孔隙率正越来越多地被用于设计无溶剂固态和准固态聚合物纳米复合电解质,以应用于锂、钠和锌基电池,但其传输作用往往被残留液体、聚合物塑化、界面化学以及热诱导结构变化所掩盖。本综述按物理状态、孔隙位置和主导导电相对文献进行分类,随后探讨了限域效应如何改变盐的物种分布、有效载流子尺寸、离子-壁配位、连通性、占据率、捕获以及界面通量。物理状态审计将固态本征传输与液体辅助传导区分开来,而对比数据表明,孔径或总孔隙率本身并不能预测电导率或阳离子选择性。在不同化学体系中,有效的传输取决于连通的离子可及路径、可逆的离子特异性相互作用,以及在热和电化学运行过程中传导结构的保持。由此产生的热-孔隙率-传输框架将几何渗透与动态离子耦合区分开来,并通过物种特异性停留时间来处理捕获现象。在选定的文献系列中,它被证明是一种诊断性模型而非通用本构模型。该综述以可证伪的测试、最低报告要求以及多孔聚合物纳米复合电解质的可持续性考量作为总结。用无溶剂固体或准固体膜取代易燃液体电解质可以提高安全性,但也会在体相传输、界面接触、极化和机械稳定性方面引入局限性。致密无机导体具有高本征电导率但顺应性有限,而聚合物则能提供柔性接触,但代价是室温迁移率较低或离子缔合更强;准固体凝胶通过保留的移动相跨越了这些状态 [1]. 对钠基和锌基体系的关注也反映了资源和加工方面的考量。钠在固定式和成本敏感型储能领域具有吸引力,而锌则提供了水系或水合电解质选项以及固有的不可燃性。这些优势仍取决于能量密度、电解质背包、腐蚀、燃料费产生、金属利用率、循环寿命和可扩展加工,因此电解质架构必须针对实际的钠+或锌2+传输状态进行设计,而非直接沿用锂体系 [2]. 孔隙率可以改善渗透、电极接触、传输路径连续性和应力适应性,但“多孔电解质”描述的是物理上不同的系统:多孔聚合物、含有多孔填料的致密聚合物、自导电框架、多孔陶瓷、渗透支架和无序对照 [3,4,5,6,7,8,9,10]。因此,相似的名义孔隙率可能对应不同的导电相和机制。 被传输的物种同样不一定是裸露的Li+、Na+或Zn2+离子。根据盐类、溶剂、聚合物配位、浓度、温度和水活度,传输可能涉及溶剂化或聚合物配位的阳离子、离子对或更大的缔合物种。因此,必须将孔径与有效的传输状态及其配位重排要求进行比较,而不是与通用的离子半径[11,12,13,14,15,16,17,18,19,20,21,22]. 因此,限域效应是非单调且具有离子特异性的。适度的限域可以改变溶剂化作用、促进解离、固定反离子、调节水活性,或创造选择性的表面辅助通道;而过度限域则可能增加重配位能垒、导致捕获、拥挤或聚集。因此,设计目标是在载体数量、迁移率、选择性、连通性和机械连续性之间取得平衡,而非追求最大表面积或最小孔径[23,24,25,26,27,28,29,30,31,32]. 物理状态标签也需要谨慎对待。被描述为“固态”的材料可能仍含有有机溶剂、离子液体或水,并主要通过这些流动相导电,这在锌凝胶中尤为明显,在锂和钠体系中也是如此。相反,低导电性的无溶剂材料可能为固有固态传输提供更清晰的证据。因此,必须独立于原始文献中使用的术语,对物理状态、流动相比例和载流相进行审核[33,34,35,36,37,38,39,40,41]. 因此,孔隙率应被视为内部离子环境的调节因子,而非电导率的独立预测指标。孔壁化学性质影响物种分布和界面电荷,而拓扑结构则控制可及性、收缩、曲折度、取向和宏观连续性;高BET比表面积可能与较差的垂直面传输并存[42,43,44]. 本综述据此根据孔隙位置和主导导电相对以多孔聚合物为中心的电解质进行分类,如图所示图1,随后探讨了涉及物种分布、阳离子/反离子运动、捕获、占据、连通性、界面、非线性传输和热量保持的循环机制,涵盖锂、钠和锌基体系[3,4,5,6,7,8,9,10,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44]. 第2节和第3节定义审计和分类法;第4节, 第五节, 第六节, 第七节和第八节综合材料和应用相关的证据;第九节探讨了交叉机制;第10节介绍了作者的框架、验证标准、局限性、可持续性以及研究重点;第11节总结了本综述。 图1.固态和准固态电解质中孔隙位置与纳米填料功能的聚合物中心分类:() 相互连接的多孔PVDF基体和充满电解质的传输通道 [) 含有MOF的三维聚合物纤维网络,提供连续的界面离子传输通道 [45]; () BN增强的聚合物电解质,结合了离子传输与增强的热学和力学功能 []; 并且 (46]; () Janus MOF/介孔二氧化硅膜,可实现不对称离子调节和定向传输[]。原始科学图表在未改变底层图像内容或数据的情况下被复制,仅为对比展示而组合。参考文献[47] 是注明出处的开放获取资源。保留了源文件自带的校准比例尺和测量标签,因为它们提供了定量的形态学信息。OpenAI ChatGPT(OpenAI,美国加利福尼亚州旧金山)仅用于辅助本作者概念示意图的视觉布局和呈现;其科学内容、因果关系、解释和结论均由作者自行开发和验证。D) Janus MOF/mesoporous-silica membranes enabling asymmetric ion regulation and directional transport [48]. The original scientific panels are reproduced without alteration to the underlying image content or data and assembled solely for comparative presentation. Refs. [45,46,47,48] are open-access sources reused with attribution. Source-native calibrated scale bars and measurement labels are retained because they provide quantitative morphological information.OpenAI ChatGPT (OpenAI, San Francisco, CA, USA) was used only to assist with the visual arrangement and presentation of this authors’ conceptual schematic; the scientific content, causal relationships, interpretation, and conclusions were developed and verified by the authors.
