First-Ever Use of LiMn₂O₄ Cathode in State-of-the-Art Ammonium-Ion Batteries: Unlocking a New Ametal Charge Carrier

Year 2025, Volume: 18 Issue: 2, 431 - 450, 31.08.2025

Melisa Uçan , Dilara ōzgenç , Yildiray Topcu , Burak Tekin

https://doi.org/10.18185/erzifbed.1673054

Abstract

The pursuit of cost-effective, high-performance, and eco-friendly energy storage solutions has driven increasing interest in aqueous ammonium-ion batteries. These systems provide enhanced safety, sustainability, and affordability, attributed to the low molar mass and small hydrated ionic radius of ammonium ions. However, identifying a cathode material capable of reversible ammonium-ion storage in aqueous electrolytes remains a key challenge. This study explores lithium manganese oxide (LiMn₂O₄) as a promising cathode material for ammonium-ion batteries. The spinel LiMn₂O₄ structure, known for its cubic symmetry and interconnected 3D ion-diffusion channels, ensures efficient charge transport and robust electrochemical performance. Additionally, its low-cost raw materials and environmental advantages make it an attractive alternative to conventional transition metal oxides. With a theoretical capacity of ~148 mAh g⁻¹, LiMn₂O₄ exhibits substantial specific capacity, contributing to improved battery energy density. The material was synthesized via a high-temperature solid-state reaction, and X-ray diffraction (XRD) confirmed the formation of a stable orthorhombic structure. Electrochemical analysis using cyclic voltammetry indicated a two-step lithium extraction process in ammonium-ion electrolytes. As cycling progressed, redox peaks associated with ammonium-ion insertion and extraction became more defined, highlighting the material's capability for efficient and reversible charge storage. Galvanostatic charge-discharge tests revealed that the MnO₂-based electrode delivered a stable specific capacity of approximately 47 mAh g⁻¹ during NH₄⁺ intercalation/de-intercalation. The study demonstrates that LiMn₂O₄ effectively supports ammonium-ion storage, offering a sustainable and high-performance cathode option for next-generation aqueous batteries. These findings provide crucial insights into the material’s electrochemical behavior and potential for advancing ammonium-ion battery technology.

Keywords

Aqueous ammonium ion batteries , Spinel cathode materials , Electrochemical energy storage

LiMn₂O₄ katodun son teknoloji amonyum iyon pillerde ilk kullanımı: yeni bir ametal şarj taşıyıcısının kilidini açma

Abstract

Uygun maliyetli, yüksek performanslı ve çevre dostu enerji depolama çözümlerinin arayışı, sulu amonyum iyon pillere olan ilginin artmasına neden oldu. Bu sistemler, amonyum iyonlarının düşük molar kütlesine ve küçük hidratlı iyonik yarıçapına atfedilen gelişmiş güvenlik, sürdürülebilirlik ve satın alınabilirlik sağlar. Bununla birlikte, sulu elektrolitlerde tersinir amonyum-iyon depolaması yapabilen bir katot malzemesinin tanımlanması önemli bir zorluk olmaya devam etmektedir. Bu çalışma, amonyum-iyon piller için umut verici bir katot malzemesi olarak lityum manganez oksidi (LiMn₂O₄) araştırıyor. Kübik simetrisi ve birbirine bağlı 3D iyon difüzyon kanalları ile bilinen spinel LiMn₂O₄ yapısı, verimli yük taşınması ve sağlam elektrokimyasal performans sağlar. Ek olarak, düşük maliyetli hammaddeleri ve çevresel avantajları, onu geleneksel geçiş metali oksitlerine çekici bir alternatif haline getirmektedir. ~148 mAh g⁻¹ teorik kapasiteye sahip LiMn₂O₄, önemli bir özgül kapasite sergileyerek pil enerji yoğunluğunun iyileştirilmesine katkıda bulunur. Materyal, yüksek sıcaklıkta bir katı hal reaksiyonu yoluyla sentezlendi ve X-ışını kırınımı (XRD), kararlı bir ortorombik yapının oluşumunu doğruladı. Döngüsel voltametri kullanılarak yapılan elektrokimyasal analiz, amonyum-iyon elektrolitlerde iki aşamalı bir lityum ekstraksiyon işlemini gösterdi. Döngü ilerledikçe, amonyum iyonu ekleme ve çıkarma ile ilişkili redoks tepe noktaları daha belirgin hale geldi ve malzemenin verimli ve geri dönüşümlü şarj depolama kapasitesini vurguladı. Galvanostatik yük-deşarj testleri, MnO₂ bazlı elektrotun NH₄⁺ interkalasyon/de-interkalasyon sırasında yaklaşık 47 mAh g⁻¹'lik kararlı bir özgül kapasite sağladığını ortaya koydu. Çalışma, LiMn₂O₄'nin amonyum iyon depolamayı etkili bir şekilde desteklediğini ve yeni nesil sulu piller için sürdürülebilir ve yüksek performanslı bir katot seçeneği sunduğunu gösteriyor. Bu bulgular, malzemenin elektrokimyasal davranışı ve amonyum-iyon pil teknolojisini ilerletme potansiyeli hakkında önemli bilgiler sağlıyor.

Keywords

Sulu amonyum iyon piller , Spinel katot malzemeleri , Elektrokimyasal enerji depolama

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