Microwave absorption characteristics of cathode materials of waste ternary lithium-ion batteries
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摘要: 廢舊三元鋰離子電池對環境和人類有很大危害性，但是其中的鋰、鎳、鈷、錳等有價金屬，具有較高的回收價值。本文以機械破碎后的三元鋰電池為原料，研究了正極材料在室溫下的表觀密度的介電特性以及隨溫度變化的微波介電特性和吸收性能。結果表明，在室溫下，正極材料在表觀密度為1.484 g·cm–3時具有最佳的介電性能。加熱過程中，正極材料在25～700 ℃之間都有良好的微波吸收性能，400 ℃時介電常數
$ {\textit{ε}}_{\rm{r}}^{{{'}}} $ 達到最大值11.96 F·m–1，隨著微波功率增大，正極粉末升到700 ℃的時間明顯縮短，最大升溫速率在320～450 ℃的范圍內。介電性能變化趨勢與微波加熱特性變化趨勢相吻合。Abstract: In recent years, lithium-ion batteries using nickel-cobalt-manganese ternary materials as cathode materials have advantages of good electrical performance, high specific energy, green environmental protection, low cost, and high discharge stability. These have been widely used in new energy vehicles and portable electronics product areas. As a new generation of rechargeable batteries, lithium batteries have a certain service life, which is generally 3–5 years. Therefore, the rapid development of lithium-ion batteries has caused a blowout increase in the number of used lithium-ion batteries. Waste ternary lithium-ion batteries are very harmful to the environment and humans, but valuable metals such as lithium, nickel, cobalt, and manganese have a high recycling value. In terms of resource recycling and environmental protection, used lithium-ion batteries have a high recycling value. At present, the recycling of waste lithium-ion batteries is facing some problems. For example, the diversity of electrode materials makes their separation and purification difficult, and the high cost can also cause some problems such as secondary pollution. Therefore, it is necessary to find green and low-cost methods for the recycling of waste lithium-ion batteries. Microwave metallurgy has outstanding advantages in this respect. Therefore, this paper used the mechanically crushed ternary lithium battery as the raw material for studying the dielectric properties of the apparent density of the positive electrode material at room temperature and the microwave dielectric properties and absorption that change with temperature. Results show that at room temperature, the cathode material has the best dielectric performance at an apparent density of 1.484 g·cm–3. During the heating process, the cathode material has good microwave absorption performance at 25–700 ℃. At 400 ℃, the dielectric constant$ {\textit{ε}}_{\rm{r}}^{'} $ reaches the maximum value of 11.96 F·M–1. With the increase in the microwave power, the time for the positive electrode powder to rise to 700 °C is significantly shortened, and the maximum heating rate is in the range of 320–450 °C. The changing trend of the dielectric properties is consistent with the changing trend of the microwave heating characteristics.-
Key words:
- lithium-ion battery /
- ternary /
- positive electrode powder /
- microwave heating /
- dielectric constant /
- heating rate
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圖 3 介電測試系統的示意圖。（a）介電測試裝置；（b）介電器件中的圓柱諧振腔
Figure 3. Schematic diagram of the dielectric test system: (a) dielectric testing device; (b) cylindrical resonant cavity in the dielectric device
圖 5 正極材料在2450 MHz微波輻射下不同密度下的介電性能。（a）
${{\varepsilon}}_{\rm{r}}^{{'}}$ ；（b）${{\varepsilon}}_{\rm{r}}^{{''}}$ ；（c）tanδFigure 5. Dielectric properties of the cathode material at different densities under 2450 MHz microwave radiation: (a)
${{\varepsilon}}_{\rm{r}}^{{'}}$ ; (b)${{\varepsilon}}_{\rm{r}}^{{''}}$ ; (c) tanδ
圖 6 正極材料在2450 MHz微波輻射下的介電性能。（a）
${{\varepsilon}}_{\rm{r}}^{{'}}$ ；（b）${{\varepsilon}}_{\rm{r}}^{{''}}$ ；（c）tanδ; (d) DpFigure 6. Dielectric properties of the cathode material under 2450-MHz microwave radiation: (a)
${{\varepsilon}}_{\rm{r}}^{{'}}$ ; (b)${{\varepsilon}}_{\rm{r}}^{{''}}$ ; (c) tanδ; (d) Dp
圖 7 不同溫度下的反射損耗RL。（a）25 °C；（b）50 °C；（c）100 °C；（d）150 °C；（e）200 °C；（f）250 °C；（g）300 °C；（h）350 °C；（i）400 °C；（j）450 °C；（k）500 °C；（l）550 °C；（m）600 °C；（n）650 °C; (o) 700 °C
Figure 7. Reflection loss (RL) at different temperatures: (a) 25 °C; (b) 50 °C; (c) 100 °C; (d) 150 °C; (e) 200 °C; (f) 250 °C; (g) 300 °C; (h) 350 °C; (i) 400 °C; (j) 450 °C; (k) 500 °C; (l) 550 °C; (m) 600 °C; (n) 650 °C; (o) 700 °C
圖 8 正極材料在500、750、1000、1500和2000 W微波功率下溫度隨時間變化曲線
Figure 8. Temperature change curve of the cathode material with time under 500, 750, 1000, 1500, and 2000 W microwave power
圖 9 正極材料在不同微波功率下的溫度和升溫速率隨時間變化曲線。（a）500 W；（b）750 W；（c）1000 W；（d）1500 W；（e）2000 W
Figure 9. Temperature change curve and heating rate-change curve of the cathode material with time under different microwave powers: (a) 500 W; (b) 750 W; (c) 1000 W; (d) 1500 W; (e) 2000 W
表 1 廢舊鋰電池正極粉末中主要元素的含量(質量分數)
Table 1. Content of the main elements in the cathode material of waste lithium batteries
% Ni Co Mn C Li Al Fe Cu 14.54 6.60 35.91 1.86 5.89 0.64 0.125 0.002 
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