2. Review Scope and Comparative Assessment Criteria
This review evaluates porous solvent-free solid and quasi-solid electrolytes within a polymer-centered framework defined by physical state, pore location, dominant conducting phase, and transport mechanism. Systems are further compared by polymer and salt–solvent chemistry, nanofiller function, pore architecture, mobile-phase inventory, ion chemistry, and operating temperature. The classification in Table 1 separates intrinsically porous polymers, porous-filler nanocomposites, framework-containing composites, infiltrated or ceramic-reinforced architectures, comparative glassy controls, and hierarchical or Janus structures so that materials with similar nominal porosity are not treated as mechanistically equivalent [3,4,5,6,7,8,9,10,23,24,25,26,27,28,29,30,42,43]. Fully inorganic porous ceramics and glasses are included only as comparative controls when they clarify the effects of pore location, phase continuity, or infiltration; they are not treated as co-equal application classes with polymer and polymer-nanocomposite electrolytes [3,4,5,6,7,8,9,10,42,43,44,49,50,51,52,53,54,55,56,57,58,59,60,61,62,63,64,65,66,67,68,69,70,71,72,73,74,75,76,77,78,79]. Physical-state terminology is used operationally. A solvent-free solid electrolyte has a continuous solid ion-conducting phase without an intentionally retained liquid, water, or ionic-liquid phase that materially carries current. A quasi-solid electrolyte (QSE) is self-standing but contains a retained mobile phase that contributes substantially to conduction; GPEs, hydrogels, and ionogels are treated as QSE subclasses according to that mobile phase. ‘Solid-like’ and ‘semi-solid’ are not used as classification terms. Source systems are reclassified by measured mobile-phase inventory and dominant conducting phase, and are reported as unresolved when those data are unavailable. Mechanical self-support alone is not evidence of intrinsic solid-state transport [33,34,35,36,37,38,39,40,41]. This is a critical evidence synthesis rather than a formal meta-analysis. Priority is given to primary studies that resolve pore accessibility, conducting-phase identity, polymer-nanofiller function, ionic speciation or relaxation, directional transport, thermal retention, or electrochemical operation. Numerical comparison is restricted to systems with sufficiently defined physical state, composition, temperature, thickness, and test configuration; missing values are not inferred [23,24,25,26,27,28,29,30,31,32,42,43,44,80,81]. Evidence is evaluated at three coupled levels: structure (accessible porosity, connectivity, wall chemistry, filler