a change in the sodium storage mechanism.

Ultrafine SnO2 nanoparticles anchored on N, P-doped porous carbon as anodes for high performance lithium-ion and sodium-ion batteries.

An ultrafine tin dioxide/N, P-doped porous carbon (SnO2/NPPC) nanocomposite is prepared through in-situ growth of tin dioxide (SnO2) nanoparticles in N, P-doped porous carbon (NPPC). Owing to the in-situ growth method, the size of SnO2 nanoparticles in SnO2/NPPC is quite small and uniform (generally less than 5.0 nm). NPPC provides a support and a conductive carbon skeleton for the SnO2 nanoparticles. The small SnO2 nanoparticles are less likely to aggregate during the discharge-charge process due to the presence of Sn-O-C bonding and nanoconfinement effect of SnO2 nanoparticles in carbon matrix. The N and P doping can provide abundant defects to facilitate the penetration of Li+ or Na+ into the interior of the electrode. In addition, the presence of Sn-N bonding can further improve the electrochemical properties of the electrodes. Thus, as an anode material for lithium-ion batteries, SnO2/NPPC possesses an enhanced rate performance, an excellent cycling stability, and a high initial Coulombic efficiency. The structure of the ultrafine SnO2 nanoparticles is well maintained in cycled SnO2/NPPC. Meanwhile, SnO2/NPPC also possesses good electrochemical performance as an anode for sodium-ion batteries. The good electrochemical properties for SnO2/NPPC materials can be ascribed to the synergetic effect between small SnO2 nanoparticles and NPPC.

Sodium Ion Conductivity in Superionic IL-Impregnated Metal-Organic Frameworks: Enhancing Stability Through Structural Disorder.

Metal-organic frameworks (MOFs) are intriguing host materials in composite electrolytes due to their ability for tailoring host-guest interactions by chemical tuning of the MOF backbone. Here, we introduce particularly high sodium ion conductivity into the zeolitic imidazolate framework ZIF-8 by impregnation with the sodium-salt-containing ionic liquid (IL) (Na0.1EMIM0.9)TFSI. We demonstrate an ionic conductivity exceeding 2 × 10-4 S · cm-1 at room temperature, with an activation energy as low as 0.26 eV, i.e., the highest reported performance for room temperature Na+-related ion conduction in MOF-based composite electrolytes to date. Partial amorphization of the ZIF-backbone by ball-milling results in significant enhancement of the composite stability towards exposure to ambient conditions, up to 20 days. While the introduction of network disorder decelerates IL exudation and interactions with ambient contaminants, the ion conductivity is only marginally affected, decreasing with decreasing crystallinity but still maintaining superionic behavior. This highlights the general importance of 3D networks of interconnected pores for efficient ion conduction in MOF/IL blends, whereas pore symmetry is a less stringent condition.

New insights into the origin of unstable sodium graphite intercalation compounds.

The thermodynamically unstable binary graphite intercalation compounds (GICs) with Na remain a main drawback preventing the implementation of Na-ion batteries in the market. In order to shed some light on the origin of Na-GICs instability, we investigate the structure and the energetics of different alkali metal (AM)-GICs by means of density functional theory (DFT) calculations with dispersion correction. We carefully consider different stages of AM-GICs for various AM concentrations and compare the results for Li, Na and K intercalation into graphite. In order to understand the compound stability, we investigated the interplay between the binding energy and the structural deformation due to the presence of AMs in graphite. Whereas the structural deformation energy linearly increases with the size of alkali metal ions, the binding energy passes through a maximum for Na-GIC. The analysis of different contributions to the binding energy allows to conclude that the alkali metal trend is broken for Li-GICs, not for Na-GICs. The high capacity for Li-GIC is a result of the small ion size of lithium. In addition to the mainly ionic binding nature, it allows to form a covalent contribution between lithium and graphite by orbital overlapping. In contrast, Na-GIC and K-GIC exhibit very small or hardly any covalent contribution. Furthermore, due to the small size of lithium the structural deformation energy cost also is small and allows van der Waals interactions between the graphite layers, which further enhance the stability of Li-GICs. For Na- and K-GICs, a higher energy amount for a structural deformation is needed and the stabilizing van der Waals interaction of graphite layers is weaker or hardly present.

