Development of Fluorine-Free Electrolytes for Aqueous-Processed Olivine-Type Phosphate Cathodes

Environmental impacts and resource availability are significant concerns for the future of lithium-ion batteries. This study focuses on developing novel fluorine-free electrolytes compatible with aqueous-processed cobalt-free cathode materials. The new electrolyte contains lithium 1,1,2,3,3-pentacya...

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Main Authors: Claudia Limachi, Klaudia Rogala, Marek Broszkiewicz, Marta Cabello, Leszek Niedzicki, Michel Armand, Władysław Wieczorek
Format: Article
Language:English
Published: MDPI AG 2024-10-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/29/19/4698
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author Claudia Limachi
Klaudia Rogala
Marek Broszkiewicz
Marta Cabello
Leszek Niedzicki
Michel Armand
Władysław Wieczorek
author_facet Claudia Limachi
Klaudia Rogala
Marek Broszkiewicz
Marta Cabello
Leszek Niedzicki
Michel Armand
Władysław Wieczorek
author_sort Claudia Limachi
collection DOAJ
description Environmental impacts and resource availability are significant concerns for the future of lithium-ion batteries. This study focuses on developing novel fluorine-free electrolytes compatible with aqueous-processed cobalt-free cathode materials. The new electrolyte contains lithium 1,1,2,3,3-pentacyanopropenide (LiPCP) salt. After screening various organic carbonates, a mixture of 30:70 wt.% ethylene carbonate and dimethyl carbonate was chosen as the solvent. The optimal salt concentration, yielding the highest conductivity of 9.6 mS·cm<sup>−1</sup> at 20 °C, was 0.8 mol·kg<sup>−1</sup>. Vinylene carbonate was selected as a SEI-stabilizing additive, and the electrolyte demonstrated stability up to 4.4 V vs. Li+/Li. LiFePO<sub>4</sub> and LiMn<sub>0.6</sub>Fe<sub>0.4</sub>PO<sub>4</sub> were identified as suitable cobalt-free cathode materials. They were processed using sodium carboxymethyl cellulose as a binder and water as the solvent. Performance testing of various cathode compositions was conducted using cyclic voltammetry and galvanostatic cycling with the LiPCP-based electrolyte and a standard LiPF6-based one. The optimized cathode compositions, with an 87:10:3 ratio of active material to conductive additive to binder, showed good compatibility and performance with the new electrolyte. Aqueous-processed LiFePO<sub>4</sub> and LiMn<sub>0.6</sub>Fe<sub>0.4</sub>PO<sub>4</sub> achieved capacities of 160 mAh·g<sup>−1</sup> and 70 mAh·g<sup>−1</sup> at C/10 after 40 cycles, respectively. These findings represent the first stage of investigating LiPCP for the development of greener and more sustainable lithium-ion batteries.
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spelling doaj-art-92a4f7520c6a409d8fbbe140a5fa2b2a2025-08-20T02:16:55ZengMDPI AGMolecules1420-30492024-10-012919469810.3390/molecules29194698Development of Fluorine-Free Electrolytes for Aqueous-Processed Olivine-Type Phosphate CathodesClaudia Limachi0Klaudia Rogala1Marek Broszkiewicz2Marta Cabello3Leszek Niedzicki4Michel Armand5Władysław Wieczorek6Faculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw, PolandFaculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw, PolandFaculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw, PolandCentre for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Alava Technology Park, Albert Einstein 48, 01510 Vitoria-Gasteiz, SpainFaculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw, PolandCentre for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Alava Technology Park, Albert Einstein 48, 01510 Vitoria-Gasteiz, SpainFaculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw, PolandEnvironmental impacts and resource availability are significant concerns for the future of lithium-ion batteries. This study focuses on developing novel fluorine-free electrolytes compatible with aqueous-processed cobalt-free cathode materials. The new electrolyte contains lithium 1,1,2,3,3-pentacyanopropenide (LiPCP) salt. After screening various organic carbonates, a mixture of 30:70 wt.% ethylene carbonate and dimethyl carbonate was chosen as the solvent. The optimal salt concentration, yielding the highest conductivity of 9.6 mS·cm<sup>−1</sup> at 20 °C, was 0.8 mol·kg<sup>−1</sup>. Vinylene carbonate was selected as a SEI-stabilizing additive, and the electrolyte demonstrated stability up to 4.4 V vs. Li+/Li. LiFePO<sub>4</sub> and LiMn<sub>0.6</sub>Fe<sub>0.4</sub>PO<sub>4</sub> were identified as suitable cobalt-free cathode materials. They were processed using sodium carboxymethyl cellulose as a binder and water as the solvent. Performance testing of various cathode compositions was conducted using cyclic voltammetry and galvanostatic cycling with the LiPCP-based electrolyte and a standard LiPF6-based one. The optimized cathode compositions, with an 87:10:3 ratio of active material to conductive additive to binder, showed good compatibility and performance with the new electrolyte. Aqueous-processed LiFePO<sub>4</sub> and LiMn<sub>0.6</sub>Fe<sub>0.4</sub>PO<sub>4</sub> achieved capacities of 160 mAh·g<sup>−1</sup> and 70 mAh·g<sup>−1</sup> at C/10 after 40 cycles, respectively. These findings represent the first stage of investigating LiPCP for the development of greener and more sustainable lithium-ion batteries.https://www.mdpi.com/1420-3049/29/19/4698fluorine-free lithium saltslithium-ion batteriesgreen chemistrysustainabilityaqueous electrodesaqueous binders
spellingShingle Claudia Limachi
Klaudia Rogala
Marek Broszkiewicz
Marta Cabello
Leszek Niedzicki
Michel Armand
Władysław Wieczorek
Development of Fluorine-Free Electrolytes for Aqueous-Processed Olivine-Type Phosphate Cathodes
Molecules
fluorine-free lithium salts
lithium-ion batteries
green chemistry
sustainability
aqueous electrodes
aqueous binders
title Development of Fluorine-Free Electrolytes for Aqueous-Processed Olivine-Type Phosphate Cathodes
title_full Development of Fluorine-Free Electrolytes for Aqueous-Processed Olivine-Type Phosphate Cathodes
title_fullStr Development of Fluorine-Free Electrolytes for Aqueous-Processed Olivine-Type Phosphate Cathodes
title_full_unstemmed Development of Fluorine-Free Electrolytes for Aqueous-Processed Olivine-Type Phosphate Cathodes
title_short Development of Fluorine-Free Electrolytes for Aqueous-Processed Olivine-Type Phosphate Cathodes
title_sort development of fluorine free electrolytes for aqueous processed olivine type phosphate cathodes
topic fluorine-free lithium salts
lithium-ion batteries
green chemistry
sustainability
aqueous electrodes
aqueous binders
url https://www.mdpi.com/1420-3049/29/19/4698
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