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Schematic illustration of interface charge redistribution between oxide cathodes and sulfide SEs after different interface engineering approaches a Initial interface. b Double-phase interface with fast Li-ion conductor CIBLs. c TPI with discontinuous ferroelectric nanoparticles. The regions with light colors correspond to the relative Li-ion deficiency. FMs ferroelectric materials.
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The space charge layer (SCL) is generally considered one of the origins of the sluggish interfacial lithium-ion transport in all-solid-state lithium-ion batteries (ASSLIBs). However, in-situ visualization of the SCL effect on the interfacial lithium-ion transport in sulfide-based ASSLIBs is still a great challenge. Here, we directly observe the ele...
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Citations
... This result means that a gradual slope of potential near the interface is constructed by LiNbO 3 in NPC-30 electrolyte, indicating a mitigated SCL between the cathode and NPC-30 [48]. The weakened SCL would decrease the interfacial polarization of the NCM811 with the NPC-30 electrolyte to promote the Li-ion transport at the interface [30,49]. In addition, the XPS of the ...
The composite solid-state electrolytes (CSEs) are one of the most promising electrolytes for advanced solid-state Li metal batteries. However, it is unclear for the effect of the induced electric field inside CSEs on the Li-ion transport. Herein, we design a compact CSE by imbedding the lithium niobate (LiNbO3) with both high ionic conductivity and dielectric constant into poly(vinylidene fluoride) matrix (NPC). The LiNbO3 significantly enhances the internal electric field of NPC along the LiNbO3 particles and establishes uniform interfacial electric field between NPC and electrodes, which fundamentally facilitates the Li-ion transport, weakens the space-charge layer and inhibits the growth of Li dendrites. Continuous fast ion-conducting channels with high concentration of Li-ions are constructed inside NPC, which contributes to a quite high ionic conductivity (7.39×10−4 S cm−1, 25°C) and ultra-low activation energy (0.112 eV). The LiNi0.8Co0.1Mn0.1O2/NPC/Li solid-state batteries exhibit quite stable cycling performance at 25°C.
... Establishing sufficient physical contact among the solid constituent particles poses a considerably greater challenge than achieving comparable contact with liquid electrolytes in conventional lithium-ion batteries, often leading to high interfacial resistance in SSBs 9,10 . Another critical issue is the formation of space charge layers at interfaces between heterogeneous solid materials, which induces lithium ion depletion at the interface and consequently results in increased interfacial resistance [11][12][13] . Moreover, addressing the chemical and electrochemical instability at the interface represents an essential challenge to be overcome 14 . ...
Introducing a coating layer (CL) at an active material (AM)/solid electrolyte (SE) interface is a pivotal approach to ensure interfacial stability in solid-state batteries (SSBs), thereby improving their durability and performance. To thermodynamically protect the interface, CLs must not only be chemically compatible with the SE and AM but also maintain Li chemical potential ( µ Li ) at the SE/CL interface within the electrochemical window of the SE. However, a general CL design principle to achieve this remains unestablished. Here we theoretically elucidate the µ Li distribution across the SE and CL in SSBs and examine the requirements for CLs to thermodynamically protect SEs. We show that the protective capability of CLs is not solely determined by their intrinsic characteristics and chemical compatibility with SEs and AMs, but is also governed by the µ Li distribution within the SE and CL. We propose a quantitative approach based on the µ Li distribution within the SE and CL to determine the required characteristics and geometries of CLs that ensure interfacial thermodynamic stability while minimizing ohmic resistance in SSBs, providing insights for CL design.
... The contact area inhibits a large interfacial resistance, making the effect unfavorable when using oxide cathode active materials and sulfide solid electrolytes. For example, for Li6PS5Cl and LiCoO2, the interface is in Li + equilibrium because of the formation of a deficiency region on the sulfide electrolyte side and a Li + enriched positive charge density region on the oxide electrode [41,42]. While the Li + deficiency region in sulfides is unfavorable for interfaces between electrolyte and electrode materials, it enhances the lithium conductivity in the hybrid electrolytes investigated here. ...