dispersion, crystallinity, and post-heating dimensions), transport/electrochemistry (conductivity, transference, speciation, relaxation, interfacial resistance, and cycling), and thermal/mechanical response (transitions, volatile loss, shrinkage, modulus, and post-heating performance) [11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,42,43,44]. These quantities are interpreted together because pore structure, polymer mobility, mobile-phase content, and electrode contact evolve jointly. The physical-state audit distinguishes solvent-free solids from QSEs and from porous supports whose apparent conductivity is dominated by infiltrated liquid [11,12,14,17,33,34,35,36,37,38,39,40,41,42,43]. Molecular free volume is not equated with experimentally accessible porosity, and total porosity is not assumed to represent through-plane connectivity [3,5,7,10,25,30,42,43,44]. 热稳定性在功能上定义为:相关的孔隙拓扑结构、传导路径、机械连续性、流动相背包以及电极接触必须在预期的操作窗口内保持稳定。仅靠高分解温度是不够的,因为软化、孔隙塌陷、挥发物损失、填料重排或接触失效可能会更早地破坏传输过程 [24,82,83,84,85]. 机理主张的权重取决于证据强度。相比于仅从电化学性能推断出的机理,直接的结构、光谱、弛豫、迁移、界面和加热后测量更受青睐,而控制成分、厚度、热历史和流动相比例,仅改变一个结构参数的匹配比较则被赋予最高权重 [23,31,33,39,42,80,81]. 这些标准共同定义了因果图谱,图2:组分和纳米填料化学决定了孔隙拓扑结构和界面相互作用;这些因素调节聚合物迁移率、流动相保留、物种分布、停留时间以及连通传输;随后,热降解和电化学降解可通过孔隙坍塌、重新分布、相间生长或接触丧失产生反馈。几何连通性是宏观电流的必要条件,但与动态耦合的离子运动截然不同,后者需要额外的瞬态、光谱或弛豫证据[23,24,25,26,27,28,29,30,31,32,42,80,81,82,83,84,85,86,87,88,89,90,91,92,93,94,95,96,97,98,99,100,101,102,103,104,105,106]. Figure 2. Causal design map connecting material composition to electrolyte architecture, thermochemical response, ion-transport mechanisms, and electrochemical performance. (A) Polymer chemistry, salt–solvent formulation, and functional nanofiller identity define the initial material inputs. (B) These inputs regulate pore-size distribution, connectivity, and pore-wall chemistry. (C) Thermal exposure modifies polymer segmental mobility, pore retention, and mobile-phase stability. (D) The resulting confined environment controls salt speciation, ion–surface residence, and possible dynamically coupled transport. (E) Their combined effects determine ionic conductivity, target-cation transference, interfacial resistance, and cycling stability. The dashed pathway indicates degradation feedback. This conceptual map was prepared by the authors from the cited literature; it does not represent experimental data. OpenAI ChatGPT (OpenAI, San Francisco, CA, USA) was used only to assist with the visual arrangement and presentation of this authors’ conceptual schematic; the scientific content, causal relationships, interpretation, and conclusions were developed and verified by the authors. 图1, 图2和图3扮演不同的角色。图1重新整合作者选定的、引用的已发表图表,以对具有代表性的实验报告架构进行分类;基础数据保持不变。图2和图3是作者准备的概念性示意图,用于整理因果关系和主要通路类别。