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  隨著綠色儲能和柔性電子紡織品的快速發(fā)展，提升水系鋅離子電池的安全性與循環(huán)性能成為科研領(lǐng)域的熱點難題。近日，浙江理工大學(xué)紡織科學(xué)與工程學(xué)院（國際絲綢學(xué)院）胡毅教授團隊在國際知名期刊《Energy Storage Materials》（影響因子20.2）在線發(fā)表了題為《A Bioinspired Flexible Hydrogel Electrolyte with β-Sheet–Directed Interphase for Dendrite-Free Zn Metal Batteries》的研究論文。本研究立足紡織染整領(lǐng)域優(yōu)勢，創(chuàng)新引入天然絲素蛋白作為結(jié)構(gòu)調(diào)控介質(zhì)，結(jié)合其在柔性可加工性、構(gòu)象可控性和界面親和性等方面的獨特特性，通過乙醇誘導(dǎo)其構(gòu)象轉(zhuǎn)變，構(gòu)建出具有高度有序β-折疊結(jié)構(gòu)的仿生界面層。這一界面層在鋅金屬負極表面有效抑制鋅枝晶生長，顯著提升電池循環(huán)壽命與安全性能。該研究不僅拓展了絲素蛋白在柔性儲能器件中的高值應(yīng)用路徑，也為紡織基礎(chǔ)材料向多功能智能化拓展提供了新的思路，有望為綠色可穿戴電子產(chǎn)品提供更高安全性、更長使用壽命的儲能解決方案。論文DOI: 10.1016/j.ensm.2025.104464。本文第一作者為浙江理工大學(xué)紡織科學(xué)與工程學(xué)院碩博連讀研究生申盼盼，通訊作者為浙江理工大學(xué)博士生導(dǎo)師胡毅教授。

  在水系鋅離子電池快速發(fā)展的背景下，鋅負極的枝晶生長與副反應(yīng)問題成為制約電池壽命與安全性的核心瓶頸。傳統(tǒng)電解液添加劑雖然能夠在一定程度上調(diào)控鋅離子的沉積行為，但多為小分子結(jié)構(gòu)，難以實現(xiàn)界面層的高穩(wěn)定性和有序功能協(xié)同。

  鑒于此，浙江理工大學(xué)紡織科學(xué)與工程學(xué)院（國際絲綢學(xué)院）博士生導(dǎo)師胡毅教授課題組，充分發(fā)揮天然蛋白纖維、結(jié)構(gòu)染整方面的學(xué)科優(yōu)勢，創(chuàng)新提出基于絲素蛋白構(gòu)象誘導(dǎo)的仿生界面調(diào)控策略。團隊以蠶繭來源的天然絲素蛋白為功能調(diào)控單元，依托其可調(diào)構(gòu)象特性與優(yōu)異界面親和性，通過微量乙醇誘導(dǎo)絲素蛋白構(gòu)象轉(zhuǎn)變，由無規(guī)卷曲/α-螺旋轉(zhuǎn)化為高度有序的β-折疊結(jié)構(gòu)，構(gòu)筑致密穩(wěn)定的氫鍵網(wǎng)絡(luò)，在鋅負極表面形成具有力學(xué)穩(wěn)定性與離子選擇性的仿生保護層。得益于該仿生界面的構(gòu)建，Zn||Zn對稱電池實現(xiàn)了超過2500小時的穩(wěn)定循環(huán)。基于該體系構(gòu)建的Zn||MnO₂全電池循環(huán)1500次后仍保持93.8%的容量，柔性鋅離子纖維電池在連續(xù)2500次循環(huán)后容量保持率超過95%。本研究不僅實現(xiàn)了對鋅沉積過程的分子層級精準(zhǔn)調(diào)控，更探索出絲素蛋白在新能源器件界面構(gòu)建中的高值應(yīng)用路徑，充分體現(xiàn)了紡織染整材料在綠色柔性儲能領(lǐng)域的跨界融合潛力，為構(gòu)建新一代安全、環(huán)保、高性能的柔性電子紡織儲能單元提供了可持續(xù)發(fā)展思路。

圖1.絲素蛋白的構(gòu)象轉(zhuǎn)變機理

Figure 1. Conformational Transition of Silk Fibroin in PAM Gel Electrolyte. (a) Schematic illustration of solvent-induced conformational transitions in silk fibroin proteins; (b) Fourier transform infrared (FTIR) spectra of SF/PAM and β-SF/PAM gel electrolytes in the 1200–2000 cm?1 region; (c) Circular dichroism (CD) spectra of SF/PAM and β-SF/PAM gel electrolytes; (d) Raman spectra of PAM, SF/PAM, and β-SF/PAM gel electrolytes; (e) SEM images of β-SF/PAM gel electrolyte microstructure; (f) corresponding energy-dispersive X-ray spectroscopy (EDS) elemental mappings of Zn, O, N, and C within the β-SF/PAM gel; (g) tensile stress–strain curves of gel electrolytes with varying β-SF contents.

