Design of Electrolyte Using Deep Eutectic Solvents for High-Performance Rechargeable Nickel-Iodine Batteries

 Abstract

Rechargeable nickel-ion batteries (RNiBs) have attracted significant attention because of their high volumetric density, low cost, environmental friendliness, and easy recyclability. In this study, a rechargeable nickel-iodine battery using a rational design of a deep eutectic solvent (DES) electrolyte based on a conversion reaction mechanism is first demonstrated. The rechargeable Ni-I2 battery with the DES electrolyte delivered a specific capacity of 201 mAh g−1 with a coulombic efficiency of 82.5% over 65 cycles at a current density of 0.3 A g−1. The energy storage mechanism can be attributed to I+/I− redox chemistry, which has been validated by ex situ Raman, X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The study provides an avenue for exploring rechargeable nickel-ion batteries with DES electrolytes based on the conversion reaction mechanism.

 

https://doi.org/10.1002/smll.202412549

Gutmann Acceptor and Donor number 溶劑給體數和受體數查詢與量測

 

溶劑給體數和受體數查詢表

https://www.stenutz.eu/chem/solv21.php?sort=5

https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.201200584

https://www.degruyter.com/document/doi/10.1351/pac197951081697/html

溶劑給體數和受體數量測

https://www.frontiersin.org/articles/10.3389/fchem.2022.861379/full

Ecofriendly Synthesis of Waste-Tire-Derived Graphite Nanoflakes by a Low-Temperature Electrochemical Graphitization Process toward a Silicon-Based Anode with a High-Performance Lithium-Ion Battery

Abstract

Here, the successful transformation of graphitic carbon with a high degree of graphitization and a nanoflake structure from pyrolytic tire carbon black was demonstrated. First, amorphous carbon black with a porous structure was obtained after pyrolysis and simple preacid treatments. Subsequently, the carbon black was converted into a highly graphitic structure at a relatively low temperature (850 °C) through a facile electrochemical route using molten salt, which is ecofriendly and has high potential for large-scale graphitization compared to conventional incineration techniques. Moreover, we further improved the crystallinity and uniformity of the product simultaneously by directly mixing the metal oxide catalyst Fe2O3 with a carbon precursor. The mechanism of this metal-catalyzed electrochemical graphitization has been discussed in detail. To confirm their potential in practical applications, the as-prepared graphitized nanoflakes were used as conductive additives for silicon anodes in lithium-ion batteries, which showed a performance comparable to those utilizing commercial Super-P additives, exhibiting an initial Coulombic efficiency of approximately 79.7% and a high capacity retention of approximately 45.8% after 100 cycles with a reversible capacity of 1220 mAh g–1 at a current rate of 400 mA g–1. Hence, successfully recovered waste-tire-derived carbon black utilizing a low-temperature Fe2O3-catalyzed electrochemical process opens a pathway in low-temperature graphitization toward a sustainable value-added application in the field of energy storage.

https://doi.org/10.1021/acsami.2c20393

Long-Chain Alkylammonium Organic–Inorganic Hybrid Perovskite for High Performance Rechargeable Aluminon-ion Battery

Abstract

Recent advances in the use of organic-inorganic hybrid perovskites have been investigated in a variety of applications, such as solar cells, photodetectors, light-emitting devices, and lasers, because of their outstanding semiconductor properties. Furthermore, the perovskite structure can host extrinsic elements, making it a promising candidate for battery applications. Previous studies have shown that organic-inorganic hybrid perovskites can be suitable anode materials for both lithium- and sodium-ion batteries. However, multivalent rechargeable batteries with perovskite materials have not yet been realized. Herein, we studied the electrochemical performance of three-dimensional (CH3NH3PbI3 (MAPbI3) and long-chain alkylammonium (C4H9NH3)2(CH3NH3)3Pb4I13 ((iBA)2(MA)3Pb4I13) thin films as electrode materials for rechargeable Al-ion batteries. Our results showed that (iBA)2(MA)3Pb4I13 presented a specific capacity of 257 mAh g–1 at a current density of 0.1 A g−1 and delivered 108 mAh g–1 after 250 cycles at a current density of 0.3 A g−1 with a retention of as high as 91%, demonstrating a crucial role of isobutyl amine (C4H9NH3) due to the unique hydrogen-bonding interaction of isobutyl amine that hinders the shuttle effect of polyiodide. The results open a new direction for the use of organic–inorganic hybrid perovskites for new secondary aluminum ion batteries.

