Research progress on the alkaline-system selective recycling technology in spent lithium-ion batteries
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摘要: 由于锂离子电池中的杂质金属在氢氧化物中溶解度差，而锂、镍、钴由于本身氢氧化物溶解度较大，或能与氨根离子形成络合物，能大量存在于碱溶液中。因此碱浸对废旧电池正极活性物质中的金属具有较高的的选择性浸出能力，且回收工艺高效、清洁。本文依据碱浸回收的工业研究现状，总结了四种碱浸回收体系，包括氨浸−热加工−还原剂体系、氨浸-还原剂-电沉积体系、氨浸−还原剂−锂吸附体系、氨浸−还原剂−氧化分离体系，并着重介绍了不同体系的原理及优点。最后，总结了废旧锂离子电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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图 1 (a)废旧锂离子电池处理流程图[23]；(b)废旧锂离子电池回收过程[17]；(c)浸出剂含量对金属浸出效率的影响(摩尔比NH3∶(NH4)2SO3:(NH4)2CO3=1∶0.5∶1, 80 oC和1 h)[17]；(d)二元体系（氨+亚硫酸铵）或三元体系（氨+亚硫酸铵+碳酸铵）中pH的变化[17]；(e)碳酸铵浓度对金属浸出效率的影响(1 mol·L−1氨溶液，0.5 mol·L−1亚硫酸铵，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]
图 2 (a) 废旧锂离子电池中有价金属回收过程图[24]；(b) 在300 ℃和500 ℃下煅烧的阴极活性粉末的SEM图[25]；(c) (NH4)2SO4浓度对Ni、Co、Li和Mn浸出效果的影响(3 mol·L−1 (NH4)2SO4，阴极粉末质量与加入溶液的体积比为100 g·L−1)[25]；(d) (NH4)2SO3浓度对Ni、Co、Li和Mn浸出效果的影响(3 mol·L−1 (NH4)SO3，阴极粉末质量与加入溶液的体积比为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]
图 4 (a)锂吸附法回收过程示意图[29]；(b)锂吸附法回收锂离子电池中Li、Co和Ni的流程[29]；(c) 初始锂离子浓度[29]; (d)每升溶液锂离子筛用量与锂离子筛上吸附的Li+、Ni2+和Co2+的量的关系[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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