Xilian Xu, Ye Chen, Dongshu Liu, Dong Zheng, Xiaojing Dai, Wenhui Shi, and Xiehong Cao · The Chemical Record · 2022
Summarise MOF-based materials for aqueous zinc-ion batteries, with emphasis on Zn storage mechanisms, MOF cathodes and derivatives, Zn deposition regulation, and future design challenges.
The review’s argument is preserved as a navigable set of section summaries.
Classifies pristine MOF cathodes into PB/PBA, Mn-MOF, V-MOF and conductive MOF examples, then distinguishes intercalation/extraction from phase-transition mechanisms.
Relevance: Core · 4 · 2.1.1 · Table 1
Synthesises advantages of MOFs in ZIBs and states future needs: conductivity, stability in weakly acidic aqueous electrolytes and higher energy density.
Relevance: Core · 17 · 3. Conclusion and Prospects
Frames aqueous ZIBs against LIBs and other aqueous batteries, introduces Zn anode benefits and dendrite/HER/corrosion problems, and motivates MOFs through porosity, active sites and tunable composition.
Relevance: Core · 3 · 1. Introduction
Describes MOFs as precursors/templates for oxides, carbons and composites that improve conductivity, stability, active-site accessibility and cycling performance.
Relevance: Supporting · 9 · 2.1.2
Extends the review beyond cathodes to Zn plating/stripping control, including MOF artificial SEIs, zincophilic hosts, Janus separators and MOF solid-state electrolytes.
Relevance: Core · 12 · 2.2
Provides the review's explicit mechanistic taxonomy for MOF cathodes: Zn2+ intercalation/extraction and phase transition, supported by PB, V-MOF-48, VHCF, Mn(BTC) and CuHCF examples.
Relevance: Core · 8 · 2.1.1.2
Classification systems are attributed to this review and are not treated as a global material registry.
For Zn anodes, the review separates interfacial barrier/flux-control layers from substrates that alter Zn nucleation and plating.
Categories: MOF-based solid electrolyte interface · MOF-based zincophilic host
13 · 2.2.1
The cathode discussion is grouped by framework chemistry and whether the MOF remains pristine or is converted to derived oxides/carbons/composites.
Categories: Prussian blue and analogues · Mn-based MOFs · V-based MOFs · conductive MOFs · MOF-derived materials
2 · Abstract
The review organises MOF-based materials by where they function in the ZIB cell, a useful scaffold for distinguishing electrode-active materials from ion-flux regulators.
Categories: cathode · Zn anode · separator · electrolyte
3 · 1. Introduction · Figure 1
The review distinguishes direct conversion of MOFs into active oxide/carbon cathodes from their use as protective or conductive scaffolds around traditional active materials.
Categories: precursors/templates for active compounds · protective layers · conductive substances
10 · 2.1.2
The review's central mechanistic distinction separates reversible ion insertion into open frameworks from structural phase transformations during cycling.
Categories: Zn2+ intercalation/extraction · phase transition
8 · 2.1.1.2
Review-defined families retain their representative materials and conduction descriptions.
MOFs with intrinsic or engineered electronic conductivity intended to overcome poor electron transport in pristine frameworks.
Conduction: High electrical conductivity lowers interfacial resistance and supports rate performance without relying solely on conductive additives.
Representative materials: Cu3(HHTP)2 · V-MOF@CNTF
Nodes / linkers: Cu · V · HHTP · conjugated redox-active linkers
8 · 2.1.1.1
Mn-containing MOF cathode materials leveraging porous frameworks and manganese redox/oxide conversion chemistry.
Conduction: Energy storage may involve transformation to MnO2/Zn(BTC), while coordinatively unsaturated Mn sites improve ion transfer kinetics.
Representative materials: Mn(BTC) · Mn-H3BTC-MOF-4
Nodes / linkers: Mn · BTC · H3BTC
6 · 2.1.1.1 · Figure 3
MOF coatings or hosts used to control Zn2+ flux, suppress water contact, alter solvation, and guide Zn nucleation/plating.
Conduction: Controls ion transport and Zn nucleation rather than serving primarily as a bulk cathode conductor.
