Anna Jodlbauer, Katharina Hogrefe, Bernhard Gadermaier, H. Martin R. Wilkening
{"title":"Ion Dynamics in Nanocrystalline Li2S-LiI – on the Influence of Local Disorder on Short-Range Hopping and Long-Range Ion Transport","authors":"Anna Jodlbauer, Katharina Hogrefe, Bernhard Gadermaier, H. Martin R. Wilkening","doi":"10.1002/smsc.202400199","DOIUrl":null,"url":null,"abstract":"The enormous interest in developing powerful Li-based batteries leads to a boost in materials research. Though Li–sulfur batteries offer very high energy densities, the nature of Li-ion dynamics in the final discharge product <span data-altimg=\"/cms/asset/61593c72-5894-49c3-b28d-e19b81853a5b/smsc202400199-math-0001.png\"></span><mjx-container ctxtmenu_counter=\"349\" ctxtmenu_oldtabindex=\"1\" jax=\"CHTML\" role=\"application\" sre-explorer- style=\"font-size: 103%; position: relative;\" tabindex=\"0\"><mjx-math aria-hidden=\"true\" location=\"graphic/smsc202400199-math-0001.png\"><mjx-semantics><mjx-mrow data-semantic-annotation=\"clearspeak:unit\" data-semantic-children=\"2,3\" data-semantic-content=\"4\" data-semantic- data-semantic-role=\"implicit\" data-semantic-speech=\"Li Subscript 2 Baseline normal upper S\" data-semantic-type=\"infixop\"><mjx-msub data-semantic-children=\"0,1\" data-semantic- data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"subscript\"><mjx-mrow><mjx-mtext data-semantic-annotation=\"clearspeak:unit\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"text\"><mjx-c></mjx-c><mjx-c></mjx-c></mjx-mtext></mjx-mrow><mjx-script style=\"vertical-align: -0.15em;\"><mjx-mn data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\" size=\"s\"><mjx-c></mjx-c></mjx-mn></mjx-script></mjx-msub><mjx-mo data-semantic-added=\"true\" data-semantic- data-semantic-operator=\"infixop,\" data-semantic-parent=\"5\" data-semantic-role=\"multiplication\" data-semantic-type=\"operator\" style=\"margin-left: 0.056em; margin-right: 0.056em;\"><mjx-c></mjx-c></mjx-mo><mjx-mi data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"5\" data-semantic-role=\"latinletter\" data-semantic-type=\"identifier\"><mjx-c></mjx-c></mjx-mi></mjx-mrow></mjx-semantics></mjx-math><mjx-assistive-mml display=\"inline\" unselectable=\"on\"><math altimg=\"urn:x-wiley:26884046:media:smsc202400199:smsc202400199-math-0001\" display=\"inline\" location=\"graphic/smsc202400199-math-0001.png\" xmlns=\"http://www.w3.org/1998/Math/MathML\"><semantics><mrow data-semantic-=\"\" data-semantic-annotation=\"clearspeak:unit\" data-semantic-children=\"2,3\" data-semantic-content=\"4\" data-semantic-role=\"implicit\" data-semantic-speech=\"Li Subscript 2 Baseline normal upper S\" data-semantic-type=\"infixop\"><msub data-semantic-=\"\" data-semantic-children=\"0,1\" data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"subscript\"><mrow><mtext data-semantic-=\"\" data-semantic-annotation=\"clearspeak:unit\" data-semantic-font=\"normal\" data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"text\">Li</mtext></mrow><mn data-semantic-=\"\" data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\">2</mn></msub><mo data-semantic-=\"\" data-semantic-added=\"true\" data-semantic-operator=\"infixop,\" data-semantic-parent=\"5\" data-semantic-role=\"multiplication\" data-semantic-type=\"operator\"></mo><mi data-semantic-=\"\" data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic-parent=\"5\" data-semantic-role=\"latinletter\" data-semantic-type=\"identifier\" mathvariant=\"normal\">S</mi></mrow>$\\left(\\text{Li}\\right)_{2} \\text{S}$</annotation></semantics></math></mjx-assistive-mml></mjx-container> has not been fully understood yet. While nanocrystalline <span data-altimg=\"/cms/asset/b56d91c6-9f28-4353-b59d-e6bbda530829/smsc202400199-math-0002.png\"></span><mjx-container