Microporous Polymer Sorbents for Direct Lithium Extraction,ACS Energy Letters

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Microporous Polymer Sorbents for Direct Lithium Extraction
ACS Energy Letters ( IF 19.3 ) Pub Date : 2024-08-13 , DOI: 10.1021/acsenergylett.4c01590
Michael A. Baird ₁ , Ryan S. Kingsbury ₂ , Yunfei Wang _{3,

4} , Albert Gang ₅ , Chenhui Zhu ₄ , Michael L. Whittaker ₆ , Brett A. Helms _{5,

7}

Affiliation

Lithium extraction from brines is essential to onshoring battery supply chains. Yet, cation-exchange sorbents often exhibit poor selectivity and require pH swings, contributing to increased capital and operating expenditures. Here, we develop lithium extraction sorbents that obviate pH swings by reversibly binding Li⁺ within aqueous brine-compatible polymers of intrinsic microporosity (AquaPIMs) bearing metal-complexing aza-crown-ether pendants. We conduct selectivity screens with synthetic and natural brines, the latter obtained from oilfield and salt lake sites across North America. Sorption selectivities for Li⁺/Na⁺, Li⁺/K⁺, Li⁺/Mg²⁺, and Li⁺/Ca²⁺change with respect to sorbent and brine composition due to pH, mixed-ion effects, and ion–polymer interactions; this behavior was pronounced for natural brines. Using an AquaPIM sorbent embodying aza-12-crown-4 pendants, we demonstrated a lithium extraction process for Smackover Formation brine (Arkansas, USA), enriching Li by a factor of 3.7 when desorbing it with pure water. Our work underscores the importance of designing sorbents based on brine composition and Li⁺/Mⁿ⁺ separation priorities.

中文翻译：

用于直接提取锂的微孔聚合物吸附剂

从盐水中提取锂对于岸上电池供应链至关重要。然而，阳离子交换吸附剂通常表现出较差的选择性，并且需要 pH 值波动，从而导致资本和运营支出增加。在这里，我们开发了锂提取吸附剂，通过将 Li ⁺可逆地结合在带有金属络合氮杂冠醚吊坠的固有微孔性盐水相容聚合物 (AquaPIM) 中，消除 pH 值波动。我们对合成盐水和天然盐水进行选择性筛选，后者从北美各地的油田和盐湖场所获得。 Li ⁺ /Na ⁺ 、Li ⁺ /K ⁺ 、Li ⁺ /Mg ²⁺和 Li ⁺ /Ca ²⁺的吸附选择性因 pH、混合离子效应和离子聚合物而随吸附剂和盐水组成而变化互动；这种行为对于天然盐水来说是明显的。使用包含 aza-12-crown-4 吊坠的 AquaPIM 吸附剂，我们演示了 Smackover 地层盐水（美国阿肯色州）的锂提取工艺，当用纯水解吸时，锂富集了 3.7 倍。我们的工作强调了根据盐水成分和 Li ⁺ / ^{Mn +}分离优先顺序设计吸附剂的重要性。

更新日期：2024-08-13

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