它们共同总结而非取代所引用的原始证据[23,24,25,26,27,28,29,30,31,32,42,43,44,45,46,47,48,64,68,69,70,71,72,73,74,75,76,77,78,79,82,107,108,109,110,111,112,113,114,115,116,117,118,119,120,121,122,123,124,125,126,127,128,129,130,131,132,133,134,135,136,137,138,139,140,141,142,143,144,145,146,147,148,149,150,151,152,153,154,155,156,157,158,159,160,161,162,163,164,165,166,167,168]. Figure 3. Dominant ion-transport pathways in porous polymer nanocomposite electrolytes. (A) Polymer segmental transport. (B) Polymer–filler interfacial transport. (C) Internal filler-channel transport through ion-accessible and macroscopically connected channels. (D) Bicontinuous transport through parallel continuous phases. Multiple mechanisms may coexist; the dominant contribution depends on phase continuity, ion accessibility, interfacial exchange, and mobile-phase inventory. This mechanistic schematic was prepared by the authors from the evidence discussed in Section 3.6. AI辅助工具在有限的辅助角色中被使用,以帮助整理和整合作者选择的、引用的视觉面板/元素,从而更清晰地呈现科学关系,并用于语言润色,包括语法和可读性。它们未被用于生成或更改实验数据、选择或伪造科学证据、进行文献分析、推导传输机制或制定科学结论。所有科学解释、图表来源选择、引用和结论均由作者进行了批判性审查和验证。 表1。多孔无溶剂固态和准固态电解质架构的聚合物中心分类,根据孔隙位置、主导导电相、机制归属所需的最低证据、常见的解释错误以及在锂、钠和锌基电化学系统中的代表性应用。
定量子集在表3和表4阐明了为什么框架电解质不应仅按MOF、COF或笼状结构标签进行分类。一种多孔有机笼QSE保留了12 wt%的碳酸丙烯酯,而据报道,一种固定阴离子的COF单离子导体在未添加有机溶剂的情况下仍能工作。尽管被描述为固态术语,但一种In-MOF/聚合物电解质仍含有14.3 wt%的残留二甲基甲酰胺。这些材料针对不同的传输目标:液体辅助系统可达到更高的总电导率,而干燥的固定阴离子通道则可能提供更纯净的单离子选择性[158,159,160,161,162,163]. 在整个类别中,反复出现的机理变量包括导电相的身份、电解质形成后内部孔隙的可达性、骨架或界面路径的连续性,以及孔壁的特定物种功能。因此,当内部空腔不可达、未被目标相填充或与宏观传输断开时,填料的表面积就变得次要了[164,165,166,167,168,202]. 表3。代表性框架和混合多孔电解质:从原始全文中提取的物理状态和传输指标。在无法获取验证值的情况下保留“未报告”。 表4。代表性框架和混合多孔电解质:孔隙描述符、电化学测试和解释的孔隙作用。 仅有四种系统表3和表4同时报告了单一特征孔径尺寸、近室温离子电导率以及锂+迁移数:CC3笼状电解质、F-COF、Li-COF-2@P75和Polymer@TpPa-COOLi。图4比较了这一有限的匹配子集。电导率或tLi没有表现出单调的排序+与孔径尺寸的关系。1.2纳米的无溶剂Li-COF-2@P75表现出最高的tLi+(0.95),但电导率低于1.8纳米的PC辅助F-COF,而Polymer@TpPa-COOLi在相当的纳米级孔径下表现出显著较低的电导率。因此,在该子集中,仅凭孔径大小无法决定性能;物理状态、壁面化学性质、固定电荷、通道连续性和离子物种仍是共同起作用的变量[147,154,156,201]. 图4。提取自有限匹配比较表3和表4用于报告单一特征孔径尺寸、近室温离子电导率和锂的系统+迁移数。图中绘制的系统为CC3多孔有机笼电解质[201],Li-COF-2@P75[147],Polymer@TpPa-COOLi[ %%],以及F-COF供体-受体电解质[ %%]。标签报告了tLi156由于子集规模较小(n = 4)且跨越了不同的物理状态和界面化学性质,因此未进行回归拟合。该对比测试旨在检验孔径是否是决定性能的唯一因素;它并非作为元分析呈现。作者的图表汇编自引用的文献数据。154]. Labels report tLi+. No regression is fitted because the subset is small (n = 4) and spans different physical states and interfacial chemistries. The comparison tests whether pore size alone organizes performance; it is not presented as a meta-analysis. Authors’ plot compiled from the cited literature data. 根据现有汇总数据,尚无法针对保留液体比例进行更强的跨系统测试。仅有少数条目报告了移动相含量,且报告的量化指标并不等同(例如,残留溶剂、电解质吸收量或配方比例)。同样,许多孔径尺寸是在原始基质上测量的,而非在负载盐的运行电解质上。因此,我们没有拟合通用的电导率与液体比例或电导率与孔径尺寸的关系。汇总数据支持一个定性结论——即液体辅助系统可以提供高总电导率,而干燥的固定阴离子通道可以提供高阳离子选择性——但它们并不支持在不同化学成分和物理状态下存在通用的孔径或保留液体最佳值[147,154,156,158,159,160,161,162,163,164,165,166,167,168,201].