Stable and Unstable Diglyme-Based Electrolytes for Batteries with Sodium or Graphite as Electrode.

We study the stability of several diglyme-based electrolytes in sodium|sodium and sodium|graphite cells. The electrolyte behavior for different conductive salts [sodium trifluoromethanesulfonate (NaOTf), NaPF6, NaClO4, bis(fluorosulfonyl)imide (NaFSI), and sodium bis(trifluoromethanesulfonyl)imide (NaTFSI)] is compared and, in some cases, considerable differences are identified. Side reactions are studied with a variety of methods, including X-ray diffraction, scanning electron microscopy, transmission electron microscopy, online electrochemical mass spectrometry, and in situ electrochemical dilatometry. For Na|Na symmetric cells as well as for Na|graphite cells, we find that NaOTf and NaPF6 are the preferred salts followed by NaClO4 and NaFSI, as the latter two lead to more side reactions and increasing impedance. NaTFSI shows the worst performance leading to poor Coulombic efficiency and cycle life. In this case, excessive side reactions lead also to a strong increase in electrode thickness during cycling. In a qualitative order, the suitability of the conductive salts can be ranked as follows: NaOTf ≥ NaPF6 > NaClO4 > NaFSI ≫ NaTFSI. Our results also explain two recent, seemingly conflicting findings on the degree of solid electrolyte interphase formation on graphite electrodes in sodium-ion batteries [ Maibach , J. ; ACS Appl. Mater. Interfaces 2017 , 9 , 12373 - 12381 ; Goktas , M. ; Adv. Energy Mater. 2018 , 8 , 1702724 ]. The contradictory findings are due to the different conductive salts used in both studies.

Intercalation chemistry of graphite: alkali metal ions and beyond.

Reversibly intercalating ions into host materials for electrochemical energy storage is the essence of the working principle of rocking-chair type batteries. The most relevant example is the graphite anode for rechargeable Li-ion batteries which has been commercialized in 1991 and still represents the benchmark anode in Li-ion batteries 30 years later. Learning from past lessons on alkali metal intercalation in graphite, recent breakthroughs in sodium and potassium intercalation in graphite have been demonstrated for Na-ion batteries and K-ion batteries. Interestingly, some significant differences proved to exist for the intercalation of Na+ and K+ into graphite compared with the Li+ case. Such different host-guest interactions are unique depending on the host materials and electrolytes, which greatly contribute to a deeper understanding of intercalation-type electrode materials for next generation alkali metal ion batteries. This review summarizes significant advances from both experimental and theoretical calculations with a focus on comparing the intercalation of three alkali metal ions (Li+, Na+, K+) into graphite and aims to clarify the intimate host-guest relationships and the underlying mechanisms. New approaches developed to achieve favorable intercalation coupled with the challenges in this field are also discussed. We also extrapolate alkali metal ion intercalation in graphite to mono-/multi-valent ions in layered electrode materials, which will deepen the understanding of intercalation chemistry and provide guidance to explore new guests and hosts.

Comparative study of density functionals for the description of lithium-graphite intercalation compounds.

The lack of description of van der Waals interactions in layered materials such as graphite and binary graphite intercalation compounds remains a main drawback of conventional density functional theory. Two fundamentally different approaches to overcome this issue are the employment of semiempirical dispersion correction scheme such as Grimme dispersion correction or nonlocal density functionals. We carefully compare these two approaches for the description of the geometric structure and the thermodynamic stability of pure graphite and Li-GICs at different lithium concentrations and stages. Based on the computed formation energies, we also evaluate the lithium-graphite intercalation potential. We find that PBE-D3(BJ) accurately reproduces the lattice parameters and the interlayer binding energy of graphite, although it underestimates the thermodynamic stability of stage-II Li-GICs mainly due to overbinding of carbon atoms in pure graphite. The nonlocal van der Waals functionals optB88-vdW, optB86b-vdW, and revPBE-vdW show a good agreement with experiments concerning stability of Li-GICs of different stages, although they overestimate the van der Waals interactions in graphite. The experimentally determined decreasing step-function behavior of Li-graphite intercalation potential can be qualitatively reproduced only by employing the revPBE van der Waals functional, whereas the other density functionals fail in the description. © 2019 Wiley Periodicals, Inc.

Sulfur Spillover on Carbon Materials and Possible Impacts on Metal-Sulfur Batteries.

