On the role of surface carbonate species in determining the cycling performance of all-solid-state batteries

Strauss, Florian; Payandeh, Seyedhosein; Kondrakov, Aleksandr; Brezesinski, Torsten

doi:10.1088/2752-5724/ac5b7d

Cited by 26 publications

(21 citation statements)

References 56 publications

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“…Specifically, Ni-rich layered oxides show a natural presence of surface impurities, such as Li 2 CO 3 and LiOH. Although contradictory results have demonstrated that Li residuals alone are already capable of somewhat stabilizing the SE/CAM interface, [84,[98][99][100][101][102] they can be incorporated into the coating during preparation and may be advantageous when included in a controlled manner. [82,84,85,98,101] This might also be the reason why nominally binary oxide-based coatings show beneficial properties if applied to NCM-type materials for SSB applications, as such oxides do not show significant lithium-ion conductivity.…”

Section: Intercalation-type (Layered) Camsmentioning

confidence: 99%

Designing Cathodes and Cathode Active Materials for Solid‐State Batteries

Minnmann

Strauss

Bielefeld

et al. 2022

Advanced Energy Materials

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CAM) in its lithiated form, that is, as present in a discharged cell. In its delithiated form, when the cell is charged, it is the only cell component that is contributing to storing energy (in conjunction with a hypothetical in situ lithiumplated anode formed during charging), thus making it the material required to be present in large quantity to achieve a high-performing cell. All other components, which may be required for large scale processing, only decrease the specific energy of the cell and are, therefore, engineered to minimize their content without affecting the function of the cell. This is evident in the research efforts made to increase the CAM content in the cathode layer, decrease the separator thickness as much as possible, and the pursuit to plate lithium metal in situ (in "anode-free" cells, which are more correctly described as "zero excess lithium metal" cells) without the use of an anode active material. [4] Thus, the CAM type and content in the cell ultimately determine the maximum specific energy that the system can provide.Moreover, the CAM contributes a significant proportion to the overall cell costs, [5] hence the necessity of steady tailoring toward reduced costs and higher energy density. So far, CAM development has mainly targeted performance optimization with LEs in LIBs. For instance, cathode electrolyte interface (CEI) formation, [6] Solid-state batteries (SSBs) currently attract great attention as a potentially safe electrochemical high-energy storage concept. However, several issues still prevent SSBs from outperforming today's lithium-ion batteries based on liquid electrolytes. One major challenge is related to the design of cathode active materials (CAMs) that are compatible with the superionic solid electrolytes (SEs) of interest. This perspective, gives a brief overview of the required properties and possible challenges for inorganic CAMs employed in SSBs, and describes stateof-the art solutions. In particular, the issue of tailoring CAMs is structured into challenges arising on the cathode-, particle-, and interface-level, related to microstructural, (chemo-)mechanical, and (electro-)chemical interplay of CAMs with SEs, and finally guidelines for future CAM development for SSBs are proposed.

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Section: Intercalation-type (Layered) Camsmentioning

confidence: 99%

Designing Cathodes and Cathode Active Materials for Solid‐State Batteries

Minnmann

Strauss

Bielefeld

et al. 2022

Advanced Energy Materials

Self Cite

127

123

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“…Figures 8 and S4 of the supporting information show the correlation between the voltage profiles and the gas evolution rates for the most evolved gases, hydrogen (H 2 , m/z = 2) and carbon dioxide (CO 2 , m/z = 44). The origin of these gases can be inferred from the analogy with gas evolution in LIBs, where CO 2 can originate either from chemical oxidation of the electrolyte associated with the release of lattice oxygen or from electrochemical oxidation of the electrolyte (or, mainly during the first cycle, from surface carbonates) [39,[59][60][61][62]. Since the released O 2 in the case of layered oxide cathode materials for LIBs is apparently highly reactive in nature, it is rarely detected directly as molecular oxygen, but indirectly as the reaction product CO 2 [63,64].…”