  通過微量乙醇誘導(dǎo)絲素蛋白由無規(guī)卷曲/α-螺旋向高度有序的β-折疊結(jié)構(gòu)轉(zhuǎn)變，構(gòu)建致密穩(wěn)定的氫鍵網(wǎng)絡(luò)，在鋅負極表面形成具有力學(xué)穩(wěn)定性與離子選擇性的仿生保護層。

圖2.β-SF調(diào)控Zn²⁺溶劑化結(jié)構(gòu)與遷移行為的機制分析

Figure 2. Mechanistic investigation of β-SF regulation on Zn²⁺ solvation structure and migration behavior. (a) Ionic conductivity of PAM, SF/PAM, and β-SF/PAM gel electrolytes; (b) Ionic mobility number of β-SF/PAM gel electrolytes; (c) Optimized models used in DFT calculations illustrating binding energies between Zn²⁺ and H₂O, PAM, and SF molecules; (d) Raman spectra of PAM, SF/PAM, and β-SF/PAM gel electrolytes; (e, f) Molecular dynamics (MD) simulation snapshots and representative Zn²⁺ solvation structures in β-SF/PAM gel electrolytes; (g、h) Radial distribution functions (RDFs) and coordination numbers for Zn²⁺–O (H₂O), Zn²⁺–O (SO₄^2?), and Zn²⁺–O (PAM) interactions; (i) Mean square displacement (MSD) curves of Zn²⁺ ions in PAM and β-SF/PAM gel electrolytes.

  實驗表明，β-SF/PAM水凝膠電解質(zhì)在鋅離子的遷移行為與界面穩(wěn)定性方面表現(xiàn)出顯著優(yōu)勢。該凝膠電解質(zhì)體系在常溫下展現(xiàn)出高達32.4 mS·cm^-1的離子電導(dǎo)率和0.80的Zn²⁺遷移數(shù)。多種表征與理論計算表明，該仿生電解質(zhì)構(gòu)建了穩(wěn)定高效的離子傳輸通道，從而賦予優(yōu)異的循環(huán)性能。

圖3.鋅負極的界面循環(huán)性能和可逆性

Fig. 3. Interfacial cycling performance and reversibility of zinc anode electrodes. symmetric cells with PAM, SF/PAM, and β-SF/PAM gel electrolytes at (a) rate capability at different current densities from 0.1 to 6 mA cm^?2 with a fixed capacity of 1 mAh cm^?2 as well as long cycling performance at (b) 1 mA cm ^?2/1 mAh cm^?2, (c) long cycle performance at 2 mA cm^?2/1 mAh cm^?2. (d) Galvanic and stripping Coulombic efficiency (CE) of Zn//PAM//Cu, Zn//SF/PAM//Cu and Zn//β-SF/PAM//Cu half-cells at 1 mAh cm^?2 and (e) the corresponding charging/discharging curves of Zn//β-SF/PAM//Cu half-cells. (f) Corresponding CA curve of Zn//Zn cell at constant overpotential of ?150 mV (g) Comparison between β-SF/PAM and other hydrogel electrolytes at different parameters.

  測試表明，β-SF/PAM凝膠電解質(zhì)顯著提升了鋅負極的循環(huán)穩(wěn)定性與可逆性。

圖4.電極/電解質(zhì)界面Zn沉積行為

Figure 4. electrode/electrolyte interface Zn deposition behavior. PAM, SF/PAM and β-SF/PAM gel electrolytes (a) Linear sweep voltammetry (LSV) curves measured at 5.0 mV s^?1; (b) Tafel curves; (c) Arrhenius curves; (d) Nucleation overpotentials; (e, f) Use of PAM and β-SF/PAM in Zn‖ Zn symmetric cells gel electrolytes after 50h cycling at 1mA cm^?2; (g) Atomic force microscopy (AFM) 3D topography of Zn anode post 50 h cycling (1 mA cm^?2/1 mAh cm^?2) in PAM electrolyte; (h) Corresponding 2D plan view; (i) Finite element method (FEM) simulation depicting zinc ion concentration distribution in PAM electrolyte; (j) AFM 3D topography of Zn anode after 50 h cycling with β-SF/PAM electrolyte under identical conditions; (k) Corresponding 2D plan view; (l) FEM simulation showing zinc ion concentration distribution in β-SF/PAM electrolyte.

