Journal of the Korean Electrochemical Society (전기화학회지)

The Korean Electrochemical Society (한국전기화학회)
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Effect of Fe and BO3 Substitution in Li1+xFexTi2-x(PO4)3-y(BO3)y Glass Electrolytes

Li1+xFexTi2-x(PO4)3-y(BO3)y 계 유리 전해질에서 Fe 및 BO3 치환 효과

  • Choi, Byung-Hyun (Department of Materials Science and Engineering, Inha University) ;
  • Jun, Hyung Tak (Department of Materials Science and Engineering, Inha University) ;
  • Yi, Eun Jeong (Department of Materials Science and Engineering, Inha University) ;
  • Hwang, Haejin (Department of Materials Science and Engineering, Inha University)
  • 최병현 (인하대학교 신소재공학과) ;
  • 전형탁 (인하대학교 신소재공학과) ;
  • 이은정 (인하대학교 신소재공학과) ;
  • 황해진 (인하대학교 신소재공학과)
  • Received : 2021.06.02
  • Accepted : 2021.07.20
  • Published : 2021.08.31
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Abstract

The effect of Fe and BO3 doping on structure, thermal, and electrical properties of Li1+xFexTi2-x(PO4)3-y(BO3)y (x = 0.2, 0.5)-based glass and glass ceramics was investigated. In addition, their crystallization behavior during sintering and ionic conductivity were also investigated in terms of sintering temperature. FT-IR and XPS results indicated that Fe2+ and Fe3+ ions in Li1+xFexTi2-x(PO4)3-y(BO3)y glass worked as a network modifier (FeO6 octahedra) and also as a network former (FeO4 tetrahedra). In the case of the glass with low substitution of BO3, boron formed (PB)O4 network structure, while boron preferred BO3 triangles or B3O3 boroxol rings with increasing the BO3 content owing to boic oxide anomaly, which can result in an increased non-bridging oxygen. The glass transition temperature (GTT) and crystallization temperature (CT) was lowered as the BO3 substitution was increased, while Fe2+ lowered the GTT and raised the CT. The ionic conductivity of Li1+xFexTi2-x(PO4)3-y(BO3)y glass ceramics were 8.85×10-4 and 1.38×10-4S/cm for x = 0.2 and 0.5, respectively. The oxidation state of doped Fe and boric oxide anomaly were due to the enhanced lithium ion conductivity of glass ceramics.

Li1+xFexTi2-x(PO4)3-y(BO3)y (x = 0.2, 0.5)계 유리에서 Fe doping과 BO3 치환이 유리 또는 결정화유리(glass-ceramics) 전해질의 구조적, 열적 및 전기적 특성에 미치는 영향을 조사하였다. 또한, Li1.5Fe0.5Ti1.5(BO3)3 유리분말을 소결하고, 소결 온도에 따른 결정상과 이온전도도 영향도 검토하였다. Li1+xFexTi2-x(PO4)3-y(BO3)y 유리에서 Fe2+ 및 Fe3+ 이온은 network modifier로서 FeO6 팔면체를 형성하거나 network former로서 유리망목구조에 들어가 FeO4 유사 사면체를 형성하면서 유리의 구조를 변화시키는 것으로 확인되었다. 한편, BO3는 BO3 또는 BO4 그룹을 형성하였는데, BO3 치환량이 작은 경우 boron은 (PB)O4 망목구조를 형성하지만, BO3 치환량이 증가하면 붕소이상현상(boric oxide anomaly)이 생겨나면서 BO4는 BO3로 변화하고 이로 인하여 비가교산소(non-bridging oxygen)가 증가하였다. BO3 치환은 유리전이온도와 결정화 온도를 낮추는 효과가 있으며, Fe 첨가량이 증가하면 Fe3+의 일부는 Fe2+로 환원되며, 유리전이온도와 연화온도를 낮아지게 하고 결정화온도를 높아지게 하는 것으로 확인되었다. Li1+xFexTi2-x(PO4)3-y(BO3)y (x = 0.2, 0.5) 유리에서 BO3 함량이 증가함에 따라 이온전도도는 증가하였으며, x = 0.2 및 0.5에서 각각 8.85×10-4 및 1.38×10-4S/cm의 이온전도도값을 나타내었다. 본 연구에서 얻어진 높은 이온전도도는 Fe3+의 산화상태 변화와 붕소이상현상에 의한 BO3 생성 및 이로 인한 비가교산소의 생성에 기인한 것으로 생각된다. Li1.5Fe0.5Ti1.5(BO3)3 유리를 800℃에서 소결한 결과 이온전도도가 급격히 저하되었는데 이는 결정화유리 분말이 고온에서 유리화되었기 때문으로 생각된다. 따라서 유리분말을 800℃에서 소결한 후, 다시 460℃에서 조핵하고, 600℃에서 결정성장을 시킨 결과, 이온전도도가 열처리전과 동등 수준으로 회복되는 것을 확인하였다.

Keywords

Acknowledgement

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF), funded by the Ministry of Education (No. 1415154009). This work was also supported by the Energy Efficiency & Resources of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Ministry of Knowledge Economy (No. 20172420108680) of South Korea.

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