非プロトン性のLi-Oの電気化学的試験のプロトコルとキャラクタリゼーション<sub> 2</sub>バッテリー
Summary
A protocol for the electrochemical testing of an aprotic Li-O2 battery with the preparation of electrodes and electrolytes and an introduction of the frequently used methods of characterization is presented here.
Abstract
We demonstrate a method for electrochemical testing of an aprotic Li-O2 battery. An aprotic Li-O2 battery is made of a Li-metal anode, an aprotic electrolyte, and an O2-breathing cathode. The aprotic electrolyte is a solution of lithium salt with aprotic solvent; and porous carbon is commonly used as the cathode substrate. To improve the performance, an electrocatalyst is deposited onto the porous carbon substrate by certain deposition methods, such as atomic layer deposition (ALD) and wet-chemistry reaction. The as-prepared cathode materials are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray absorption near edge structure (XANES). A Swagelok-type cell, sealed in a glass chamber filled with pure O2, is used for the electrochemical test on a battery test system. The cells are tested under either capacity-controlled mode or voltage controlled mode. The reaction products are investigated by electron microscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, and Raman spectroscopy to study the possible pathway of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). This protocol demonstrates a systematic and efficient arrangement of routine tests of the aprotic Li-O2 battery, including the electrochemical test and characterization of battery materials.
Introduction
1996年に、アブラハムと江1は、多孔質炭素陰極、有機電解液、およびLi-金属アノードから成る第一の可逆非水性のLi-O 2バッテリーを報告しました。それ以来、何らかの他の既存のエネルギー貯蔵システムのそれを超えて、非常に高い理論エネルギー密度に、アノードにおけるリチウムの酸化による電流の流れとカソードにおける酸素の還元を（誘導のLi-O 2電池全体の反応のLi + + O 2 + E – ↔のLi 2 O 2）は 、最近大きな関心を受けている1-8。
次の要件を有するカソード材料は、Li-O 2電池の高性能化のニーズに応えることができるだろう：（1）高速酸素拡散。 （2）良好な電気およびイオン伝導性を。 （3）高比表面積; （4）安定性。両方のカソードの表面積及び気孔率は、のために重要です。リチウムO 2電池の電気化学的性能9-12多孔質構造は、O 2でのLiカチオンの反応から生成された固体の放電生成物の付着を可能にします。より大きな表面積は、電気化学反応を促進電気触媒粒子を収容するためにそれ以上の活性部位を提供します。このような電極触媒は、13-17。基板の元の多孔質表面構造の保存と、基板と触媒粒子の良好な制御に強い接着を提供する特定の堆積法によってカソード材料に添加されるように調製された材料は、試験されます非プロトン性のLi-O 2電池のカソードとしてスウェージロック型細胞です。しかし、電池の性能は、カソード材料の性質に依存するだけでなく、非プロトン性電解質18〜22とリチウム金属アノードの種類のみならず。23-26より影響は、材料の量および濃度を含み、そしてP充電/放電試験に用いrocedure。適切な条件およびプロトコルを最適化し、電池材料の全体的な性能を向上させるであろう。
電気化学的試験の結果に加えて、電池性能にも自然のままの材料との反応生成物を特徴づけることによって評価することができる。27-33走査電子顕微鏡（SEM）は、カソード材料の表面の微細構造および形態を調査するために使用され放電生成物の進化。透過型電子顕微鏡（TEM）エッジ構造（XANES）の近くに、X線吸収、及びX線光電子分光法（XPS）は、特に、触媒ナノ粒子のために、素子の超微細構造、化学的状態、およびコンポーネントを決定するために用いることができます。高エネルギーX線回折（XRD）を直接結晶放電生成物を識別するために使用されます。可能な電解液の分解は減衰全反射フーリエ変換によって決定することができる変換赤外線（ATR-FTIR）及びラマンスペクトル。
この記事では、電池材料および付属品の準備、電気化学的性能試験、自然のままの材料および反応生成物の特性を含む非プロトン性のLi-O 2電池の通常の試験の体系的かつ効率的な配置を示しているプロトコルです。詳細なビデオプロトコルは、フィールドに新しい実践者は、Li-O 2電池の性能試験および特性評価に関連した多くの一般的な落とし穴を避けるのを助けることを意図しています。
Protocol
Representative Results
Discussion
空気へのLi-O 2電池システムの感度を考慮すると、特にCO 2および湿度、プロトコルのステップの多くは、干渉を低減し、副反応を避けるために必要です。例えば、スウェージロック型の細胞はO 2 <0.5ppmの及びH 2 O <0.5 ppm以下でアルゴンを充填したグローブボックス内で組み立てられます。そして、すべてのカソード材料、電解質溶媒及び塩、ガラス繊維、ス…
Disclosures
The authors have nothing to disclose.
Acknowledgements
Research at Argonne National Laboratory was funded by U.S. Department of Energy, FreedomCAR and Vehicle Technologies Office. Use of the Advanced Photon Source and research carried out in the Electron Microscopy Center at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.
Materials
| 1-Methyl-2-pyrrolidinone (NMP), 99.5% | Sigma-Aldrich | 328634 | |
| Battery test system | MACCOR | Series 4000 Automated Test System | |
| Dimethyl carbonate (DMC), ≥99% | Sigma-Aldrich | 517127 | |
| Ethyl alcohol, ≥99.5% | Sigma-Aldrich | 459844 | |
| Formaldehyde solution, 37 wt. % in H2O | Sigma-Aldrich | 252549 | |
| Graphitized Carbon black, >99.95% | Sigma-Aldrich | 699632 | |
| Iron(III) chloride (FeCl3), 97% | Sigma-Aldrich | 157740 | |
| Kapton polyimide tubing | Cole-Parmer | EW-95820-09 | |
| Kapton polymide tape | Cole-Parmer | EW-08277-80 | |
| Kapton window film | SPEX Sample Prep | 3511 | |
| Lithium Chip (99.9% Lithium) | MTI Corporation | EQ-Lib-LiC25 | |
| Lithium trifluoromethanesulfonate (LiCF3SO3) | Sigma-Aldrich | 481548 | |
| Palladium hexafluoroacetylacetonate (Pd(hfac)2), 99.9% | Aldrich | 401471 | |
| Poly(vinylidene fluoride) (PVDF) | Aldrich | 182702 | |
| Potassium permanganate (KMnO4), ≥99.0% | Sigma-Aldrich | 223468 | |
| Sodium hydroxide (NaOH), ≥97.0% | Sigma-Aldrich | 221465 | |
| Tetraethylene glycol dimethyl ether (TEGDME), ≥99% | Aldrich | 172405 | |
| Toray 030 carbon paper | ElectroChem Inc. | 590637 | |
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