DOI: 10.1016/j.nanoen.2023.108273

用 EIS(Electrochemical Impedance Spectroscopy) 計算擴散係數(diffusion coefficient)

 參考文獻資料:

 Appendix A. Supplementary data : SnO2/super P nanocomposites as anode materials for Na-ion batteries with enhanced electrochemical performance

https://doi.org/10.1016/j.jallcom.2015.10.212

EIS(Electrochemical Impedance Spectroscopy) 建模參考

 參考文獻:https://www.nature.com/articles/s41598-017-01025-7

電化學阻抗譜（EIS）被用作阻抗分析方法，以闡明電池的阻抗回應34,35。鋰電池（LiB）典型的Nyquist圖通常在高頻和中頻範圍內顯示半圓。關於半圓的歸屬，已有不同的研究報告：

 

- 第一大半圓：

  - 據報導主要歸因於正極，第二個半圓歸因於負極36,37。

  - 但Osaka等人則認為第一個半圓屬於負極，第二個半圓屬於正極。

 

然而，通過系統比較SOC50的負極/負極對稱電池、SOC50的正極/正極對稱電池以及SOC50的正極/負極全電池後，我們得出結論：在採用石墨作為負極、NCM111作為正極的層壓全電池中，第一個半圓歸因於正極，第二個半圓歸因於負極。

 

Nyquist圖的其他特徵

除了正極和負極的兩個主要半圓外，Nyquist圖中還包括：

- 一個近似45°的直線，代表活性材料內部的擴散過程。

- 在超低頻（低於1 mHz）下出現幾乎垂直的直線，表示純電容行為。

 

等效電路模型

基於鋰離子電池中的元件和介面，我們提出了圖11(a)所示的等效電路。具體模型包括：

 

- 電化學反應：

  - 正極和負極的電化學反應通過介面電容與串聯的Warburg阻抗相連接的電荷轉移電阻並聯表示。

- 串聯電阻（Rs）：

  - 等效串聯電阻。

- 外部電感元件：

  - 包括線圈和電阻器（L1和R1），與測量設備之間的電極連接及受損的集流體相關。

- 正極部分模型：

  - 由兩種不同半徑的活性材料組成。

  - 兩組擴散元件和電荷轉移電阻的串聯連接與電解質之間的電容及顆粒之間的電連接並聯。

  - 顆粒中電容的變化用恒相元件（CPE）表示，兩種半徑顆粒的電容器並聯連接，並簡化為一個CPE35。

- SEI層的影響：

  - 假設鋰離子通過遷移進入SEI。

  - SEI的阻抗由電阻和SEI層電容並聯組成34,38,40。

 

### EIS結果分析

圖11(b,c)展示了參考電池和添加MG的電池的典型EIS曲線及擬合數據。主要結果包括：

 

- 等效串聯電阻（ESR）：

  - 未添加MG的電池：0.104 Ω/cm²

  - 添加MG的電池：0.094 Ω/cm²

  - 添加MG減少了9.6%的體積電阻。

 

- 正極電荷轉移電阻（Rc）標準化值：

  - 未添加MG的電池：0.106 Ω/cm²

  - 添加MG的電池：0.072 Ω/cm²

  - 添加MG後，正極電荷轉移電阻減少了32%。

 

- 負極電荷轉移電阻（Ra）：

  - 未添加MG的電池：0.44 Ω/cm²

  - 添加MG的電池：0.4 Ω/cm²

  - 添加MG後，負極電荷轉移電阻減少了9%。

 

