Li+ concentration and morphological changes at the anode and cathode interphases inside solid-state lithium metal batteries
Irregular Li heterostructure growth at the interphase between the solid electrolyte and anode reduces solid-state Li metal battery (SSLMB) performance, but the fundamental cause is still elusive. Measuring and imaging Li ^+ ion diffusion in operando inside an SSLMB using a commercially standard cell...
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| Language: | English |
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IOP Publishing
2025-01-01
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| Series: | JPhys Energy |
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| Online Access: | https://doi.org/10.1088/2515-7655/adafda |
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| author | Chun Huang Matthew D Wilson Ben Cline Abeiram Sivarajah Wiebe Stolp Matthieu N Boone Thomas Connolley Chu Lun Alex Leung |
| author_facet | Chun Huang Matthew D Wilson Ben Cline Abeiram Sivarajah Wiebe Stolp Matthieu N Boone Thomas Connolley Chu Lun Alex Leung |
| author_sort | Chun Huang |
| collection | DOAJ |
| description | Irregular Li heterostructure growth at the interphase between the solid electrolyte and anode reduces solid-state Li metal battery (SSLMB) performance, but the fundamental cause is still elusive. Measuring and imaging Li ^+ ion diffusion in operando inside an SSLMB using a commercially standard cell configuration are extremely challenging because the ultra-light Li element exhibits a minute signal-to-noise ratio using most x-ray-related characterization methods, and the weak x-ray signals of Li ^+ are buried by strong signals of other heavy transition metal elements in the cathode and battery enclosure. Here, we pioneer novel operando correlative imaging of coupling x-ray Compton scattering with computed tomography (XCS-CT), which is able to quantify the interplay between spatially resolved Li ^+ ion diffusion kinetics and Li ^0 metal structure growth at the interphases of both the anode and cathode sides inside a full-cell SSLMB using a solid polymer electrolyte (SPE) and commercially standard cell configuration during (dis)charging. We show a 61% increase in the efficiency of extracting Li ^+ ions from the cathode LiNi _0.6 Mn _0.2 Co _0.2 O _2 to the anode during charging at 0.1 C compared with at 1 C due to restricted Li ^+ ion diffusion at the higher rate inside SSLMB. However, this led to the formation of a more irregular interfacial morphology, consisting not only of Li ^0 dendrites, but also sub-surface pore formation at the anode/SPE interphase. We find that surprisingly, the irregular Li ^0 structure initiation and growth are accelerated during the first Li stripping step, not the Li plating step, and the root cause is the onset imbalance of Li ^+ ion diffusion and redox reactions between the anode and cathode. These insights highlight the benefits of asymmetric charging and discharging rates as a promising solution to improving SSLMB performance with SPEs. The operando correlative XCS-CT imaging technique has the potential to study the relationship between active ion concentrations and buried morphological changes for a variety of battery chemistries. |
| format | Article |
| id | doaj-art-59cc3719a6534d95b3003e9b23e913fe |
| institution | OA Journals |
| issn | 2515-7655 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | IOP Publishing |
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| series | JPhys Energy |
| spelling | doaj-art-59cc3719a6534d95b3003e9b23e913fe2025-08-20T02:12:50ZengIOP PublishingJPhys Energy2515-76552025-01-017202500910.1088/2515-7655/adafdaLi+ concentration and morphological changes at the anode and cathode interphases inside solid-state lithium metal batteriesChun Huang0https://orcid.org/0000-0001-6548-2977Matthew D Wilson1Ben Cline2Abeiram Sivarajah3https://orcid.org/0009-0005-2330-6138Wiebe Stolp4https://orcid.org/0000-0003-0282-4401Matthieu N Boone5Thomas Connolley6https://orcid.org/0000-0002-1851-3467Chu Lun Alex Leung7https://orcid.org/0000-0002-4153-7512Department of Materials, Imperial College London , London SW7 2AZ, United Kingdom; The Faraday Institution , Didcot OX11 0RA, United Kingdom; Research Complex at Harwell , Rutherford Appleton Laboratory, Didcot OX11 0FA, United KingdomSTFC-UKRI , Rutherford Appleton Laboratory, Didcot