There is currently intense research on sulfur/carbon composite materials as positive electrodes for rechargeable batteries. Such composites are commonly prepared by ball milling or (melt/solution) impregnation to achieve intimate contact between both elements with the hope to improve battery performance. Herein, we report that sulfur shows an unexpected "spillover" effect when in contact with porous carbon materials under ambient conditions. When sulfur and porous carbon are gently mixed in a 1:1 mass ratio, complete surface coverage takes place within just a few days along with the loss of the sulfur bulk properties (crystallinity, melting point, Raman signals). Sulfur spillover also occurs in the presence of a liquid phase. Consequences of this phenomenon are discussed by considering a sodium-sulfur cell with a solid electrolyte membrane.

Editorial: The Energy Challenge, Batteries, and Why Simple Math Matters.

"Despite the great progress we have seen in the last 20 years, we are still far from having a sustainable energy supply … When discussing the Energiewende, the relevant numbers are so large that they are hard to realize. How can we understand the dimension of the Energiewende in a more concrete way? …". Read more in the Editorial by Philipp Adelhelm.

From Lithium-Ion to Sodium-Ion Batteries: Advantages, Challenges, and Surprises.

Mobile and stationary energy storage by rechargeable batteries is a topic of broad societal and economical relevance. Lithium-ion battery (LIB) technology is at the forefront of the development, but a massively growing market will likely put severe pressure on resources and supply chains. Recently, sodium-ion batteries (SIBs) have been reconsidered with the aim of providing a lower-cost alternative that is less susceptible to resource and supply risks. On paper, the replacement of lithium by sodium in a battery seems straightforward at first, but unpredictable surprises are often found in practice. What happens when replacing lithium by sodium in electrode reactions? This review provides a state-of-the art overview on the redox behavior of materials when used as electrodes in lithium-ion and sodium-ion batteries, respectively. Advantages and challenges related to the use of sodium instead of lithium are discussed.

Cell Concepts of Metal-Sulfur Batteries (Metal = Li, Na, K, Mg): Strategies for Using Sulfur in Energy Storage Applications.

There is great interest in using sulfur as active component in rechargeable batteries thanks to its low cost and high specific charge (1672 mAh/g). The electrochemistry of sulfur, however, is complex and cell concepts are required, which differ from conventional designs. This review summarizes different strategies for utilizing sulfur in rechargeable batteries among membrane concepts, polysulfide concepts, all-solid-state concepts as well as high-temperature systems. Among the more popular lithium-sulfur and sodium-sulfur batteries, we also comment on recent results on potassium-sulfur and magnesium-sulfur batteries. Moreover, specific properties related to the type of light metal are discussed.

A comparative study on the impact of different glymes and their derivatives as electrolyte solvents for graphite co-intercalation electrodes in lithium-ion and sodium-ion batteries.

The abundance of sodium has recently sparked considerable interest in sodium-ion batteries (NIBs). Their similarity to conventional lithium-ion technology is obvious; however, the cell chemistry often significantly deviates. Graphite, although being the standard negative electrode in Li-ion batteries, is largely inactive for Na-ion storage in conventional non-aqueous carbonate-based electrolytes, for example. Very recently, it has been demonstrated that graphite can be activated for Na-ion storage in cells with ether-based electrolytes. The storage mechanism is based on co-intercalation of solvent molecules along with the Na-ions, forming ternary graphite intercalation compounds (t-GICs). This process is highly reversible but yet poorly understood. Here, we provide a comprehensive study on the formation and the stability of t-GICs. A series of ether solvents are being discussed: linear glymes with different chain lengths (mono-, di-, tri-, and tetraglyme), several derivatives with side groups as well as tetrahydrofuran (THF) as a cyclic ether and one crown ether. We show that the redox potentials shift depending on the ether chain length and mixing of ethers might enable tailoring of the redox behaviour. The inferior behaviour of triglyme is likely due to the less ideal ion coordination. Complementary experiments with lithium are made and demonstrate the superior behaviour of sodium. We find that the increase in graphene layer spacing during intercalation only slightly depends on the chain length and is in the range of 250%, and still mechanical stability is preserved. We further show the t-GICs possess chemical stability and demonstrate that the kinetically favoured charge transfer is probably due to the absence of a solid electrolyte interphase.