ctxtmenu_counter=\"350\" ctxtmenu_oldtabindex=\"1\" jax=\"CHTML\" role=\"application\" sre-explorer- style=\"font-size: 103%; position: relative;\" tabindex=\"0\"><mjx-math aria-hidden=\"true\" location=\"graphic/smsc202400199-math-0002.png\"><mjx-semantics><mjx-mrow data-semantic-annotation=\"clearspeak:unit\" data-semantic-children=\"2,3\" data-semantic-content=\"4\" data-semantic- data-semantic-role=\"implicit\" data-semantic-speech=\"Li Subscript 2 Baseline normal upper S\" data-semantic-type=\"infixop\"><mjx-msub data-semantic-children=\"0,1\" data-semantic- data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"subscript\"><mjx-mrow><mjx-mtext data-semantic-annotation=\"clearspeak:unit\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"text\"><mjx-c></mjx-c><mjx-c></mjx-c></mjx-mtext></mjx-mrow><mjx-script style=\"vertical-align: -0.15em;\"><mjx-mn data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\" size=\"s\"><mjx-c></mjx-c></mjx-mn></mjx-script></mjx-msub><mjx-mo data-semantic-added=\"true\" data-semantic- data-semantic-operator=\"infixop,\" data-semantic-parent=\"5\" data-semantic-role=\"multiplication\" data-semantic-type=\"operator\" style=\"margin-left: 0.056em; margin-right: 0.056em;\"><mjx-c></mjx-c></mjx-mo><mjx-mi data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"5\" data-semantic-role=\"latinletter\" data-semantic-type=\"identifier\"><mjx-c></mjx-c></mjx-mi></mjx-mrow></mjx-semantics></mjx-math><mjx-assistive-mml display=\"inline\" unselectable=\"on\"><math altimg=\"urn:x-wiley:26884046:media:smsc202400199:smsc202400199-math-0002\" display=\"inline\" location=\"graphic/smsc202400199-math-0002.png\" xmlns=\"http://www.w3.org/1998/Math/MathML\"><semantics><mrow data-semantic-=\"\" data-semantic-annotation=\"clearspeak:unit\" data-semantic-children=\"2,3\" data-semantic-content=\"4\" data-semantic-role=\"implicit\" data-semantic-speech=\"Li Subscript 2 Baseline normal upper S\" data-semantic-type=\"infixop\"><msub data-semantic-=\"\" data-semantic-children=\"0,1\" data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"subscript\"><mrow><mtext data-semantic-=\"\" data-semantic-annotation=\"clearspeak:unit\" data-semantic-font=\"normal\" data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"text\">Li</mtext></mrow><mn data-semantic-=\"\" data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\">2</mn></msub><mo data-semantic-=\"\" data-semantic-added=\"true\" data-semantic-operator=\"infixop,\" data-semantic-parent=\"5\" data-semantic-role=\"multiplication\" data-semantic-type=\"operator\"></mo><mi data-semantic-=\"\" data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic-parent=\"5\" data-semantic-role=\"latinletter\" data-semantic-type=\"identifier\" mathvariant=\"normal\">S</mi></mrow>$\\left(\\text{Li}\\right)_{2} \\text{S}$</annotation></semantics></math></mjx-assistive-mml></mjx-container> shows enhanced ion dynamics compared to its coarse-grained counterpart, the interaction of <span data-altimg=\"/cms/asset/26371ccb-26c6-459f-b979-2a6b395ec5ce/smsc202400199-math-0003.png\"></span><mjx-container ctxtmenu_counter=\"351\" ctxtmenu_oldtabindex=\"1\" jax=\"CHTML\" role=\"application\" sre-explorer- style=\"font-size: 103%; position: relative;\" tabindex=\"0\"><mjx-math aria-hidden=\"true\" location=\"graphic/smsc202400199-math-0003.png\"><mjx-semantics><mjx-mrow data-semantic-annotation=\"clearspeak:unit\" data-semantic-children=\"2,3\" data-semantic-content=\"4\" data-semantic- data-semantic-role=\"implicit\" data-semantic-speech=\"Li Subscript 2 Baseline normal upper S\" data-semantic-type=\"infixop\"><mjx-msub data-semantic-children=\"0,1\" data-semantic- data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"subscript\"><mjx-mrow><mjx-mtext