Section: In Situ Gas Analysismentioning

confidence: 99%

P2-type layered high-entropy oxides as sodium-ion cathode materials

et al. 2022

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P2-type layered oxides with the general Na-deficient composition NaxTMO2 (x < 1, TM: transition metal) are a promising class of cathode materials for sodium-ion batteries. The open Na+ transport pathways present in the structure lead to low diffusion barriers and enable high charge/discharge rates. However, a phase transition from P2 to O2 structure occurring above 4.2 V, combined with metal dissolution at low potentials upon discharge, results in rapid capacity degradation. In this work, we demonstrate the positive effect of configurational entropy on the stability of the crystal structure during battery operation. Three different compositions of layered P2-type oxides were synthesized by solid-state chemistry, Na0.67(Mn0.55Ni0.21Co0.24)O2, Na0.67(Mn0.45Ni0.18Co0.24Ti0.1Mg0.03)O2, and Na0.67(Mn0.45Ni0.18Co0.18Ti0.1Mg0.03Al0.04Fe0.02)O2 with low, medium and high configurational entropy, respectively. The high-entropy cathode material shows lower structural transformation and Mn dissolution upon cycling in a wide voltage range from 1.5 to 4.6 V. Advanced operando techniques and post-mortem analysis were used to probe the underlying reaction mechanism thoroughly. Overall, the high-entropy strategy is a promising route for improving the electrochemical performance of P2 layered oxide cathodes for advanced sodium-ion battery applications.

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“…Both components were also detected prior to cycling (Figure d), the difference being that the higher binding-energy peak increased strongly in intensity. , It is known that Ni-rich NCM CAMs release lattice oxygen during charge because of structural instabilities (including electrochemical oxidation of surface carbonates). The evolved oxygen can undergo follow-up reactions with thiophosphate SEs, thus being responsible, at least to some degree, for the formation of oxygenated decomposition products. − Note that the NCM851005 CAM was the only oxygen source in the cathode. However, chemical reactions with the protective surface coating cannot be ruled out.…”

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confidence: 99%

A High-Entropy Multicationic Substituted Lithium Argyrodite Superionic Solid Electrolyte

Lin

Cherkashinin

Schäfer

et al. 2022

ACS Materials Lett.

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Bulk-type solid-state batteries (SSBs) constitute a promising next-generation technology for electrochemical energy storage. However, in order for SSBs to become competitive with mature battery technologies, (electro)chemically stable, superionic solid electrolytes are much needed. Multicomponent or high-entropy lithium argyrodites have recently attracted attention for their favorable material characteristics. In the present work, we report on increasing the configurational entropy of the Li 6+a P 1−x M x S 5 I solid electrolyte system and examine how this affects the structureconductivity/stability relationships. Using electrochemical impedance spectroscopy and 7 Li pulsed field gradient nuclear magnetic resonance (NMR) spectroscopy, multicationic substitution is demonstrated to result in a very low activation energy for Li diffusion of ∼0.2 eV and a high room-temperature ionic conductivity of ∼13 mS cm −1 (for Li 6.5 [P 0.25 Si 0.25 Ge 0.25 Sb 0.25 ]S 5 I). The transport properties are rationalized from a structural perspective by means of complementary neutron powder diffraction and magic-angle spinning NMR spectroscopy measurements. The Li 6.5 [P 0.25 Si 0.25 Ge 0.25 Sb 0.25 ]S 5 I solid electrolyte was also tested in high-loading SSB cells with a Ni-rich layered oxide cathode and found by X-ray photoelectron spectroscopy to suffer from interfacial side reactions during cycling. Overall, the results of this study indicate that optimization of conductivity is equally important to optimization of stability, and compositionally complex lithium argyrodites represent a new playground for a rational design of (potentially advanced) superionic solid electrolytes.

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On the role of surface carbonate species in determining the cycling performance of all-solid-state batteries

Cited by 26 publications

References 56 publications

Designing Cathodes and Cathode Active Materials for Solid‐State Batteries

Designing Cathodes and Cathode Active Materials for Solid‐State Batteries

P2-type layered high-entropy oxides as sodium-ion cathode materials

A High-Entropy Multicationic Substituted Lithium Argyrodite Superionic Solid Electrolyte

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