Representative materials: Cu3(BTC)2 MOF layer · ZIF-7 coated Zn · ZIF-8-500 · Zn@ZIF
Nodes / linkers: Cu · Zn · BTC · imidazolate · benzimidazolate-like ZIF channels
13 · 2.2.1
Materials produced by converting MOFs into active metal oxides, porous carbons or composites while retaining useful morphology and channels.
Conduction: Derived conductive carbon networks and porous frameworks provide electron pathways, ion diffusion channels and volume-change accommodation.
Representative materials: a-V2O5@C · MnO2/CC · MnOx@N-C · Co-Mn3O4/CNA
Nodes / linkers: V · Mn · Co · Zn · MIL-88(V) · ZIF-67 · ZIF-8 · Co-MOF templates
11 · 2.1.2 · Table 2
MOF-containing separator/electrolyte materials that regulate Zn2+ flux and suppress side reactions during Zn plating/stripping.
Conduction: Zn2+ conduction is mediated by channels, solvated mobile Zn2+ and water-assisted transport; rGO supplies electronic conduction in Janus separators.
Representative materials: MOF/rGO Janus separator · ZnMOF-808 solid-state electrolyte · water@ZnMOF-808
Nodes / linkers: Zn · not fully specified in review · MOF-808-type linker · not fully specified in review
16 · 2.2.2
Open hexacyanoferrate-type frameworks used as intercalation hosts for multivalent ions, including Zn2+.
Conduction: Supports Zn2+ insertion/extraction through interstitial sites; capacity and lifespan remain concerns for many PBA examples.
Representative materials: FeHCF · CoFe(CN)6 · CuHCF · VHCF · K2MnFe(CN)6
Nodes / linkers: Fe · Co · Cu · V · Mn · cyanide/hexacyanoferrate
5 · 2.1.1.1
Vanadium-containing MOFs with pore structures and redox-active V sites for Zn-ion storage.
Conduction: V-MOF-48 is interpreted as Zn2+ intercalation/extraction with minimal V valence change; conductivity and channels drive rate performance.
Representative materials: V-MOF-48@CNTF · V-MOF (MIL-47) nanorod
Nodes / linkers: V · MIL-47-type vanadium framework · not fully specified in review
7 · 2.1.1.1 · Figure 4
Review-level synthesis principles remain separate from primary-study recipes.
Prepare conductive vanadium-based MOF arrays on carbon nanotube fibres to couple active MOF chemistry with conductive, hierarchical channelled supports.
Claimed effects: High conductivity, hierarchical channels and abundant active sites promote reversible Zn2+ insertion/extraction.
Controlling variables: reaction time · carbon nanotube fibre support · MOF nanowire-bundle morphology
Representative materials: V-MOF-48@CNTF
Caveat: The review's performance interpretation is secondary and depends on the original V-MOF@CNTF study.
7 · 2.1.1.1 · Figure 4
Use MOF coatings as electrolyte reservoirs or selective barriers that block direct Zn/water contact and regulate Zn2+ flux and solvation.
Claimed effects: Suppresses dendrite growth, water decomposition, byproducts and corrosion during Zn plating/stripping.
Controlling variables: MOF coating identity · pore size · electrolyte compatibility · Zn2+ solvation structure
Representative materials: Cu3(BTC)2 MOF layer · ZIF-7 coated Zn
Caveat: The review emphasises anode coatings as more developed than MOF separators/electrolytes.
13 · 2.2.1 · Figure 9
Use anionic MOF/rGO Janus separators or ZnMOF-808 solid electrolytes to guide Zn2+ flux, conduction and dendrite-free stripping/plating.
Claimed effects: Uniform Zn2+ flux, reduced Zn/Zn2+ redox barrier, water-assisted Zn2+ conduction and reduced concentration polarisation.
Controlling variables: anionic MOF layer · rGO conductive layer · water uptake · single-ion conductor design
Representative materials: MOF/rGO Janus separator · water@ZnMOF-808
Caveat: The review explicitly says research on MOF-based separators and electrolytes remains in infancy.
16 · 2.2.2 · Figure 11
Use MIL-88(V) as a precursor for carbonisation and in situ electrochemistry-induced conversion to form a-V2O5@C.
Claimed effects: Combines amorphous V2O5 and porous carbon to create active sites, multichannel ion diffusion and continuous electron pathways.