... The lithium-ion conduction in the space-charge layer is highly dependent on the charge-carrier concentration as well as the specific atomic configuration [40]. When two different materials (i.e., sulfide and oxide) are in contact, the space-charge layer is dependent on the chemical potential difference between them [41][42][43][44][45]. The contact area inhibits a large interfacial resistance, making the effect unfavorable when using oxide cathode active materials and sulfide solid electrolytes. ...
... The contact area inhibits a large interfacial resistance, making the effect unfavorable when using oxide cathode active materials and sulfide solid electrolytes. For example, for Li 6 PS 5 Cl and LiCoO 2 , the interface is in Li + equilibrium because of the formation of a deficiency region on the sulfide electrolyte side and a Li + enriched positive charge density region on the oxide electrode [41,42]. While the Li + deficiency region in sulfides is unfavorable for interfaces between electrolyte and electrode materials, it enhances the lithium conductivity in the hybrid electrolytes investigated here. ...
Despite the variety of solid electrolytes available, no single solid electrolyte has been found that meets all the requirements of the successor technology of lithium-ion batteries in an optimum way. However, composite hybrid electrolytes that combine the desired properties such as high ionic conductivity or stability against lithium are promising. The addition of conductive oxide fillers to sulfide solid electrolytes has been reported to increase ionic conductivity and improve stability relative to the individual electrolytes, but the influence of the mixing process to create composite electrolytes has not been investigated. Here, we investigate Li3PS4 (LPS) and Li7La3Zr2O12 (LLZO) composite electrolytes using electrochemical impedance spectroscopy and distribution of relaxation times. The distinction between sulfide bulk and grain boundary polarization processes is possible with the methods used at temperatures below 10 °C. We propose lithium transport through the space-charge layer within the sulfide electrolyte, which increases the conductivity. With increasing mixing intensities in a high-energy ball mill, we show an overlay of the enhanced lithium-ion transport with the structural change of the sulfide matrix component, which increases the ionic conductivity of LPS from 4.1 × 10−5 S cm−1 to 1.7 × 10−4 S cm−1.
... This phenomenon introduces complications that extend to the TEM lamella itself. Leakage current values for MIM TEM lamella devices, in a short circuit, have been reported to range from 10 − 5 to 10 − 2 A at 0.1 V [12,16,[20][21][22]. The implications of this extend far beyond measurement accuracy, potentially distorting in situ TEM observations by masking intrinsic material behavior with short-circuit effects [19]. ...
... Up to now, operando TEM studies of electrically biased lamellae using MEMS chips were typically employed at relatively low magnification 6 , with sub-nanometer resolution achieved in only a few cases [7][8][9][10][11] ; revealing electric field-related phenomena but not necessarily implying device operando conditions. Independent of spatial resolution, I-V measurements on scaled-down/ micron-scale samples with thicknesses of less than 100 nm (maximum/required thickness for an electron transparent TEM sample) are technically challenging due to complex multi-step sample preparation that includes micromanipulation and electrical contacting. ...
... Independent of spatial resolution, I-V measurements on scaled-down/ micron-scale samples with thicknesses of less than 100 nm (maximum/required thickness for an electron transparent TEM sample) are technically challenging due to complex multi-step sample preparation that includes micromanipulation and electrical contacting. The use of conductive materials such as carbon, platinum, or tungsten with electron (EBID) and/or ion beam induced deposition (IBID) to attach and/or contact the sample via a FIB gas injection system (GIS) on MEMS-based chips has been, to date, the standard practice in the electron microscopy community [7][8][9][10][11][12][13][14] . However, FIB (GIS)-deposited materials can spread over tens of microns on a MEMS chip surface 13 , forming undesirable stray leakage current pathways between the chip leads and the surroundings, affecting the TEM lamella itself (Fig. S1) 15 . ...
... The original unit cell of STO is in Pm-3m space group with lattice constants of 3.905 Å × 3.905 Å × 3.905 Å. The projection vector and upward vector were assigned to be [110] and [1][2][3][4][5][6][7][8][9][10] of the original unit cell, respectively. Both pristine and HRS supercells were assigned as the same thickness of 182.25 Å. ...