data-semantic-annotation=\"clearspeak:unit\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"text\"><mjx-c></mjx-c><mjx-c></mjx-c></mjx-mtext></mjx-mrow><mjx-script style=\"vertical-align: -0.15em;\"><mjx-mn data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\" size=\"s\"><mjx-c></mjx-c></mjx-mn></mjx-script></mjx-msub><mjx-mo data-semantic-added=\"true\" data-semantic- data-semantic-operator=\"infixop,\" data-semantic-parent=\"5\" data-semantic-role=\"multiplication\" data-semantic-type=\"operator\" style=\"margin-left: 0.056em; margin-right: 0.056em;\"><mjx-c></mjx-c></mjx-mo><mjx-mi data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"5\" data-semantic-role=\"latinletter\" data-semantic-type=\"identifier\"><mjx-c></mjx-c></mjx-mi></mjx-mrow></mjx-semantics></mjx-math><mjx-assistive-mml display=\"inline\" unselectable=\"on\"><math altimg=\"urn:x-wiley:26884046:media:smsc202400199:smsc202400199-math-0003\" display=\"inline\" location=\"graphic/smsc202400199-math-0003.png\" xmlns=\"http://www.w3.org/1998/Math/MathML\"><semantics><mrow data-semantic-=\"\" data-semantic-annotation=\"clearspeak:unit\" data-semantic-children=\"2,3\" data-semantic-content=\"4\" data-semantic-role=\"implicit\" data-semantic-speech=\"Li Subscript 2 Baseline normal upper S\" data-semantic-type=\"infixop\"><msub data-semantic-=\"\" data-semantic-children=\"0,1\" data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"subscript\"><mrow><mtext data-semantic-=\"\" data-semantic-annotation=\"clearspeak:unit\" data-semantic-font=\"normal\" data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"text\">Li</mtext></mrow><mn data-semantic-=\"\" data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\">2</mn></msub><mo data-semantic-=\"\" data-semantic-added=\"true\" data-semantic-operator=\"infixop,\" data-semantic-parent=\"5\" data-semantic-role=\"multiplication\" data-semantic-type=\"operator\"></mo><mi data-semantic-=\"\" data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic-parent=\"5\" data-semantic-role=\"latinletter\" data-semantic-type=\"identifier\" mathvariant=\"normal\">S</mi></mrow>$\\left(\\text{Li}\\right)_{2} \\text{S}$</annotation></semantics></math></mjx-assistive-mml></mjx-container> with another binary such as LiI seems to be rather unexplored. Herein, an equimolar mixture of <span data-altimg=\"/cms/asset/ecf925af-1f4e-430e-b8c8-b3f108b80a3c/smsc202400199-math-0004.png\"></span><mjx-container ctxtmenu_counter=\"352\" ctxtmenu_oldtabindex=\"1\" jax=\"CHTML\" role=\"application\" sre-explorer- style=\"font-size: 103%; position: relative;\" tabindex=\"0\"><mjx-math aria-hidden=\"true\" location=\"graphic/smsc202400199-math-0004.png\"><mjx-semantics><mjx-mrow data-semantic-annotation=\"clearspeak:unit\" data-semantic-children=\"2,3\" data-semantic-content=\"4\" data-semantic- data-semantic-role=\"implicit\" data-semantic-speech=\"Li Subscript 2 Baseline normal upper S\" data-semantic-type=\"infixop\"><mjx-msub data-semantic-children=\"0,1\" data-semantic- data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"subscript\"><mjx-mrow><mjx-mtext data-semantic-annotation=\"clearspeak:unit\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"text\"><mjx-c></mjx-c><mjx-c></mjx-c></mjx-mtext></mjx-mrow><mjx-script style=\"vertical-align: -0.15em;\"><mjx-mn data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\" size=\"s\"><mjx-c></mjx-c></mjx-mn></mjx-script></mjx-msub><mjx-mo data-semantic-added=\"true\" data-semantic- data-semantic-operator=\"infixop,\" data-semantic-parent=\"5\" data-semantic-role=\"multiplication\" data-semantic-type=\"operator\" style=\"margin-left: 0.056em; margin-right: 0.056em;\"><mjx-c></mjx-c></mjx-mo><mjx-mi data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"5\" data-semantic-role=\"latinletter\" data-semantic-type=\"identifier\"><mjx-c></mjx-c></mjx-mi></mjx-mrow></mjx-semantics></mjx-math><mjx-assistive-mml