Research progress on the alkaline-system selective recycling technology in spent lithium-ion batteries
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摘要: 由于鋰離子電池中的雜質金屬在氫氧化物中溶解度差，而鋰、鎳、鈷由于本身氫氧化物溶解度較大，或能與氨根離子形成絡合物，能大量存在于堿溶液中。因此堿浸對廢舊電池正極活性物質中的金屬具有較高的的選擇性浸出能力，且回收工藝高效、清潔。本文依據堿浸回收的工業研究現狀，總結了四種堿浸回收體系，包括氨浸?熱加工?還原劑體系、氨浸-還原劑-電沉積體系、氨浸?還原劑?鋰吸附體系、氨浸?還原劑?氧化分離體系，并著重介紹了不同體系的原理及優點。最后，總結了廢舊鋰離子電池的回收方法及前景。Abstract: Due to the issue of raw material depletion, lithium-ion batteries are becoming less value-added. In addition, the highly toxic organic electrolytes contained in them cause serious harm to humans and the environment. That is why the effective recovery of spent lithium-ion batteries is of great importance for the development and sustainable use of lithium-ion batteries. Currently, recovery of metals present in spent lithium-ion batteries mainly relies on hydrometallurgical extraction: The main metals are extracted through acid or alkali media followed by recovery of metal compounds through further processing or the resynthesis of high-performance materials. Among them, acid leaching is a short and highly efficient process; however, this process dissolves all the metal ions in the solution, making it difficult to subsequently separate and purify the valuable metals. Contrarily, the hydroxide of impure metal in lithium-ion batteries shows low solubility, whereas lithium, nickel, and cobalt have high solubility, allowing for the formation of complexes with ammonia ions that can exist in alkali solution in large quantities. Thus, alkaline leaching has better selective leaching of metals in electrode materials due to the high solubility of lithium, nickel, and cobalt ammonia complexes and has a more efficient and cleaner recovery process, which is of outstanding importance in the industry. Most research was mainly focused on various acid recovery systems and scales, and the research progress on the alkaline recovery process was insufficient. Here, based on the industrial research status of alkali leaching recovery, four alkali leaching recovery systems, which include the ammonia leaching-reductant-hot working system, ammonia leaching-reductant-electrodeposition system, ammonia leaching-reductant-lithium adsorption system, and ammonia leaching-reductant-oxidation separation system, were reviewed along with their principles and advantages. Finally, a brief summary of the recovery methods for spent lithium-ion batteries was expressed.
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Key words:
- spent lithium-ion batteries /
- recovery /
- alkaline leaching /
- selectivity /
- metal-ammonia complex
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圖 1 (a)廢舊鋰離子電池處理流程圖[23]；(b)廢舊鋰離子電池回收過程[17]；(c)浸出劑含量對金屬浸出效率的影響(摩爾比NH3∶(NH4)2SO3:(NH4)2CO3=1∶0.5∶1, 80 oC和1 h)[17]；(d)二元體系（氨+亞硫酸銨）或三元體系（氨+亞硫酸銨+碳酸銨）中pH的變化[17]；(e)碳酸銨濃度對金屬浸出效率的影響(1 mol·L?1氨溶液，0.5 mol·L?1亞硫酸銨，80 oC和1 h) [17]
Figure 1. (a) Flow chart of recycling waste lithium-ion batteries[23]; (b) the recycling process of waste lithium-ion batteries[17]; (c) the effect of leaching agent content on metal leaching efficiency (NH3∶(NH4)2SO3:(NH4)2CO3=1∶0.5∶1, 80 °C, and 1 h)[17]; (d) change in pH in a binarysystem (ammonia + ammonium sulfite) or ternary system (ammonia + ammonium sulfite + ammonium carbonate)[17]; (e) the effect of ammonium carbonate concentration on metal leaching efficiency (1 mol·L?1 ammonia solution, 0.5 mol·L?1 ammonia sulfite solution, 80 °C, and 1 h) [17]
圖 2 (a) 廢舊鋰離子電池中有價金屬回收過程圖[24]；(b) 在300 ℃和500 ℃下煅燒的陰極活性粉末的SEM圖[25]；(c) (NH4)2SO4濃度對Ni、Co、Li和Mn浸出效果的影響(3 mol·L?1 (NH4)2SO4，陰極粉末質量與加入溶液的體積比為100 g·L?1)[25]；(d) (NH4)2SO3濃度對Ni、Co、Li和Mn浸出效果的影響(3 mol·L?1 (NH4)SO3，陰極粉末質量與加入溶液的體積比為100 g·L?1)[25]
Figure 2. (a) Diagram of the valuable metal recovery process from waste lithium-ion batteries[24]; (b) the SEM images of the cathode active powder calcined at 300 ℃ and 500 ℃[25]; (c) the effect of (NH4)2SO4 concentration on Ni, Co, Li, and Mn leaching efficiencies (3 mol·L?1 (NH4)2SO4, the ratio of the mass of cathode powder to volume of added solution is 100 g·L?1) [25]; (d) the effect of (NH4)2SO3 concentration on Ni, Co, Li, and Mn leaching efficiencies (3 mol·L?1 (NH4)2SO3, the ratio of the mass of cathode powder to volume of added solution is 100 g·L?1) [25]
圖 4 (a)鋰吸附法回收過程示意圖[29]；(b)鋰吸附法回收鋰離子電池中Li、Co和Ni的流程[29]；(c) 初始鋰離子濃度[29]; (d)每升溶液鋰離子篩用量與鋰離子篩上吸附的Li+、Ni2+和Co2+的量的關系[29]
Figure 4. (a) Schematic diagram of lithium adsorption recovery process[29]; (b) the process of recovering Li, Co, and Ni in lithium-ion batteries by lithium adsorption[29]; (c) initial lithium-ion concentration[29]; (d) the amount of lithium-ion sieve per liter of solution relationship with the amounts of Li+, Ni2+, and Co2+ adsorbed on the lithium-ion sieve[29]
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