此外，圖11(c)所示的擴散曲線在低頻下的斜率相對於圖11(b)較小，這表明添加MG提高了電化學雙電層電容。

EC-Lab 操作與Biologic設備保養連結匯總

 1.EC-Lab中阻抗擬合與等效電路

https://mp.weixin.qq.com/s/_knoa_gr-Xe4puvmnBdRqQ

2.如何在EIS測量中檢驗並修正系統的時間方差

https://mp.weixin.qq.com/s/q2peohdNiTnU40nrYpCtrA

3.歐姆降對電化學測試的影響

https://mp.weixin.qq.com/s/Ag2ZznnT0BNiggAKiGa5Xg

4.歐姆降補償的方法

https://mp.weixin.qq.com/s/Aoo8GaN-uTqwZZ5Hsifzbw

5.multisine技術eis測量模式

https://mp.weixin.qq.com/s/FLrue9SdzMT84njBJP-_Mg

6.如何採用EC-Lab檢查和校正非穩態EIS測量 ——（1）腐蝕中的案例

https://mp.weixin.qq.com/s/d_hhKKX8iaYeLmbX7HxfZw

7.如何把每圈實驗的數據分開保存

https://mp.weixin.qq.com/s/hdzAIZcqaalsVpyRHEHl9g

8.EC-Lab中的Cell Characteristics

https://mp.weixin.qq.com/s/_3ulb3x0OxJTGTks7xtEZw

9.這麼多GCPL，如何選擇？

https://mp.weixin.qq.com/s/TvkuVDjAagiiaHCtxaRwVw

10.實驗過程中提示「overload」怎麼辦？

https://mp.weixin.qq.com/s/miH15f96emH_lHeG89Gv6A

11.EC-Lab不同實驗資料檔類型

https://mp.weixin.qq.com/s/fumwNabD4uY2SDtxc7lXiQ

12.EC-Lab資料保存技巧

https://mp.weixin.qq.com/s/TYLF1JvLO6rWSAXOzUFL6w

13.EC-Lab保存實驗設定技巧

https://mp.weixin.qq.com/s/O3XukhOYvi1LseIwjB-vvw

14.EC-Lab狀態列的顏色變來變去

https://mp.weixin.qq.com/s/6xnaIpIFJhhUBSW0CKE-Qw

15.實驗序列中Current range的轉換技巧

https://mp.weixin.qq.com/s/qN_mDxhDYSYir_xFFpVt9Q

16.BioLogic電化學工作站維護方法

https://mp.weixin.qq.com/s/nRN-nF0f9BryQcaFYfPlZQ

17.BioLogic電化學工作站連接電腦的方法

https://mp.weixin.qq.com/s/uvxnpHAjN5FjPUMZoH7_7A

18.「Channel X is locked」怎麼辦？

https://mp.weixin.qq.com/s/97zma6QTkYDiPKSoE4lA7A

19.電容-電壓曲線在光伏電池特性分析的應用

https://mp.weixin.qq.com/s/u6ghgNAbGmiJy0yRkhGp8A

20.EC-Lab在鋼筋混凝土腐蝕測試的應用

https://mp.weixin.qq.com/s/ydGZbZ5fZWitvqfGk5PMTw

Bifunctional TiN@N-doped-graphene catalyst based high sulfur content cathode for reversible Aluminum-Sulfur batteries

 Abstract

Aluminum-sulfur (Al-S) batteries are drawing extensive attentions for the development of economical battery systems owing to the high theoretical capacity of 1672 mAh g−1 and low-cost naturally abundant electrode materials, Al and S. However, Al-S batteries are beset by poor reversibility and low actual capacity, only few reversible Al-S cells have been reported until now. In this work, factors affecting Al–S batteries performance are explored and explained, such as the inactive discharge product(Al2S3), polysulfides diffusion and the self-discharge reaction on the surface of SEI-layer-free aluminum anode. And we demonstrate an improved Al–S battery by effectively adjust the voltage window and develop TiN@N-doped-graphene catalyst materials to modify the sulfur cathode. This catalyst is for the first time applied in Al–S batteries and explored its positive effects during the reversible Al-S reactions. Comprehensive electrochemical testing and ex-situ characterization certificates that, in the discharging process, the shuttle effect of polysulfides is suppressed based on the strong adsorption of catalyst; in the charging process, sulfide redox kinetics are promoted and the decomposition reaction barrier is reduced by the catalyst. The Al-S cell delivers an initial capacity of ∼993 mAh g−1 and maintains a capacity of ∼500 mAh g−1 after 200 cycles.