display=\"inline\" unselectable=\"on\"><math altimg=\"urn:x-wiley:26884046:media:smsc202400199:smsc202400199-math-0004\" display=\"inline\" location=\"graphic/smsc202400199-math-0004.png\" xmlns=\"http://www.w3.org/1998/Math/MathML\"><semantics><mrow data-semantic-=\"\" data-semantic-annotation=\"clearspeak:unit\" data-semantic-children=\"2,3\" data-semantic-content=\"4\" data-semantic-role=\"implicit\" data-semantic-speech=\"Li Subscript 2 Baseline normal upper S\" data-semantic-type=\"infixop\"><msub data-semantic-=\"\" data-semantic-children=\"0,1\" data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"subscript\"><mrow><mtext data-semantic-=\"\" data-semantic-annotation=\"clearspeak:unit\" data-semantic-font=\"normal\" data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"text\">Li</mtext></mrow><mn data-semantic-=\"\" data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\">2</mn></msub><mo data-semantic-=\"\" data-semantic-added=\"true\" data-semantic-operator=\"infixop,\" data-semantic-parent=\"5\" data-semantic-role=\"multiplication\" data-semantic-type=\"operator\"></mo><mi data-semantic-=\"\" data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic-parent=\"5\" data-semantic-role=\"latinletter\" data-semantic-type=\"identifier\" mathvariant=\"normal\">S</mi></mrow>$\\left(\\text{Li}\\right)_{2} \\text{S}$</annotation></semantics></math></mjx-assistive-mml></mjx-container> and LiI is treated in a high-energy ball mill, and both the overall and local structural changes are studied by X-ray powder diffraction and <span data-altimg=\"/cms/asset/0743c32b-ce30-47a1-abde-b52316c48feb/smsc202400199-math-0005.png\"></span><mjx-container ctxtmenu_counter=\"353\" ctxtmenu_oldtabindex=\"1\" jax=\"CHTML\" role=\"application\" sre-explorer- style=\"font-size: 103%; position: relative;\" tabindex=\"0\"><mjx-math aria-hidden=\"true\" location=\"graphic/smsc202400199-math-0005.png\"><mjx-semantics><mjx-mrow data-semantic-children=\"2,3\" data-semantic-collapsed=\"(5 (c 4) 2 3)\" data-semantic- data-semantic-role=\"text\" data-semantic-speech=\"Superscript 6 comma 7 Baseline Li\" data-semantic-type=\"punctuated\"><mjx-msup data-semantic-children=\"0,1\" data-semantic- data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"superscript\"><mjx-mrow data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"empty\"></mjx-mrow><mjx-script style=\"vertical-align: 0.363em;\"><mjx-mrow size=\"s\"><mjx-mn data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\"><mjx-c></mjx-c><mjx-c></mjx-c><mjx-c></mjx-c></mjx-mn></mjx-mrow></mjx-script></mjx-msup><mjx-mtext data-semantic-annotation=\"clearspeak:unit\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"text\"><mjx-c></mjx-c><mjx-c></mjx-c></mjx-mtext></mjx-mrow></mjx-semantics></mjx-math><mjx-assistive-mml display=\"inline\" unselectable=\"on\"><math altimg=\"urn:x-wiley:26884046:media:smsc202400199:smsc202400199-math-0005\" display=\"inline\" location=\"graphic/smsc202400199-math-0005.png\" xmlns=\"http://www.w3.org/1998/Math/MathML\"><semantics><mrow data-semantic-=\"\" data-semantic-children=\"2,3\" data-semantic-collapsed=\"(5 (c 4) 2 3)\" data-semantic-role=\"text\" data-semantic-speech=\"Superscript 6 comma 7 Baseline Li\" data-semantic-type=\"punctuated\"><msup data-semantic-=\"\" data-semantic-children=\"0,1\" data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"superscript\"><mrow data-semantic-=\"\" data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"empty\"></mrow><mrow><mn data-semantic-=\"\" data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\">6,7</mn></mrow></msup><mtext