OX11 0QX, United KingdomSTFC-UKRI , Rutherford Appleton Laboratory, Didcot OX11 0QX, United KingdomDepartment of Materials, Imperial College London , London SW7 2AZ, United KingdomRadiation Physics, Department of Physics and Astronomy, Ghent University , Proeftuinstraat 86/N12, 9000 Gent, BelgiumRadiation Physics, Department of Physics and Astronomy, Ghent University , Proeftuinstraat 86/N12, 9000 Gent, BelgiumDiamond Light Source , Didcot OX11 0QX, United KingdomResearch Complex at Harwell , Rutherford Appleton Laboratory, Didcot OX11 0FA, United Kingdom; Department of Mechanical Engineering, University College London , London WC1E 7JE, United KingdomIrregular Li heterostructure growth at the interphase between the solid electrolyte and anode reduces solid-state Li metal battery (SSLMB) performance, but the fundamental cause is still elusive. Measuring and imaging Li ^+ ion diffusion in operando inside an SSLMB using a commercially standard cell configuration are extremely challenging because the ultra-light Li element exhibits a minute signal-to-noise ratio using most x-ray-related characterization methods, and the weak x-ray signals of Li ^+ are buried by strong signals of other heavy transition metal elements in the cathode and battery enclosure. Here, we pioneer novel operando correlative imaging of coupling x-ray Compton scattering with computed tomography (XCS-CT), which is able to quantify the interplay between spatially resolved Li ^+ ion diffusion kinetics and Li ^0 metal structure growth at the interphases of both the anode and cathode sides inside a full-cell SSLMB using a solid polymer electrolyte (SPE) and commercially standard cell configuration during (dis)charging. We show a 61% increase in the efficiency of extracting Li ^+ ions from the cathode LiNi _0.6 Mn _0.2 Co _0.2 O _2 to the anode during charging at 0.1 C compared with at 1 C due to restricted Li ^+ ion diffusion at the higher rate inside SSLMB. However, this led to the formation of a more irregular interfacial morphology, consisting not only of Li ^0 dendrites, but also sub-surface pore formation at the anode/SPE interphase. We find that surprisingly, the irregular Li ^0 structure initiation and growth are accelerated during the first Li stripping step, not the Li plating step, and the root cause is the onset imbalance of Li ^+ ion diffusion and redox reactions between the anode and cathode. These insights highlight the benefits of asymmetric charging and discharging rates as a promising solution to improving SSLMB performance with SPEs. The operando correlative XCS-CT imaging technique has the potential to study the relationship between active ion concentrations and buried morphological changes for a variety of battery chemistries.https://doi.org/10.1088/2515-7655/adafdasolid-state batteriescorrelative imaginglithium ion concentrationmicrostructurex-ray Compton scatteringmass transport |
| spellingShingle | Chun Huang Matthew D Wilson Ben Cline Abeiram Sivarajah Wiebe Stolp Matthieu N Boone Thomas Connolley Chu Lun Alex Leung Li+ concentration and morphological changes at the anode and cathode interphases inside solid-state lithium metal batteries JPhys Energy solid-state batteries correlative imaging lithium ion concentration microstructure x-ray Compton scattering mass transport |
| title | Li+ concentration and morphological changes at the anode and cathode interphases inside solid-state lithium metal batteries |
| title_full | Li+ concentration and morphological changes at the anode and cathode interphases inside solid-state lithium metal batteries |
| title_fullStr | Li+ concentration and morphological changes at the anode and cathode interphases inside solid-state lithium metal batteries |
| title_full_unstemmed | Li+ concentration and morphological changes at the anode and cathode interphases inside solid-state lithium metal batteries |
| title_short | Li+ concentration and morphological changes at the anode and cathode interphases inside solid-state lithium metal batteries |
| title_sort | li concentration and morphological changes at the anode and cathode interphases inside solid state lithium metal batteries |
| topic | solid-state batteries correlative imaging lithium ion concentration microstructure x-ray Compton scattering mass transport |
| url | https://doi.org/10.1088/2515-7655/adafda |
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