Controlling variables: MOF precursor identity · carbonisation · electrochemical conversion
Representative materials: a-V2O5@C
Caveat: Post-treatment complexity and cost are later identified as barriers for MOF-derived materials.
10 · 2.1.2 · Figure 7
Vary the Mn2+ to H3BTC ratio to form Mn-H3BTC-MOF-x with unsaturated Mn sites, exposing more active sites and reducing steric hindrance.
Claimed effects: More free active sites, more d orbitals, less steric hindrance, and faster ion transfer kinetics.
Controlling variables: Mn2+ to H3BTC molar ratio · hydrothermal reaction conditions · coordination saturation
Representative materials: Mn-H3BTC-MOF-4
Caveat: The review frames this as a promising example, not a general proof that all unsaturated Mn-MOFs will be stable in aqueous electrolyte.
6 · 2.1.1.1 · Figure 3
Use ZIF-67 as a sacrificial template to form MnO2 nanosheet-assembled hollow polyhedra anchored on carbon cloth.
Claimed effects: Unique 3D features increase accessible active sites and improve conductivity relative to commercial MnO2.
Controlling variables: ZIF-67 template morphology · redox reaction conditions · carbon cloth support
Representative materials: MnO2/CC
Caveat: The review does not provide a full recipe; quantitative claims should be traced to the original paper.
10 · 2.1.2 · Figure 7
Use ZIF-derived particles or ZIF-8 layers to provide Zn nucleation sites, ordered porous channels and adsorption sites for Zn2+.
Claimed effects: Improves Zn nucleation uniformity, reduces polarisation, suppresses dendrites and can raise Coulombic efficiency.
Controlling variables: annealing temperature · residual Zn distribution · N adsorption sites · porous channel order
Representative materials: ZIF-8-500 · Zn@ZIF
Caveat: ZIF-8-400 and ZIF-8-600/800 are described as less favourable, showing temperature-dependent trade-offs.
14 · 2.2.1 · Figure 10
These are the review authors’ synthesis, not newly measured results.
Conductive MOFs are presented as a route to reduce electron-transport limitations, lower interfacial resistance and improve rate performance.
Evidence basis: multi_reference
Caveat: The review calls for further conductive MOF development because many MOFs remain poorly conducting.
8 · 2.1.1.1
Hydrated Zn2+ is much larger than bare Zn2+, creating slow intercalation/extraction kinetics that open MOF frameworks can help alleviate.
Evidence basis: review_reasoning
Caveat: This is mechanistic context; individual host kinetics need primary validation.
8 · 2.1.1.2
For PB/FeFe(CN)6 and V-MOF-48 examples, Zn storage is interpreted as reversible Zn2+ insertion/extraction rather than wholesale redox dissolution.
Evidence basis: multi_reference
Caveat: The review relies on ex situ XRD/FTIR/XPS from the cited studies.
8 · 2.1.1.2 · Figure 5
Coordination-unsaturated Mn sites in Mn-H3BTC-MOF-4 are interpreted as increasing active sites and d-orbital availability while decreasing steric hindrance, improving kinetics.
Evidence basis: single_reference
Caveat: This is a review interpretation of one structural-engineering example.
6 · 2.1.1.1
MOF anode coatings can regulate Zn2+ diffusion, nucleation and dendrite growth via ion-transportable pores and adjustable physicochemical properties.
Evidence basis: multi_reference
Caveat: The most mature evidence is for modified Zn anodes, not separators or electrolytes.
12 · 2.2
MOF-derived cathodes can improve capacity, rate capability and lifespan by combining porous frameworks, conductive carbon and active cathode phases, but post-treatment complexity, yield and cost are barriers.
Evidence basis: multi_reference
Caveat: The review treats these values as literature examples rather than direct comparative experiments.
11 · 2.1.2
A Cu3(BTC)2 MOF layer is interpreted as creating an interfacial electrolyte environment that blocks water contact and forms a Zn2+-conductive self-repairing SEI.
Evidence basis: single_reference
Caveat: Specific to the Zn(TFSI)2-TFEP phase-separation design.
13 · 2.2.1 · Figure 9
The review attributes MOF promise in ZIBs to redox-active sites, porosity, large surface area and accessible electrode-electrolyte interfaces.