data-semantic-=\"\" data-semantic-annotation=\"clearspeak:unit\" data-semantic-font=\"normal\" data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"text\">Li</mtext></mrow>$^{6,7} \\text{Li}$</annotation></semantics></math></mjx-assistive-mml></mjx-container> nuclear magnetic resonance (NMR), respectively . Besides the formation of amorphous regions, evidences are found for the generation of anion-mixed sites that give rise to facile Li<span data-altimg=\"/cms/asset/bc46c912-6a79-48c1-9f0f-38c263f941f4/smsc202400199-math-0006.png\"></span><mjx-container ctxtmenu_counter=\"354\" ctxtmenu_oldtabindex=\"1\" jax=\"CHTML\" role=\"application\" sre-explorer- style=\"font-size: 103%; position: relative;\" tabindex=\"0\"><mjx-math aria-hidden=\"true\" location=\"graphic/smsc202400199-math-0006.png\"><mjx-semantics><mjx-mrow><mjx-msup data-semantic-children=\"0,1\" data-semantic- data-semantic-role=\"unknown\" data-semantic-speech=\"Superscript plus\" data-semantic-type=\"superscript\"><mjx-mrow data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"empty\"></mjx-mrow><mjx-script style=\"vertical-align: 0.363em;\"><mjx-mo data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"addition\" data-semantic-type=\"operator\" size=\"s\"><mjx-c></mjx-c></mjx-mo></mjx-script></mjx-msup></mjx-mrow></mjx-semantics></mjx-math><mjx-assistive-mml display=\"inline\" unselectable=\"on\"><math altimg=\"urn:x-wiley:26884046:media:smsc202400199:smsc202400199-math-0006\" display=\"inline\" location=\"graphic/smsc202400199-math-0006.png\" xmlns=\"http://www.w3.org/1998/Math/MathML\"><semantics><mrow><msup data-semantic-=\"\" data-semantic-children=\"0,1\" data-semantic-role=\"unknown\" data-semantic-speech=\"Superscript plus\" data-semantic-type=\"superscript\"><mrow data-semantic-=\"\" data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"empty\"></mrow><mo data-semantic-=\"\" data-semantic-parent=\"2\" data-semantic-role=\"addition\" data-semantic-type=\"operator\">+</mo></msup></mrow>$^{&#x00026;amp;amp;amp;amp;amp;amp;amp;amp;amp;plus;}$</annotation></semantics></math></mjx-assistive-mml></mjx-container> exchange on the 2D exchange NMR timescale. Compared to a coarse-grained reference sample, the overall (bulk) ionic conductivity of nanocrystalline <span data-altimg=\"/cms/asset/9932c886-cf80-4d07-8f27-48880292160a/smsc202400199-math-0007.png\"></span><mjx-container ctxtmenu_counter=\"355\" ctxtmenu_oldtabindex=\"1\" jax=\"CHTML\" role=\"application\" sre-explorer- style=\"font-size: 103%; position: relative;\" tabindex=\"0\"><mjx-math aria-hidden=\"true\" location=\"graphic/smsc202400199-math-0007.png\"><mjx-semantics><mjx-mrow data-semantic-annotation=\"clearspeak:unit\" data-semantic-children=\"2,3\" data-semantic-content=\"4\" data-semantic- data-semantic-role=\"implicit\" data-semantic-speech=\"Li Subscript 2 Baseline normal upper S\" data-semantic-type=\"infixop\"><mjx-msub data-semantic-children=\"0,1\" data-semantic- data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"subscript\"><mjx-mrow><mjx-mtext data-semantic-annotation=\"clearspeak:unit\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"text\"><mjx-c></mjx-c><mjx-c></mjx-c></mjx-mtext></mjx-mrow><mjx-script style=\"vertical-align: -0.15em;\"><mjx-mn data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\" size=\"s\"><mjx-c></mjx-c></mjx-mn></mjx-script></mjx-msub><mjx-mo data-semantic-added=\"true\" data-semantic- data-semantic-operator=\"infixop,\" data-semantic-parent=\"5\" data-semantic-role=\"multiplication\" data-semantic-type=\"operator\" style=\"margin-left: 0.056em; margin-right: 0.056em;\"><mjx-c></mjx-c></mjx-mo><mjx-mi data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"5\" data-semantic-role=\"latinletter\" data-semantic-type=\"identifier\"><mjx-c></mjx-c></mjx-mi></mjx-mrow></mjx-semantics></mjx-math><mjx-assistive-mml