  研究表明，β-折疊絲素蛋白構(gòu)建的仿生界面層在抑制水系副反應(yīng)與鋅枝晶形成方面發(fā)揮關(guān)鍵作用。該體系顯著提升析氫起始電位與腐蝕電位，有效緩解水分解和自腐蝕行為。

圖5.β-SF調(diào)控鋅負極界面機制

Fig. 5. β-SF modulates the interfacial mechanism of Zn anode. (a) XRD patterns of Zn anode electrodes of PAM, SF/PAM and β-SF/PAM gel electrolytes of Zn//Zn cells after 50 h cycling at 1 mA cm^?2; (b) adsorption models of β-SF molecules on the surface of Zn (100), (101), and (002) and corresponding adsorption energies; XPS spectra of PAM @ Zn, SF/PAM @ Zn and β-SF/PAM @Zn anode XPS spectra of (c) Zn 2p; (d) N1s; (e) C1s; (f) S 2p; (g) Mechanism of action diagrams of PAM and β-SF/PAM electrolytes

  進一步研究發(fā)現(xiàn)，β-折疊絲素蛋白在鋅負極表面構(gòu)建致密穩(wěn)定的仿生界面層，有效誘導(dǎo)Zn²⁺沿低能(002)晶面擇優(yōu)沉積，顯著抑制枝晶生成。

圖6.全電池的性能及其應(yīng)用

Fig 6. Demonstration of full cell performance and applications. (a) CV curves of Zn‖β-SF/PAM‖MnO₂ full cells at various scan rates (1, 2, 3, 4, and 5 mV s^?1) in the range of 0 to 1.8 V; (b, c) multiplicity performance and charge/discharge curves of Zn‖β-SF/PAM‖MnO₂ full cells at different current densities; (d) different electrolyte systems for the Cycling performance of Zn||MnO₂ full cells at 1 A g^?1 and (e) Charge-discharge curves of Zn‖β-SF/PAM‖MnO₂ full cells under specified cycles. (f) Schematic structure of the Zn‖β-SF/PAM‖MnO₂ fiber full cell; (g) Capacity retention of the Zn‖β-SF/PAM‖MnO₂ fiber cell under deformations such as twisting, winding, and knotting; (h) The fiber cell supplies power to the electromyography sensing (EMG) module, and it monitors the human body''''s vital features in real time and transmits the data wirelessly; (i) The flexible fiber battery fabric powers an ACEL flexible light-emitting module with emergency response capabilities; (j) the fiber battery charges a smartphone.

  在實際應(yīng)用評估中，構(gòu)建的Zn‖MnO₂全電池表現(xiàn)出優(yōu)異的倍率性能與循環(huán)穩(wěn)定性，1500次循環(huán)后容量保持率達93.8%。進一步構(gòu)建的鋅離子纖維電池在彎折、打結(jié)狀態(tài)下仍維持92%以上容量，具備優(yōu)異柔韌性與機械穩(wěn)定性。結(jié)合紡織工藝開發(fā)的集成電子織物系統(tǒng)實現(xiàn)了生命體征監(jiān)測、發(fā)光警示與能量供給，展現(xiàn)出在智能紡織與柔性儲能領(lǐng)域的廣闊應(yīng)用前景。

  總而言之，本研究基于生物基絲素蛋白的分子構(gòu)象調(diào)控策略，構(gòu)建了一種具有優(yōu)異界面穩(wěn)定性與離子傳輸性能的β-SF/PAM凝膠電解質(zhì)。該電解質(zhì)不僅顯著提升了Zn²⁺遷移效率，抑制枝晶生長與副反應(yīng)，還在剛?cè)峒婢叩碾娊赓|(zhì)結(jié)構(gòu)中實現(xiàn)了良好的電化學(xué)穩(wěn)定性與循環(huán)壽命。進一步應(yīng)用于柔性鋅離子纖維電池后，展現(xiàn)出優(yōu)異的柔韌性與能量輸出能力，成功驅(qū)動智能可穿戴系統(tǒng)穩(wěn)定運行。該工作不僅拓展了絲素蛋白在柔性能源材料中的高值利用路徑，也為綠色、高效、可紡織的一體化儲能系統(tǒng)構(gòu)建提供了全新思路與實踐基礎(chǔ)。

  在此，感謝浙江省自然科學(xué)基金項目（LY21E030023）和浙江理工大學(xué)嵊州創(chuàng)新研究院基金項目（SYY2024C000008）的支持！

  通訊作者簡介：胡毅，男，博士，教授，博士生導(dǎo)師。浙江理工大學(xué)紡織科學(xué)與工程學(xué)院（國際絲綢學(xué)院）副院長，主要從事非水介質(zhì)染整新技術(shù)和柔性電子智能紡織品研究。以第一作者或通訊作者在Advanced Functional Materials, Nano Letters, Energy Storage Materials, Nano Energy, Chemical Engineering Journal等刊物上發(fā)表SCI論文70余篇，授權(quán)和轉(zhuǎn)化國家發(fā)明專利30余項。獲得國家級教學(xué)成果二等獎和浙江省教學(xué)成果特等獎各1項；主持獲得中國紡織工業(yè)聯(lián)合會教學(xué)成果一、二、三等獎，浙江省自然科學(xué)獎三等獎和中國商業(yè)聯(lián)合會科技進步獎二等獎各1項。

  原文鏈接：https://doi.org/10.1016/j.ensm.2025.104464