Evidence basis: review_reasoning
Caveat: These advantages do not remove conductivity and aqueous stability limitations.
3 · 1. Introduction
The review's outlook prioritises enhancing MOF conductivity, improving structural stability in weakly acidic aqueous electrolyte, and increasing energy density.
Evidence basis: review_reasoning
Caveat: This is the review authors' synthesis of future needs.
17 · 3. Conclusion and Prospects
PB/PBA cathodes offer wide ion channels and high operating voltage, but practical ZIB use is hindered by low capacity and limited lifespan.
Evidence basis: multi_reference
Caveat: Some strategies improve stability, but the review still characterises capacity below about 80-90 mAh g-1 as inadequate.
5 · 2.1.1.1
Several MOF cathodes undergo phase transitions during cycling, including VHCF cubic-to-rhombohedral conversion, Mn(BTC) transformation, and CuHCF/ZnHCF two-phase behaviour.
Evidence basis: multi_reference
Caveat: Phase transition behaviour is material- and cycling-condition-specific.
8 · 2.1.1.2
Poor electrical conductivity and chemical instability in aqueous solution limit practical use of pristine MOF cathodes.
Evidence basis: review_reasoning
Caveat: This limitation motivates conductive MOFs and MOF-derived materials.
11 · 2.1.2
MOF-based separators and electrolytes are promising for uniform Zn plating/stripping, but the review states that this subfield remains in its infancy.
Evidence basis: review_reasoning
Caveat: Use as outlook context rather than mature consensus.
17 · 2.2.2
Aqueous ZIBs are attractive for scalable and portable storage because they combine safety, low cost, high theoretical Zn capacity and aqueous electrolyte conductivity.
Evidence basis: multi_reference
Caveat: The review also notes Zn dendrites, HER and corrosion restrict practical cycle life.
2 · 1. Introduction
Compact ZIF-7 coatings are described as size-selective channels that reject large charged complexes while allowing properly sized coordinated ion complexes to migrate.
Evidence basis: single_reference
Caveat: This is a review summary of one original coating study.
14 · 2.2.1 · Figure 9
MOF-derived zincophilic hosts are used to control the initial nucleation process, which strongly affects final Zn deposition morphology.
Evidence basis: multi_reference
Caveat: The review notes that methods often focus on morphology and less often on initial nucleation.
14 · 2.2.1
Every row remains visibly secondary and links to a primary dossier only where the mapping is verified.
| Material | Property | Reported value | Context and quality | Primary evidence | Review source |
|---|---|---|---|---|---|
| Secondaryalpha-V2O5@C | capacity retention | 91.4% after 20000 cycles at 40 A g-1 | 0.3-1.9 V; 3 M Zn(CF3SO3)2; Table 2 Table · Exact Reported | No verified corpus mapping | 11 · 2.1.2 · Table 2 |
| SecondaryCoFe(CN)6 | capacity retention | 93.4% after 2200 cycles at 3.0 A g-1 | 0.7-2.0 V; 4 M Zn(OTF2); Table 1 Table · Exact Reported | No verified corpus mapping | 4 · 2.1.1.1 · Table 1 |
| SecondaryCu3(HHTP)2 | specific capacity | 228 mAh g-1 at 0.05 A g-1 | 0.5-1.5 V; 3 M Zn(CF3SO3)2; Table 1 Table · Exact Reported | research_0188 | 4 · 2.1.1.1 · Table 1 |
| SecondaryFeHCF | capacity retention | 73% after 10,000 cycles at 3.0 A g-1 | 0-2.3 V; 21 M C2F6LiNO4S2 + 1 M C4F12N2O8S4Zn electrolyte; Table 1 Table · Exact Reported | No verified corpus mapping | 4 · 2.1.1.1 · Table 1 |
