[논문]리튬 금속 전극상 고분자/무기물 나노복합막 형성: 리튬층의 효과적 표면성장 제어 및 전기화학적 특성 향상

정요한; 석도형; 이상현; 신원호; 손희상

doi:10.14579/membrane_journal.2020.30.1.30

리튬 금속 전극상 고분자/무기물 나노복합막 형성: 리튬층의 효과적 표면성장 제어 및 전기화학적 특성 향상
Polymer/Inorganic Nanohybrid Membrane on Lithium Metal Electrode: Effective Control of Surficial Growth of Lithium Layer and Its Improved Electrochemical Performance 원문보기

멤브레인 = Membrane Journal, v.30 no.1, 2020년, pp.30 - 37

정요한 (광운대학교 화학공학과) , 석도형 (광운대학교 화학공학과) , 이상현 (광운대학교 화학공학과) , 신원호 (광운대학교 전자재료공학과) , 손희상 (광운대학교 화학공학과)

초록
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리튬 덴드라이트의 효과적인 억제를 위해 유/무기 복합체를 리튬메탈 전극의 보호층으로 사용하였다. 유기물로는 PVDF-HFP가 사용되었으며 무기물로는 TiO₂가 사용되었다. 유기물로 사용된 PVDF-HFP는 높은 유연성을 가지는 고분자로서 무기물의 matrix 역할을 하며, 무기물로 사용된 TiO₂ 나노입자는 보호막의 기계적 강도와 이온전도성을 향상시켜주는 역할을 하였다. 합성된 보호막은 SEM, AFM, XRD를 통하여 PVDF-HFP matrix에 TiO₂가 잘 분산되어 있는 형태인 것을 확인할 수 있었다. 또한 전기화학적 분석 결과, 향상된 기계적 물성과 이온전도성으로 인해 polymer-inorganic composite은 비교 샘플(untreated 와 PVDF-HFP 보호층) 대비 100번째 사이클까지 80%의 높은 쿨롱 효율 및 20 mV 미만의 낮은 과전압을 나타내었다.

Abstract ▼ AI-Helper

Polymer/inorganic composites were used as a protective layer of lihitum metal electrode for effective suppression of lithium dendrite. PVDF-HFP was used as an polymer material and TiO2 nanoparticle was used as an inorganic material. PVDF-HFP is a highly flexible polymer that acts as a matrix of inorganic materials while TiO2 nanoparticle improves the mechanical strength and ion conductivity of the protective layer. The as-synthesized protective hybrid membrane exhibited good dispersion of TiO2 in the PVDF-HFP matrix by SEM, AFM and XRD analyses. Furthermore, the electrochemical analysis showed that the polymer-inorganic composite retained high coulombic efficiency of 80% and low overpotential, less than 20 mV until the 100th cycles due to the improved mechanical properties and ion conductivity in comparison to the control sample (untreated and PVDF-HFP polymers/Cu).

주제어

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제안 방법

In the SEM image, TiO₂ nanoparticles are observed as white dots, which exhibits well dispersion of TiO₂ nanoparticles on the PVDF-HFP matrix. For more detailed analysis, the elemental mapping analysis was performed. As shown in Fig.
In this study, a composite of PVDF-HFP and TiO₂ (PVDF-HFP@TiO₂ membrane) was designed as a protective layer of lithium metal for effective suppression of lithium dendrite. The designed protective layer was found to effectively inhibit lithium dendrite by improved ion conductivity and mechanical properties.
In this study, the polymer-inorganic hybrid layer was designed as a protective layer for effective suppression of lithium dendrite on the electrode. PVDF-HFP was used as a polymer material and TiO₂ was used as an inorganic material.
To confirm that the design proceeded as intended, we analyzed the presence of TiO₂ in the polymer and analyzed the electrochemical properties of the designed hybrid membrane. The morphology and elemental distribution of the surface of the PVDF-HFP/TiO₂ hybrid membrane were observed by scanning electron microscope (SEM) and energy-dispersive X-ray spectroscopy (EDS) to identify the elements in TiO₂ and PVDF-HFP.

대상 데이터

hybrid membrane coated Cu electrode as a working electrode. Electrolyte contained 1 M of LiTFSI in 1,3-dioxolane (DOL)/1,2-dimethoxyethane (DME) (1 : 1 = v : v). Coin cells were fabricated in a glove box filled with argon.
5%) were used as the solvent to be used in the interfacial synthesis method. Polyvinylidene fluoride-co-hexafluoropropylene, (PDVF-HFP, Sigma-Aldrich) was used as a polymer, and N-methyl-2-pyrrolidone (NMP, Sigma-Aldrich) was used as a solvent to dissolve polymer and nanoparticle precursors.

이론/모형

Subsequently, an electrochemical Li|Cu half-cell was fabricated using PVDF-HFP/TiO₂ hybrid membrane on Cu substrate in a glove box. Then, the lithium layer was formed between Cu and PVDF-HFP/TiO₂ hybrid membrane via the electrochemical deposition method.

성능/효과

From characterizations, it is found that the designed protective layer has the structure in which TiO₂nanoparticles were evenly dispersed in the PVDF-HFP matrix. As a result of the electrochemical analysis, the untreated samples maintained stable coulombic efficiency until the 55^th cycles, while PVDF-HFP@TiO₂ hybrid membrane showed high coulombic efficiency, 80% until the 100^th cycles. Furthermore, from the voltage profiles and voltage-time curves, the untreated sample represented the high overpotential of 200 mV in the last cycle, but PVDF-HFP@TiO₂ hybrid membrane maintained a low overpotential, less than 20 mV.
The diffraction peaks of PVDF-HFP indicate (100) and (020) planes, and peaks of TiO₂ anatase represent (101), (004), (200), (105), and (204) planes. From these results, the film prepared in this study is considered a polymer-inorganic composite of PVDF-HFP and TiO₂, it is expected that the lithium dendrite can be effectively suppressed and the improved lithium-ion transport can be achieved by the addition of TiO₂ [18,19].

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