石榴石型锂7La3Zr2(LLZO)及相关氧化锂因其高锂12选择性、名义稳定性及刚性而备受关注。钠系统使用不同的陶瓷材料家族,包括钠超离子导体(NASICON)型材料、β-氧化铝、硫化物和卤化物导体,它们的传输路径和界面会产生不同的孔隙约束;全无机锌+导体仍不够成熟,大多数锌体系依赖于水合相或聚合物限制相。在这些化学体系中,刻意制造的孔隙率可以降低有效厚度、实现渗透并提高保形性,但同时会移除承载和导电的横截面[2+ conductors remain less developed, and most zinc systems rely on hydrated or polymer-confined phases. Across these chemistries, deliberate porosity can reduce effective thickness, enable infiltration, and improve conformity, but simultaneously removes load-bearing and conducting cross-section [66,203,204,205,206,207]. 当孔隙简单地取代导电陶瓷时,相对于完全致密相,膜的固有电导率会降低。因此,只有当厚度减小、接触改善、渗透性增强或定向排列能充分补偿截面积损失时,多孔陶瓷才能提升细胞层面的性能。相对密度、晶粒尺寸、晶界化学、孔隙取向和机械强度因此成为相互关联的描述指标。否则,测得的低电阻可能反映的是液体或聚合物的渗透,而非更快的陶瓷传导[68,69,70,71,72,73].
一个可信的高温或宽温性能声明需要不止一条电导率曲线。电解质应在反复加热和冷却后进行评估,并比较暴露前后的电导率、厚度、质量、模量、界面电阻和电化学稳定性。电池级测试应区分暂时的温度激活与永久性的性能提升或退化。如图5所示,最有用的指标是在定义的温度、时间、压力和荷电状态协议下保持的功能性能[203,204,205,206,207,208,209,210,211,212,213,214,215,216,217,218,219,220,229]. 图5。多孔聚合物纳米复合电解质的功能热稳健性。()蜂窝状多孔PVDF-HFP基体在加热过程中保持其外部尺寸,而饱和电解质的薄膜则损失了大量移动相,这表明仅靠尺寸稳定性不足以保证导电相的保留[)三维MOF含聚合物纤维网络限制了聚合物软化,提高了机械强度,并维持了温度依赖的离子传输[229]. () LATP纳米颗粒的读档会改变PEO的形貌、电导率、分解行为和尺寸保持能力;适度读档是有益的,而过度读档则会促进团聚[) 作者的合成将聚合物软化、孔隙塌陷、流动相流失、填料团聚和界面空洞与材料级控制策略联系起来。图表(46]. ()原样复制了参考文献[]中的原始科学图像,未对底层图像内容或数据进行任何修改;仅添加了图表组合和解释性解读。参考文献[228]. (] 是一项开放获取资源,经注明出处后重复使用;参考文献 [] 根据 CC BY-NC-ND 4.0 协议发布;参考文献 [] 仍受原出版商版权保护。原始版权和许可条款仍归各自来源所有。OpenAI ChatGPT(OpenAI,美国加利福尼亚州旧金山)仅用于辅助作者选择的引用图表和图形元素的视觉排版与整合;未用于生成或修改基础实验数据或科学图像。–C) reproduce the original scientific images from Refs. [46,228,229] without alteration to the underlying image content or data; only panel assembly and explanatory interpretation were added. Ref. [46] is an open-access source reused with attribution; Ref. [229] is published under CC BY-NC-ND 4.0; and Ref. [228] remains under the original publisher’s copyright. The original copyright and license terms remain with the respective sources. OpenAI ChatGPT (OpenAI, San Francisco, CA, USA) was used only to assist with the visual arrangement and integration of author-selected, cited panels and graphical elements; it was not used to generate or alter the underlying experimental data or scientific images. 图5将主要的受热诱导失效模式与其相应的材料级控制策略相结合。聚合物软化可通过交联或热稳定基质来缓解;孔隙塌陷可通过刚性连接支架来缓解;流动相流失可通过低挥发性或强约束导电相来缓解;填料团聚可通过受控读档和表面功能化来缓解;界面空洞化可通过柔性或梯度层来缓解。预期的结果不仅是延迟分解,而且是在热应力和机械应力下保持连接的、离子选择性的通道和电化学功能[46,47,203,204,205,206,207,208,209,210,211,212,213,214,215,216,217,218,219,220,228,229].