50 days' free access to the article. (Anyone clicking on this link before May 15, 2022)

https://authors.elsevier.com/c/1eo~w8Z1RX~52K

Intercalation of Zinc Monochloride Cations by Deep Eutectic Solvents for High-Performance Rechargeable Non-aqueous Zinc Ion Batteries

Abstract

Zinc ion batteries have been extensively studied with an aqueous electrolyte system. However, the batteries suffer from a limited potential window, gas evolution, cathode dissolution, and dendrite formation on the anode. Considering these limitations, we developed an alternative electrolyte system based on deep eutectic solvents (DESs) because of their low cost, high stability, biodegradability, and non-flammability, making them optimal candidates for sustainable batteries. The DES electrolyte enables reversible Zn plating/stripping and effectively suppresses zinc dendrite formation. Furthermore, in-depth characterizations reveal that the energy storage mechanism can be attributed to [ZnCl]+ ion intercalation and the intermediate complex ion plays a pivotal role in electrochemical reactions, which deliver a high reversible capacity of 310 mAh g–1 at 0.1 A g–1and long-term stability (167 mAh g–1 at a current density of 0.3 A g–1 after 300 cycles, Coulombic efficiency: ∼98%). Overall, this work represents our new finding in rechargeable batteries with the DES electrolyte.

https://pubs.acs.org/doi/abs/10.1021/acsami.1c19453

Rational design of a polysulfide catholyte electrocatalyst by interfacial engineering based on novel MoS2/MoN heterostructures for superior room-temperature Na–S batteries

Abstract

A suitable electrocatalyst plays an essential role in room-temperature Na–S (RT/Na–S) batteries owing to the more severe dissolution of polysulfides and sluggish kinetics of the conversion of polysulfides during charging and discharging processes. In this study, a novel MoS2/MoN heterostructure synthesized via NH3 annealing was introduced as an electrocatalyst into RT/Na–S batteries to promote the evolution of polysulfides in the catholyte with an initial specific capacity of 703 mA h g−1 and retains 392 mA h g−1 after 300 cycles. The density-functional theory (DFT) calculations, ex-situ XPS and Raman spectra were utilized to reveal moderate anchoring and the fast redox kinetics of polysulfides, significantly enhancing the cycling performance and electrochemical performance of the RT-Na/S batteries when compared with those of the RT-Na/S batteries containing pure MoS2 or MoN as the catalyst. The work provides a new strategy for guiding the design of high‐performance catalysts with manipulated chemical components and optimized adsorption ability.

https://www.sciencedirect.com/science/article/pii/S2211285521008429

Hydrogenated Anatase and Rutile TiO2 for Sodium-Ion Battery Anodes

Defective transition metal oxides prepared via a hydrogenation treatment have attracted growing attention for use as electrode materials of batteries and supercapacitors due to their improved electrochemical properties. In this work, two TiO2 phases, namely, rutile (TiO2-R) and anatase (TiO2-A), and their hydrogenated phases (denoted with the prefix “H”) are investigated as anodes for sodium-ion batteries. The charge–discharge properties of both phases can be enhanced via a high-pressure hydrogenation treatment. For example, H-TiO2-A exhibits exceptional high-rate performance (100 mA h g–1 at 10,000 mA g–1 vs 5 mA h g–1 at the same current rate for TiO2-A) and great cycling stability (80% capacity retention after 4500 cycles). The introduction of oxygen vacancies increases the electronic and ionic conductivity of TiO2 and the disordered structure offers more active sites for electrochemical reactions. The H-TiO2-R and H-TiO2-A electrodes are compared for sodium-ion battery applications. The superior performance of the former electrode is supported by the generalized gradient approximation Perdew–Burke–Ernzerhof density functional calculation.

