Preparation and performance of 3D-printed positive electrode for lithium-ion battery
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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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Key words:
- lithium ion battery /
- ternary material /
- printing ink /
- thickener /
- rheology
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圖 1 三元鎳鈷錳酸鋰正極制備流程圖
Figure 1. Flow chart of the preparation of the ternary lithium nickel–cobalt–manganese oxide material positive electrode
圖 2 4種不同增稠劑所制備的正極墨水打印形貌圖. （a）聚丙烯酸鈉；（b）聚丙烯酰胺；（c）羥丙基纖維素；（d）羥乙基纖維素
Figure 2. Printed topographies of positive inks prepared using four different thickeners: (a) sodium polyacrylate; (b) polyacrylamide; (c) hydroxypropyl cellulose; (d) hydroxyethyl cellulose
圖 3 羥乙基/羥丙基纖維素混合配比所制備的正極墨水打印形貌圖
Figure 3. Printed topography of positive ink prepared using hydroxyethyl/hydroxypropyl cellulose
圖 4 不同增稠劑所制備正極打印墨水的表觀黏度－剪切速率曲線
Figure 4. Apparent viscosity–shear rate curves of positive printing ink prepared using different thickeners
圖 5 以羥乙基/羥丙基纖維素為增稠劑的正極打印墨水的模量－應力曲線
Figure 5. Modulus–stress curves of positive printing ink prepared using a hydroxyethyl/hydroxypropyl mixed thickener
圖 6 不同質量分數增稠劑的打印電極形貌圖. （a）1%；（b）3%；（c）5%
Figure 6. Printed electrode topographies of inks with different mass fractions of thickeners: (a) 1%; (b) 3%; (c) 5%
圖 7 墨水在不同黏度下速度分布云圖. （a）31.39 Pa·s；（b）27.58 Pa·s；（c）24.64 Pa·s；（d）23.58 Pa·s；（e）22.73 Pa·s；（f）20.26 Pa·s
Figure 7. Speed distributions of inks with different viscosities: (a) 31.39 Pa·s；(b) 27.58 Pa·s；(c) 24.64 Pa·s；(d) 23.58 Pa·s；(e) 22.73 Pa·s；(f) 20.26 Pa·s
圖 9 3D打印三元材料電極的循環性能曲線
Figure 9. Cycle performances of 3D-printed ternary material electrode
圖 10 不同電流密度下LNCM523打印電極的倍率性能曲線
Figure 10. Magnification performances of LNCM523 printed electrode at different current densities
表 1 不同增稠劑的具體參數
Table 1. Specific parameters of different thickeners
Thickener type Appearance Molecular weight Decomposition temperature /℃ Density/（g?mL?1） Hydroxyethyl cellulose White to light yellow fibrous or powdery solid 144673 288?290 0.75 Hydroxypropyl cellulose White or light yellow solid powder 100000 — 0.5 Polyacrylamide White powder > 5 million >300 1.189 Sodium polyacrylate White powder 8?10 million — 1.32 
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表 2 不同增稠劑含量的正極打印墨水黏度測試
Table 2. Viscosities of positive printing inks with different thickener contents
Thickener mass fraction/% Rotating speed/
(r·min?1)Torque/
%Viscosity/
(Pa·s)1 10 71.8 12.36 2 10 84.3 15.49 3 10 85.1 20.26 4 10 86.2 23.60 5 10 87.8 26.56
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