| SecondaryMn-H3BTC-MOF-4 | specific capacity | 138 mAh g-1 at 0.1 A g-1 | 1.0-1.9 V; 2 M Zn(CF3SO3)2; Table 1 Table · Exact Reported | No verified corpus mapping | 4 · 2.1.1.1 · Table 1 |
| SecondaryMnO2/CC | specific capacity | 282.1 mAh g-1 at 0.5 A g-1 | 0.8-1.8 V; 2 M ZnSO4 + 0.1 M MnSO4; Table 2 Table · Exact Reported | No verified corpus mapping | 11 · 2.1.2 · Table 2 |
| SecondaryMnOx@N-C | retained capacity | 305 mAh g-1 after 600 cycles at 0.5 A g-1 | 0.8-1.8 V; 2 M ZnSO4 + 0.2 M MnSO4; Table 2 Table · Exact Reported | No verified corpus mapping | 11 · 2.1.2 · Table 2 |
| SecondaryMOF@Zn anode with Cu3(BTC)2 layer and Zn(TFSI)2-TFEP electrolyte | Zn plating/stripping efficiency | 99.1% for 350 cycles | MOF-encapsulated Zn(TFSI)2-TFEP electrolyte on Zn anode; text/figure discussion Text · Exact Reported | No verified corpus mapping | 14 · 2.2.1 · Figure 9 |
| SecondaryV-MOF (MIL-47) nanorod | specific capacity | 320 mAh g-1 at 0.1 A g-1 | 0.4-1.4 V; 3 M Zn(CF3SO3)2; Table 1 Table · Exact Reported | No verified corpus mapping | 4 · 2.1.1.1 · Table 1 |
| SecondaryZIF-8-500 coated nickel grid Zn plating substrate | Coulombic efficiency | about 98.6% over 200 cycles at 2.0 mA cm-2 and 1.0 mAh cm-2 | Bare Zn foil anode, 2 M ZnSO4 electrolyte; text discussion Text · Approximate | No verified corpus mapping | 15 · 2.2.1 · Figure 10 |
| SecondaryZnMOF-808 | inherent conductivity | 3 x 10^-7 S cm-1 at room temperature | Dry ZnMOF-808 solid-state electrolyte before water uptake; text discussion Text · Exact Reported | No verified corpus mapping | 16 · 2.2.2 · Figure 11 |
Open questions are presented as review-author priorities, not conclusions from the primary database.
Zn anode research is still described as immature, with low Coulombic efficiency and poor lifespan remaining significant challenges.
Proposed direction: Develop advanced materials and efficient methods that promote reversible reactions and suppress dendrites, HER and corrosion.
3 · 1. Introduction
Weakly acidic aqueous ZIB electrolytes can reduce MOF capacity and stability when MOFs are used as cathodes or interfacial components.
Proposed direction: Improve structural stability of MOFs in weakly acidic aqueous solution.
17 · 3. Conclusion and Prospects
Most MOFs suffer poor electrical conductivity because of insulating organic ligands and limited p-d orbital overlap.
Proposed direction: Develop conductive MOFs to reduce voltage polarisation and accelerate electrochemical kinetics.
17 · 3. Conclusion and Prospects
PBA offers high voltage but low capacity, whereas V-/Mn-based MOFs can show capacity but lower voltage, poorer cycling or stability challenges.
Proposed direction: Design MOF-based ZIBs that jointly improve discharge voltage, capacity and cycle life.
17 · 3. Conclusion and Prospects
MOF-derived materials can perform well but often require complex or harsh preparation, suffer low yield and incur high cost.
Proposed direction: Simplify post-treatment and explore affordable MOF-derived cathode routes.
11 · 2.1.2
MOF separator and electrolyte studies are less developed than MOF-modified Zn anodes.
Proposed direction: Further explore MOF-based separators and electrolytes for uniform Zn dissolution/deposition.
17 · 2.2.2
Mappings show which printed review references have a verified counterpart in the frozen primary corpus.