display=\"inline\" unselectable=\"on\"><math altimg=\"urn:x-wiley:26884046:media:smsc202400199:smsc202400199-math-0007\" display=\"inline\" location=\"graphic/smsc202400199-math-0007.png\" xmlns=\"http://www.w3.org/1998/Math/MathML\"><semantics><mrow data-semantic-=\"\" data-semantic-annotation=\"clearspeak:unit\" data-semantic-children=\"2,3\" data-semantic-content=\"4\" data-semantic-role=\"implicit\" data-semantic-speech=\"Li Subscript 2 Baseline normal upper S\" data-semantic-type=\"infixop\"><msub data-semantic-=\"\" data-semantic-children=\"0,1\" data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"subscript\"><mrow><mtext data-semantic-=\"\" data-semantic-annotation=\"clearspeak:unit\" data-semantic-font=\"normal\" data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"text\">Li</mtext></mrow><mn data-semantic-=\"\" data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\">2</mn></msub><mo data-semantic-=\"\" data-semantic-added=\"true\" data-semantic-operator=\"infixop,\" data-semantic-parent=\"5\" data-semantic-role=\"multiplication\" data-semantic-type=\"operator\"></mo><mi data-semantic-=\"\" data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic-parent=\"5\" data-semantic-role=\"latinletter\" data-semantic-type=\"identifier\" mathvariant=\"normal\">S</mi></mrow>$\\left(\\text{Li}\\right)_{2} \\text{S}$</annotation></semantics></math></mjx-assistive-mml></mjx-container>-LiI increases by two orders of magnitude. Besides the anion-mixing effect, this increase benefits from nanosize effects that include the formation of defect-rich interfacial regions. NMR relaxation measurements fully support this result and reveal heterogeneous dynamics with lower activation energies for both the localized hopping processes and long-range ion transport in nm-sized <span data-altimg=\"/cms/asset/69672b30-ad73-4029-85cb-ed6a85772e35/smsc202400199-math-0008.png\"></span><mjx-container ctxtmenu_counter=\"356\" ctxtmenu_oldtabindex=\"1\" jax=\"CHTML\" role=\"application\" sre-explorer- style=\"font-size: 103%; position: relative;\" tabindex=\"0\"><mjx-math aria-hidden=\"true\" location=\"graphic/smsc202400199-math-0008.png\"><mjx-semantics><mjx-mrow data-semantic-annotation=\"clearspeak:unit\" data-semantic-children=\"2,3\" data-semantic-content=\"4\" data-semantic- data-semantic-role=\"implicit\" data-semantic-speech=\"Li Subscript 2 Baseline normal upper S\" data-semantic-type=\"infixop\"><mjx-msub data-semantic-children=\"0,1\" data-semantic- data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"subscript\"><mjx-mrow><mjx-mtext data-semantic-annotation=\"clearspeak:unit\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"text\"><mjx-c></mjx-c><mjx-c></mjx-c></mjx-mtext></mjx-mrow><mjx-script style=\"vertical-align: -0.15em;\"><mjx-mn data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\" size=\"s\"><mjx-c></mjx-c></mjx-mn></mjx-script></mjx-msub><mjx-mo data-semantic-added=\"true\" data-semantic- data-semantic-operator=\"infixop,\" data-semantic-parent=\"5\" data-semantic-role=\"multiplication\" data-semantic-type=\"operator\" style=\"margin-left: 0.056em; margin-right: 0.056em;\"><mjx-c></mjx-c></mjx-mo><mjx-mi data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic- data-semantic-parent=\"5\" data-semantic-role=\"latinletter\" data-semantic-type=\"identifier\"><mjx-c></mjx-c></mjx-mi></mjx-mrow></mjx-semantics></mjx-math><mjx-assistive-mml display=\"inline\" unselectable=\"on\"><math altimg=\"urn:x-wiley:26884046:media:smsc202400199:smsc202400199-math-0008\" display=\"inline\" location=\"graphic/smsc202400199-math-0008.png\" xmlns=\"http://www.w3.org/1998/Math/MathML\"><semantics><mrow data-semantic-=\"\" data-semantic-annotation=\"clearspeak:unit\" data-semantic-children=\"2,3\" data-semantic-content=\"4\" data-semantic-role=\"implicit\" data-semantic-speech=\"Li