Advanced nanomaterials are at the core of innovation for the microelectronics industry. Designing, characterizing, and testing two-terminal devices, such as metal-insulator-metal structures, is key to improving material stack design and integration. Electrical biasing within in situ transmission electron microscopy using MEMS-based platforms is a promising technique for nano-characterization under operando conditions. However, conventional focused ion beam sample preparation can introduce parasitic current paths, limiting device performance and leading to overestimated electrical responses. Here we demonstrate con-nectivity of TEM lamella devices obtained from a novel electrical contacting method based solely on van der Waals forces. This method reduces parasitic leakage currents by at least five orders of magnitude relative to reported preparation approaches. Our methodology enables operation of stack devices inside a microscope with device currents as low as 10 pA. We apply this approach to observe in situ biasing-induced defect formation, providing valuable insights into the behavior of an SrTiO 3-based memristor.
... Article resistance. 61 In situ HAAD-STEM investigation by Wang et al. 62 reported a redistribution of Li species over the LiCoO 2 / LPSCl interface on changing the potential, which induces the appearance of an additional resistance. Based on these studies, as well as on the fact that the R 4 and R 4 * peaks are present only for the discharged full cell, i.e., at high lithiation degree of the active material, we could tentatively ascribe these peaks to a SCL process. ...
Despite the high ionic conductivity and attractive mechanical properties of sulfide-based solid-state batteries, this chemistry still faces key challenges to encompass fast rate and long cycling performance, mainly arising from dynamic and complex solid–solid interfaces. This work provides a comprehensive assessment of the cell performance-determining factors ascribed to the multiple sources of impedance from the individual processes taking place at the composite cathode with high-voltage LiNi0.6Mn0.2Co0.2O2, the sulfide argyrodite Li6PS5Cl separator, and the Li metal anode. From a multiconfigurational approach and an advanced deconvolution of electrochemical impedance signals into distribution of relaxation times, we disentangle intricate underlying interfacial processes taking place at the battery components that play a major role on the overall performance. For the Li metal solid-state batteries, the cycling performance is highly sensitive to the chemomechanical properties of the cathode active material, formation of the SEI, and processes ascribed to Li diffusion in the cathode composite and in the space-charge layer. The outcomes of this work aim to facilitate the design of sulfide solid-state batteries and provide methodological inputs for battery aging assessment.
... After that, the ball-milled powder was heat-treated at 550 °C for 5 h in an atmosphere of flowing argon. The total conductivity of the synthesized LPSC solid electrolyte, measured using stainless steel blocking electrodes, was 3.2 × 10 −3 S cm −1 , as reported previously 16,55 . ...
A critical current challenge in the development of all-solid-state lithium batteries (ASSLBs) is reducing the cost of fabrication without compromising the performance. Here we report a sulfide ASSLB based on a high-energy, Co-free LiNiO2 cathode with a robust outside-in structure. This promising cathode is enabled by the high-pressure O2 synthesis and subsequent atomic layer deposition of a unique ultrathin LixAlyZnzOδ protective layer comprising a LixAlyZnzOδ surface coating region and an Al and Zn near-surface doping region. This high-quality artificial interphase enhances the structural stability and interfacial dynamics of the cathode as it mitigates the contact loss and continuous side reactions at the cathode/solid electrolyte interface. As a result, our ASSLBs exhibit a high areal capacity (4.65 mAh cm⁻²), a high specific cathode capacity (203 mAh g⁻¹), superior cycling stability (92% capacity retention after 200 cycles) and a good rate capability (93 mAh g⁻¹ at 2C). This work also offers mechanistic insights into how to break through the limitation of using expensive cathodes (for example, Co-based) and coatings (for example, Nb-, Ta-, La- or Zr-based) while still achieving a high-energy ASSLB performance.
... Such performance suggests that the long-term cycling of the Li-In | LPSCl-LZCO | LCO cell might be conducted at the specific currents higher than those usually adopted in literature. At present, 10−30 mA g -1 are the most commonly applied specific currents for demonstrating the cycling stability of allsolid-state cells based on LiCoO 2 and LiNi 0.8 Mn 0.1 Co 0.1 O 2 9,51,52 . Cycling at higher specific currents like 150−200 mA g -1 are much less frequently conducted 12,50 ; recently, a Li 2 In 1/3 Sc 1/3 Cl 4 solid electrolyte with good cycling performance was reported to enable long-term cycling at a specific current as high as 540 mA g -1 53 . ...
