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3D打印鋰離子電池正極的制備及性能

Preparation and performance of 3D-printed positive electrode for lithium-ion battery

  • 摘要: 采用擠出式3D打印技術制備鋰離子電池電極,選取三元鎳鈷錳酸鋰(LiNi0.5Co0.2Mn0.3O2)作為正極活性材料,以去離子水、羥乙基纖維素和其他添加劑為溶劑來制備性能穩定且適合3D打印技術的鋰離子電池正極墨水,利用流變儀、X射線衍射儀、電池測試儀、ANSYS模擬等探究了增稠劑種類和含量、墨水黏度、打印工藝等對墨水流變性質和可打印性能的影響。結果表明:選取羥乙基纖維素/羥丙基纖維素質量比為1∶1混合且質量分數為3%時,所制備的墨水黏度為20.26 Pa·s,此時墨水具有較好的流變性,打印過程出墨均勻,打印電極光滑平整,滿足后期墨水的可打印性要求,經模擬分析,墨水黏度對墨水流動性影響明顯;電極材料經超聲分散、打印、燒結等過程后未造成原有晶體結構的改變;電極首次充放電容量分別為226.5和119.4 mA·h·g?1,經過20次循環后,電池充放電容量的變化率減小并趨于穩定,3D打印電極表現出良好的循環穩定性。

     

    Abstract: Miniaturized batteries are widely utilized in microscale devices, and 3D printing technology has great advantages in the manufacture of miniaturized battery electrodes. Lithium–nickel–cobalt–manganate material (LiNi0.5Co0.2Mn0.3O2) is gradually becoming a mainstream cathode material for lithium-ion batteries due to its high energy density, high rate of performance, high stability, and low cost. In this study, we prepared lithium-ion-battery electrodes using extrusion-based three-dimensional (3D) printing technology, and we selected ternary nickel–cobalt–manganese hydride as the positive active material. Subsequently, using deionized water, hydroxyethyl cellulose, and other additives, positive inks was prepared for the lithium-ion battery that exhibited stable performance and adequate 3D printing. The effects of thickener type and content, ink viscosity, and the printing process on the rheological properties and printability of the ink were investigated using a rheometer, X-ray diffraction, a battery tester, and ANSYS simulation analysis. The results show that when the mass ratio of hydroxyethyl cellulose/hydroxypropyl cellulose is 1∶1 and the mass fraction is 3%, the viscosity of the prepared ink is 20.26 Pa·s, and it shows good rheology and uniformity in printing. At present, the printing electrode has good rheology, steady ink outflow, and a smooth surface, which satisfies the printability requirements of the ink. Additionally, the simulation results show that the fluidity of the ink is significantly influenced by its viscosity. The electrode preparation process, e.g., ultrasonic dispersion, printing, or sintering, does not lead to a change in the crystal structure of the electrode material. The first-charge and discharge capacities of the electrodes are 226.5 and 119.4 mA·h·g?1, respectively. After 20 cycles, the change rates of the charge and discharge capacities in the battery decrease and then tend to become stable. Lastly, the 3D printed electrode exhibits good cycle stability.

     

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