Subscript 2 Baseline normal upper S\" data-semantic-type=\"infixop\"><msub data-semantic-=\"\" data-semantic-children=\"0,1\" data-semantic-parent=\"5\" data-semantic-role=\"unknown\" data-semantic-type=\"subscript\"><mrow><mtext data-semantic-=\"\" data-semantic-annotation=\"clearspeak:unit\" data-semantic-font=\"normal\" data-semantic-parent=\"2\" data-semantic-role=\"unknown\" data-semantic-type=\"text\">Li</mtext></mrow><mn data-semantic-=\"\" data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic-parent=\"2\" data-semantic-role=\"integer\" data-semantic-type=\"number\">2</mn></msub><mo data-semantic-=\"\" data-semantic-added=\"true\" data-semantic-operator=\"infixop,\" data-semantic-parent=\"5\" data-semantic-role=\"multiplication\" data-semantic-type=\"operator\"></mo><mi data-semantic-=\"\" data-semantic-annotation=\"clearspeak:simple\" data-semantic-font=\"normal\" data-semantic-parent=\"5\" data-semantic-role=\"latinletter\" data-semantic-type=\"identifier\" mathvariant=\"normal\">S</mi></mrow>$\\left(\\text{Li}\\right)_{2} \\text{S}$</annotation></semantics></math></mjx-assistive-mml></mjx-container>-LiI.","PeriodicalId":29791,"journal":{"name":"Small Science","volume":"23 1","pages":""},"PeriodicalIF":11.1000,"publicationDate":"2024-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Small Science","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1002/smsc.202400199","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The enormous interest in developing powerful Li-based batteries leads to a boost in materials research. Though Li–sulfur batteries offer very high energy densities, the nature of Li-ion dynamics in the final discharge product has not been fully understood yet. While nanocrystalline shows enhanced ion dynamics compared to its coarse-grained counterpart, the interaction of with another binary such as LiI seems to be rather unexplored. Herein, an equimolar mixture of and LiI is treated in a high-energy ball mill, and both the overall and local structural changes are studied by X-ray powder diffraction and nuclear magnetic resonance (NMR), respectively . Besides the formation of amorphous regions, evidences are found for the generation of anion-mixed sites that give rise to facile Li exchange on the 2D exchange NMR timescale. Compared to a coarse-grained reference sample, the overall (bulk) ionic conductivity of nanocrystalline -LiI increases by two orders of magnitude. Besides the anion-mixing effect, this increase benefits from nanosize effects that include the formation of defect-rich interfacial regions. NMR relaxation measurements fully support this result and reveal heterogeneous dynamics with lower activation energies for both the localized hopping processes and long-range ion transport in nm-sized -LiI.
期刊介绍:
Small Science is a premium multidisciplinary open access journal dedicated to publishing impactful research from all areas of nanoscience and nanotechnology. It features interdisciplinary original research and focused review articles on relevant topics. The journal covers design, characterization, mechanism, technology, and application of micro-/nanoscale structures and systems in various fields including physics, chemistry, materials science, engineering, environmental science, life science, biology, and medicine. It welcomes innovative interdisciplinary research and its readership includes professionals from academia and industry in fields such as chemistry, physics, materials science, biology, engineering, and environmental and analytical science. Small Science is indexed and abstracted in CAS, DOAJ, Clarivate Analytics, ProQuest Central, Publicly Available Content Database, Science Database, SCOPUS, and Web of Science.