利用改質石墨烯修飾電極以提高電池在高電壓 下的性能和穩定性

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格維克(Victor Nicolas LE GLANIC) 查詢紙本館藏

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能源工程研究所

論文名稱

利用改質石墨烯修飾電極以提高電池在高電壓下的性能和穩定性
(Modification of the current collector with graphene to enhance the performance and stability of batteries at high voltage)

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至系統瀏覽論文 (2025-9-21以後開放)

摘要(中)

鋰離子電池如今在能量存儲方面得到了廣泛的投資，無論是用於嵌入式設備
還是固定應用。這些電池在零售市場上擁有最佳的電氣性能。從製造出來的那一刻起，
日曆和循環老化都會影響鋰離子電池的性能。老化過程的一個重要部分是電流收集器
的腐蝕，特別是在正極的鋁基底的情況下尤為明顯。一般來說，鋁由於形成了不透水
的原生氧化鋁膜而能夠抵抗腐蝕。然而，在某些電化學條件下，腐蝕會影響電流收集
器的界面。這在高壓鋰離子電池的情況下尤為明顯，這些電池更容易受到腐蝕的影響。
許多防腐策略已被提出。
以往關於通過電化學剝離法製備的氟化石墨烯（FG）的研究表明，這種氟化
電化學剝離石墨烯（F-ECG）似乎是一種有希望的疏水材料，可以解決腐蝕問題，同時
通過石墨烯的獨特性能提高鋁電池電流收集器的電氣性能。本研究展示了應用基於石
墨烯的材料於能量存儲設備的調查，重點關注負極鋁電池電流收集器。
其結果展示了石墨烯基材料應用於儲能裝置的研究，重點關注負極鋁電池集
流體。通過 EPD 在織構鋁箔上逐層塗覆不同結構的保護膜，然後分析其形貌、厚度、
元素組成以及 LSV 電化學和半電池表徵。結果表明，雙層 F-ECG 500s 和 F-ECG 700s
EPD 持續時間的特定條件允許達到 1.63V 的電位極限，這表明與其他無塗層鋁蝕刻樣
品相比，腐蝕保護得到了改善。單層 F-ECG 的半電池測試表明，該結果表明，所提出
的 Al 上的 FECG 改性劑有助於提高循環穩定性，這為未來高性能 LIB 鋪平了道路.

摘要(英)

Lithium-ion batteries are nowadays widely invested in term of energy storage whether
for embedded devices or stationary applications. Those batteries have the best electrical
properties available on the retail market. The unstable cycle stability affects the performance
of the lithium-ion batteries from the moment they are manufactured. An important process
that occurs as a part of the ageing is corrosion of the current collectors, especially prominent
in the case of the aluminum substrate for the positive electrode. Generally, aluminum resists
corrosion due to the formation of a non-permeable film of native aluminum oxide.
Nevertheless, at certain electrochemical conditions corrosion affects the interface of the
current collector. This is especially the case for high-voltage lithium-ion batteries which are
more affected by the corrosion affect.
Many strategies of anti-corrosion have been proposed. Previous works on fluorinated
graphene (FG) obtained by fluorination of the electrochemically exfoliated graphene (F-ECG)
seems to be a promising hydrophobic material to solve corrosion issue while increasing the
electrical properties of aluminum batteries current collector thank to graphene unique
properties.
This work shows the investigation of graphene-based material applied to energy
storage devices focusing on the negative aluminum battery current collector. The different iii
structures of protective film were layer-by-layer coated on the textured Al foil by EPD, then
we analysis the morphology, thickness, elemental composition and the LSV electrochemical
as well as the half-cell characterization. Result show that the specific condition of dual layer
F-ECG 500s and F-ECG 700s EPD duration allows to achieve a potential limit of 1.63V,
suggesting the improved corrosion protection compared to other non-coated aluminum etched
sample. The half-cell testing with single layer F-ECG shows that this result shows that the
proposed FECG modifier on the Al can help to increase the cycling stability, which pay a way
toward performant LIB in the future.

關鍵字(中)

★ 儲能
★ 鋰離子電池
★ 石墨烯
★ 防腐
★ 奈米材料

關鍵字(英)

★ energy storage
★ Li-ion batteries
★ graphene
★ anti-corrosion
★ nanomaterial

論文目次

Abstract ..................................................................................................................................... ii
Table of contents ...................................................................................................................... iv
List of figures ........................................................................................................................... vi
List of tables ............................................................................................................................vii
1. INTRODUCTION ......................................................................................................... 1
1.1 Graphene/ polymeric nanocomposite as an anticorrosion material on aluminum ....... 3
2. MOTIVATION .............................................................................................................. 5
3. METHODOLOGY ........................................................................................................ 8
3.1 Experimental flow chart .............................................................................................. 8
3.2 Synthesis of electrochemically exfoliated graphene (ECG) ........................................ 8
3.3 Synthesis of Fluorinated electrochemically exfoliated graphene (F-ECG) [23] ............ 9
3.4 Coating the nanocomposite on a metallic substrate [23] ............................................. 10
3.5 Material characterizations .......................................................................................... 11
3.6 Electrochemical characterization ............................................................................... 12
4. RESULTS AND DISCUSSION .................................................................................. 13
4.1 Morphology ............................................................................................................... 13
4.1.1 Cold Field Emission Scanning Electron Microscope (CEF-SEM) images ........ 13
4.1.2 Thickness measurements and roughness of F-ECG coated aluminum foil ........ 16
4.2 Hydrophobicity .......................................................................................................... 19
4.2.1 Contact angle measurements. ............................................................................. 19
4.3 Electrochemical properties......................................................................................... 20
4.3.1 Sheet resistance measurements ........................................................................... 20
4.3.2 XPS analysis - Confirmed presence of FAl3 among F-ECG/Al ........................ 22
4.3.3 Linear sweep voltammetry ................................................................................. 254.3.4 Cyclability .......................................................................................................... 27
4.4 Other discussions ....................................................................................................... 31
4.4.1 Reducing the oxygen side reaction with NH3 annealing doping. ....................... 31
4.4.2 Results on dual-layer coating (F-ECG + ECG) .................................................. 31
4.4.3 Controlling the EPD uniformity over large area ................................................ 34
4.4.4 Improving the Adhesion of ECG Coating on Aluminum Surface ..................... 37
5. CONCLUSION ............................................................................................................ 39
6. REFERENCES ............................................................................................................ 40

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指導教授

蘇清源(SU Ching-Yuan)

審核日期

2023-9-21

推文