8. 电极-电解质界面与锂/钠/锌应用
在电池界面处,体相离子传输与电荷转移、接触力学、电子泄漏、局部应力以及金属沉积相耦合。如果电池结构产生非均匀离子供应、惰性金属存储、寄生反应或机械薄弱的穿透路径,那么较低的体相电阻也将毫无益处[84,85,87,94,95,101,102,103,104,105,106,252,253,254,255,256,257,258,259,260,261,262]. 最终的失效形貌取决于化学成分。锂和钠固态系统可能会出现空洞、裂纹、剥落和亚表面金属渗透,而水系或准固态锌系统则更多表现出粗糙沉积、腐蚀、钝化和与水相关的副反应。图6对比了这些结果,并且表6总结了特定应用的设计和测试要求[102,105,106,252]. 表6.针对特定应用的孔隙电解质结构、设计目标、关键测试条件,以及在锂、钠和锌基电池中必须排除的主要失效模式。 图6。将界面接触失效和离子通量局部化与金属沉积失效及稳定化联系起来的跨化学证据。()实验验证的局部锂沉积、拉伸应力积累、电解质开裂和锂丝生长相场分析[)磁共振成像、X射线断层扫描、扫描电子显微镜和元素映射显示钠/β″-氧化铝/钠电池中与极化相关的空隙形成、界面剥落和裂纹辅助钠渗透[85]. () 锌在液体和透明质酸凝胶电解质中的沉积,显示出当溶剂化和界面离子分布得到调节时,会向更紧凑的形貌转变[,]。下方的示意图是作者的跨化学合成。原始科学图表在未改变底层图像内容或数据的情况下被复制,仅为进行对比展示而组合。参考文献[] 采用 CC BY 4.0 协议发布,并在注明出处的情况下可供重复使用。OpenAI ChatGPT(OpenAI,美国加利福尼亚州旧金山)仅用于辅助作者所选引用图表和图形元素的视觉排版与整合;未用于生成或修改基础实验数据或科学图像。102]. (D–F) Zn deposition in liquid and hyaluronic-acid gel electrolytes, showing a transition toward a more compact morphology when solvation and interfacial ion distribution are regulated [252]. The lower scheme is the authors’ cross-chemistry synthesis. The original scientific panels are reproduced without alteration to the underlying image content or data and assembled solely for comparative presentation. Refs. [85,102,252] are available under CC BY 4.0 and are reused with attribution. OpenAI ChatGPT (OpenAI, San Francisco, CA, USA) was used only to assist with the visual arrangement and integration of author-selected, cited panels and graphical elements; it was not used to generate or alter the underlying experimental data or scientific images.
锌金属体系的独特之处在于锌2+具有二价性、强溶剂化特性,且通常通过保留的水相进行传输。因此,孔隙几何结构与水活度、阴离子分布及配位化学共同发挥作用。较低的水活度可抑制析氢反应和腐蚀,而过强的锌2+结合作用会增加脱溶剂化或配体交换的能垒,并减少移动载流子的数量。有效的孔壁化学应能富集并重新分布锌2+,同时避免将选择性配位转化为深度捕获[230,231,232,233,234,235,236,237]. 动态桥接配体策略提供了一个分子范例。据报道,三(2-吡啶甲基)胺可可逆地配位Zn2+同时吸引OTf−向界面移动,从而降低界面水活性并促进阴离子衍生的富无机相[274]。对于多孔聚合物和水凝胶,相关的设计原则是动态交换:配位应足够持久以重组溶剂化和阴离子化学,但又足够不稳定以保持Zn2+的迁移性。 一致地,%%中的透明质酸凝胶会改变锌的%%溶剂化和离子分布,并产生比液体电解质更致密的沉积物[%%]。这支持了受控的表面沉积,而非像锂或钠中观察到的裂纹辅助内部丝状物那样具有普遍的等效性;腐蚀、析氢、钝化和配体交换动力学仍然是独立的变量。图6C modifies Zn2+ solvation and ion distribution and yields a more compact deposit than the liquid electrolyte [252]. This supports regulated surface deposition, not a universal equivalence with the crack-assisted internal filaments observed for Li or Na; corrosion, hydrogen evolution, passivation, and ligand-exchange kinetics remain separate variables. 物理状态也必须明确。自支撑水凝胶主要通过保留的水分导电,因此多孔聚合物骨架无法建立固态锌的固有传输通道。2+水/流动相含量及其在循环过程中的演变应与电导率和界面数据一并提供[230,231,232,233,234,235,236,237,238,239,240,241,274]. 当形貌与库仑效率、气体析出或腐蚀控制、锌利用率、面积容量、含水量以及电解质与容量比相结合时,界面稳定性的证据最为充分;仅凭循环后平滑的表面无法排除亚表面腐蚀、钝化、失活锌或水相重分布[238,239,240,241,252].