https://pubs.acs.org/doi/abs/10.1021/acsaem.1c00571#

Cell voltage and cell energy density calculation

Reference: https://pubs.acs.org/doi/suppl/10.1021/acsenergylett.0c00913/suppl_file/nz0c00913_si_001.pdf

EC-Lab EIS 擬合結果error 值 和 deviation 偏差值之判讀

 

經EC-Lab EIS成功擬合結果可得下表

藍色框框為deviation (dev)

紅色框框為 error ratio ( X2/ I Z I )

一般來說，dev偏差值要<1，但超過5個elements的fitting, 後面elements 的dev都可以容許比較大一點，以這範例來說R2與R3 略大於1是OK的。

而 error ratio ( X2/ I Z I ) <0.1。

一般在擬合時，會先看dev值是否<1，在查核 error ratio。

官方Youtube頻道參考影片:(影片標題及連結)

Description of the fitting window – ZFit tutorial, part.4 - BioLogic

Tips and tricks - ZFit tutorial, part.5 - BioLogic 

ZSim and ZFit as learning tools. Part V – How to choose the proper equivalent circuit? 

ZSim and ZFit as learning tools. Part VII – Equivalent circuits identifiability 

ZFit: How to have confidence in results using std err.?

固態電池相關知識影片

5.1 贺艳兵：固态电池电解质和界面研究

https://www.bilibili.com/video/BV1RC4y1t786 

5.2 固态电池研究及产业化

https://www.bilibili.com/video/BV1Ea4y1x7eh 

5.3  加拿大西安大略大學孫學良-全固態電池：電池界面設計、新型固態電解質和電極

https://www.bilibili.com/video/BV1ei4y1x7Ta 

5.4  查爾姆斯理工大學熊仕昭-固態電池與鋰負極界面設計

https://www.bilibili.com/video/BV1bZ4y1H7Bv 

5.5  中科院化學所郭玉國-金屬鋰固態電池研究進展

https://www.bilibili.com/video/BV1FK4y147Fz 

新穎電池相關知識影片

4.1 方国赵：锌离子电解液与电极界面研究

https://www.bilibili.com/video/BV1oa4y1E7Xm  

4.2 Operando XAFS在電池研究中的應用

https://www.bilibili.com/video/BV11t4y117Ga 

4.3 華南師範大學邢麗丹-離子溶劑化層結構對電解液及電極/電解液界面性質的影響機理

https://www.bilibili.com/video/BV16K4y1t7xd  

碳材料與MXene相關知識影片彙整

3-1  劉婧：拉曼光譜原理及其在碳材料中的應用

https://www.bilibili.com/video/BV1jg4y1q7Zz  

3-2 四川大學林紫鋒-二維Mxene及其電化學儲能

https://www.bilibili.com/video/BV1nZ4y1p7b6

電池相關教學影片彙整

 1.基礎知識篇: 

山東科技大學劉瑞《鋰離子電池》前沿課程（目前有7部，持續更新中）

https://www.bilibili.com/video/BV1Zi4y1x7b5  

2.電池材料分析篇

2-1廈門大學李劍鋒-電化學拉曼光譜分析

https://www.bilibili.com/video/BV1ta4y177g4  

2-2 復旦大學蔡文斌-電化學紅外光譜方法和應用

https://www.bilibili.com/video/BV1iV411U7ok  

2-3 山東科技大學劉瑞-用於電池材料研究的X射線粉末衍射基礎

https://www.bilibili.com/video/BV19z4y1X73b 

2-4  XRD在電化學中的應用

https://www.bilibili.com/video/BV1ve411s73g 

2-5  XPS實驗技術及在電池領域的應用

https://www.bilibili.com/video/BV1yv411q7ii 

2-6 掃描電鏡工作原理及製樣方法

 https://www.bilibili.com/video/BV1Ta4y147er   

Three-Dimensional Molybdenum Diselenide Helical Nanorod Arrays for High-Performance Aluminum-Ion Batteries