To enable the development of all-solid-state batteries, an inorganic solid-state electrolyte should demonstrate high ionic conductivity (i.e., > 1 mS cm⁻¹ at 25 °C), compressibility (e.g., > 90% density under 250−350 MPa), and cost-effectiveness (e.g., < $50/kg). Here we report the development and preparation of Li1.75ZrCl4.75O0.5 oxychloride solid-state electrolyte that demonstrates an ionic conductivity of 2.42 mS cm⁻¹ at 25 °C, a compressibility enabling 94.2% density under 300 MPa and an estimated raw materials cost of $11.60/kg. As proof of concept, the Li1.75ZrCl4.75O0.5 is tested in combination with a LiNi0.8Mn0.1Co0.1O2-based positive electrode and a Li6PS5Cl-coated Li-In negative electrode in lab-scale cell configuration. This all-solid-state cell delivers a discharge capacity retention of 70.34% (final discharge capacity of 70.2 mAh g⁻¹) after 2082 cycles at 1 A g⁻¹, 25 °C and 1.5 tons of stacking pressure.
... As a further step, active fillers can contribute supplementary ion transport channels, encompassing interfacial and bulk transport mechanisms [18] . Although different fillers have been added to increase the ionic conductivity of CSEs, the value remains relatively insufficient (less than 1 × 10 −4 S cm −1 ) for practical application, arguably due to the space-charge layer (SCL) between the polymer and ceramic phases that hinders Li + across-phase transport [15,19] . ...
Composite solid-state electrolytes have received significant attention due to their combined advantages as inorganic and polymer electrolytes. However, conventional ceramic fillers offer limited ion conductivity enhancement for composite solid-state electrolytes due to the space-charge layer between the polymer matrix and ceramic phase. In this study, we develop a ferroelectric ceramic ion conductor (LiTaO3) as a functional filler to simultaneously alleviate the space-charge layer and provide an extra Li⁺ transport pathway. The obtained composite solid-state electrolyte comprising LiTaO3 filler and poly (vinylidene difluoride) matrix (P-LTO15) achieves an ionic conductivity of 4.90 × 10⁻⁴ S cm⁻¹ and a Li⁺ transference number of 0.45. The polarized ferroelectric LiTaO3 creates a uniform electric field and promotes homogenous Li plating/stripping, providing the Li symmetrical batteries with an ultrastable cycle life for 4000 h at 0.1 mA cm⁻² and a low polarization overpotential (~50 mV). Furthermore, the solid-state NCM811/P-LTO15/Li full batteries achieve an ultralong cycling performance (1400 cycles) at 1 C and a high discharge capacity of 102.1 mAh g⁻¹ at 5 C. This work sheds light on the design of functional ceramic fillers for composite solid-state electrolytes to effectively enhance ion conductivity and battery performance.
... In sum, these results indicate that even with significant noise, nanoscale interfacial potentials can be directly measured by AD reconstruction from focal series imaging, addressing a key gap in the methods available for characterizing energy materials. For example, space charge layers at solid-state battery electrode|electrolyte interfaces, which can cause carrier accumulation/depletion and degrade device performance, [18,19] are often ~ 1 V in magnitude and ~ 10 nm wide [20,21] and have rarely been imaged. Instead, their occurrence has largely been inferred from electrochemical measurements, resulting in obvious uncertainty in experimental interpretation. ...
Measuring interfacial electrostatic potentials is vital to understanding many fundamental materials properties. A variety of TEM methods exist for measuring electric potentials from the phase shift produced on an electron wave as it passes through a sample. However, most are either experimentally challenging or poorly suited to resolving nanoscale features. Here, we demonstrate the viability of a simple, automatic differentiation-based exit wave reconstruction from a focal series of images to accurately measure the nanoscale electric potentials. The analysis suggests that under optimal measurement conditions, electric potentials can be resolved to less than 0.06 V in magnitude and less than 1 nm in spatial extent.Graphical abstract