| Reference | Study | Role and context | Corpus mapping |
|---|---|---|---|
| Ref. 582019 | Title unavailable | secondary_benchmark · PBA_cathode · mechanism_contextUsed by the review for FeHCF voltage-window effects, Zn storage mechanism and long-cycle stability. | Unmapped |
| Ref. 602019 | Title unavailable | secondary_benchmark · PBA_cathodeSupports CoFe(CN)6 pristine MOF cathode performance in Table 1. | Unmapped |
| Ref. 692020 | Title unavailable | Mn_MOF · phase_transitionCited for early Mn(BTC) MOF cathodes and their conversion/phase-transformation behaviour. | Unmapped |
| Ref. 702021 | Title unavailable | secondary_benchmark · structural_engineering · Mn_MOFSupports the coordinatively unsaturated Mn-H3BTC-MOF structural-engineering example and benchmark. | Unmapped |
| Ref. 712019 | Title unavailable | V_MOF · conductive_array · intercalation_mechanismUsed for V-MOF@CNTF synthesis/performance and V-MOF-48 intercalation/extraction mechanism. | Unmapped |
| Ref. 732019 | Title unavailable | secondary_benchmark · conductive_MOFTable 1 benchmark for conductive Cu3(HHTP)2 cathode performance. | research_0188 |
| Ref. 742014 | Title unavailable | conductive_MOF · conductivity_contextCited by the review for ways to achieve conductivity in MOFs through guest molecules and orbital interactions. | research_0088 |
| Ref. 802019 | Title unavailable | conductive_MOF · Cu_HHTPThe review cites this for Stoddart group's use of Cu3(HHTP)2 as a ZIB cathode. | research_0188 |
| Ref. 832016 | Title unavailable | mechanism_context · PBA_cathodeSupports the PB/FeFe(CN)6 Zn2+ intercalation/extraction mechanism discussed with Figure 5. | Unmapped |
| Ref. 872021 | Title unavailable | phase_transition · PBA_cathodeCited for VHCF cubic-to-rhombohedral phase transition during cycling. | Unmapped |
| Ref. 882016 | Title unavailable | phase_transition · CuHCFUsed for CuHCF ageing and persistent phase-transition behaviour in ZIBs. | Unmapped |
| Ref. 952018 | Title unavailable | secondary_benchmark · MOF_derived_cathodeSupports MnOx@N-C Table 2 benchmark for MOF-derived porous carbon/oxide cathodes. | Unmapped |
| Ref. 962020 | Title unavailable | secondary_benchmark · MOF_derived_cathodeSupports MnO2/carbon-cloth performance in Table 2 and the ZIF-67-derived MnO2/CC example. | Unmapped |
| Ref. 982020 | Title unavailable | secondary_benchmark · MOF_derived_cathodeTable 2 benchmark for alpha-V2O5@C rate/life performance. | Unmapped |
| Ref. 1012020 | Title unavailable | synthesis_strategy · MOF_derived_cathodeSupports the MIL-88(V)-derived amorphous V2O5/carbon composite strategy discussed in text and Figure 7. | Unmapped |
| Ref. 1022020 | Title unavailable | synthesis_strategy · MOF_derived_cathodeCited for the ZIF-67 self-sacrificing template route to MnO2 nanosheet-assembled hollow polyhedra on carbon cloth. | Unmapped |
| Ref. 1082020 | Title unavailable | Zn_anode · MOF_SEI · ion_fluxSupports the compact ZIF-7 coating example for selective ion-complex migration and dendrite-free Zn plating/stripping. | Unmapped |
| Ref. 1092020 | Title unavailable | secondary_benchmark · Zn_anode · MOF_SEISupports the Cu3(BTC)2 MOF-confined Zn(TFSI)2-TFEP interfacial electrolyte/SEI example and Zn plating efficiency benchmark. | Unmapped |
| Ref. 1102019 | Title unavailable | secondary_benchmark · Zn_anode · zincophilic_hostSupports the ZIF-8-derived zincophilic host and Coulombic-efficiency benchmark. | Unmapped |
| Ref. 1192020 | Title unavailable | Zn_anode · zincophilic_hostSupports in situ ZIF-8 layer on Zn foil and Zn2+ adsorption/nucleation regulation discussion. | Unmapped |
| Ref. 1252021 | Title unavailable | separator · Zn_fluxSupports the Janus MOF/rGO separator example for uniform Zn2+ flux and improved Zn plating/stripping. | Unmapped |
| Ref. 1262019 | Title unavailable | secondary_benchmark · solid_state_electrolyte · Zn_transportSupports ZnMOF-808 SSE and water-driven Zn2+ conductivity discussion. | Unmapped |
| Ref. 1272019 | Title unavailable | stability_context · outlookSupports the review's statement that many MOFs have low endurance to acidic aqueous solution. | Unmapped |