 The rechargeable aluminum-ion battery (AIB) is a promising candidate for next-generation high-performance batteries, but its cathode materials require more development to improve their capacity and cycling life. We have demonstrated the growth of MoSe2 three-dimensional helical nanorod arrays on a polyimide substrate by the deposition of Mo helical nanorod arrays followed by a low-temperature plasma-assisted selenization process to form novel cathodes for AIBs. The binder-free 3D MoSe2-based AIB shows a high specific capacity of 753 mAh g–1 at a current density of 0.3 A g–1 and can maintain a high specific capacity of 138 mAh g–1 at a current density of 5 A g–1 with 10 000 cycles. Ex situ Raman, XPS, and TEM characterization results of the electrodes under different states confirm the reversible alloying conversion and intercalation hybrid mechanism during the discharge and charge cycles. All possible chemical reactions were proposed by the electrochemical curves and characterization. Further exploratory works on interdigital flexible AIBs and stretchable AIBs were demonstrated, exhibiting a steady output capacity under different bending and stretching states. This method provides a controllable strategy for selenide nanostructure-based AIBs for use in future applications of energy-storage devices in flexible and wearable electronics.

https://doi.org/10.1021/acsnano.0c02831

Transparent Flexible Heteroepitaxy of NiO Coated AZO Nanorods Arrays on Muscovites for Enhanced Energy Storage Application

Transparent flexible energy storage devices are considered as important chains in the next‐generation, which are able to store and supply energy for electronic devices. Here, aluminum‐doped zinc oxide (AZO) nanorods (NRs) and nickel oxide (NiO)‐coated AZO NRs on muscovites are fabricated by a radio frequency (RF) magnetron sputtering deposition method. Interestingly, AZO NRs and AZO/NiO NRs are excellent electrodes for energy storage application with high optical transparency, high conductivity, large surface area, stability under compressive and tensile strain down to a bending radius of 5 mm with 1000 bending cycles. The obtained symmetric solid‐state supercapacitors based on these electrodes exhibit good performance with a large areal specific capacitance of 3.4 mF cm−2, long cycle life 1000 times, robust mechanical properties, and high chemical stability. Furthermore, an AZO/NiO//Zn battery based on these electrodes is demonstrated, yielding a discharge capacity of 195 mAh g−1 at a current rate of 8 A g−1 and a discharge capacity of over 1000 cycles with coulombic efficiency to 92%. These results deliver a concept of opening a new opportunity for future applications in transparent flexible energy storage.

https://doi.org/10.1002/smll.202000020

High-Performance Rechargeable Aluminum–Selenium Battery with a New Deep Eutectic Solvent Electrolyte: Thiourea-AlCl3

Aluminum–sulfur batteries (ASBs) have attracted substantial interest due to their high theoretical specific energy density, low cost, and environmental friendliness, while the traditional sulfur cathode and ionic liquid have very fast capacity decay, limiting cycling performance because of the sluggishly electrochemical reaction and side reactions with the electrolyte. Herein, we demonstrate, for the first time, excellent rechargeable aluminum–selenium batteries (ASeBs) using a new deep eutectic solvent, thiourea-AlCl3, as an electrolyte and Se nanowires grown directly on a flexible carbon cloth substrate (Se NWs@CC) by a low-temperature selenization process as a cathode. Selenium (Se) is a chemical analogue of sulfur with higher electronic conductivity and lower ionization potential that can improve the battery kinetics on the sluggishly electrochemical reaction and the reduction of the polarization where the thiourea-AlCl3 electrolyte can stabilize the side reaction during the reversible conversion reaction of Al–Se alloying processes during the charge–discharge process, yielding a high specific capacity of 260 mAh g–1 at 50 mA g–1 and a long cycling life of 100 times with a high Coulombic efficiency of nearly 93% at 100 mA g–1. The working mechanism based on the reversible conversion reaction of the Al–Se alloying processes, confirmed by the ex situ Raman, XRD, and XPS measurements, was proposed. This work provides new insights into the development of rechargeable aluminum–chalcogenide (S, Se, and Te) batteries

https://pubs.acs.org/doi/10.1021/acsami.0c03882