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Multi-metal–Organic Frameworks and Their Derived Materials for Li/Na-Ion Batteries

  • Weiwei Sun
  • Xuxu Tang
  • Yong WangEmail author
Review article
  • 125 Downloads

Abstract

Lithium-ion and sodium-ion batteries are widely regarded as green energy storage power devices to support the development of modern electronic and information technology systems. Therefore, the design of advanced cathode and anode materials with higher energy and power densities is crucial to satisfy the increasing demand for next-generation high-performance batteries. To address this, researchers have explored metal–organic frameworks that possess extremely large surface areas, uniform ordered pores and controllable functional groups for application in the fields of energy storage, adsorption, catalysis, separation, etc. In addition, multi-metal–organic frameworks (MMOFs) and their derivatives have also been reported to provide better tunability to allow for the control of size, porosity, structure and composition, resulting in enhanced electronic and ion conductivities and richer redox chemistries at desirable potentials. Moreover, the synergistic effects between two or more metal components in MMOFs and their derivatives can accommodate large volume expansions during stepwise Li-/Na-ion insertion and extraction processes to allow for the improvement of structural stability in electrodes as well as enhanced cyclability. Based on all of this, this review will discuss and summarize the most recent progress in the synthesis, electrochemical performance and design of MMOFs and their derivatives. In addition, future trends and prospects in the development of MMOF-based materials and their application as high-performance Li/Na storage electrode materials are presented.

Graphic Abstract

Recent advances in multi-metal–organic frameworks and their derived materials for applications in lithium-/sodium-ion batteries are summarized and critically discussed.

Keywords

Metal–organic frameworks Lithium-ion battery Sodium-ion battery Multi-metallic oxide Multi-metallic sulfide Electrochemical performance 

1 Introduction

Increasing energy demands have plagued society as a whole due to the vast consumption of fossil fuels that have resulted in fuel shortages and environmental pollution. Based on this, sustainable economic development requires cost-effective, efficient and environmentally benign energy sources [1, 2, 3, 4, 5, 6]. To address this, Sony introduced commercial lithium-ion batteries (LIBs) in 1991, and since then, LIBs have become the most popular power source for portable electronic devices, electrical vehicles and backup electricity storage units due to advantageous features such as high voltages, high energy densities, long cycle lifespans, low self-discharge rates and wider operational temperature windows [7, 8]. And although introduced at around the same time as LIBs, the commercial application of sodium-ion batteries (SIBs) has largely been ignored. However, SIBs have emerged in recent years as a potentially powerful alternative to LIBs due to the natural abundance of sodium (23,600 ppm), much lower costs and similar electrochemical properties [9, 10, 11, 12, 13]. LIBs and SIBs operate through similar processes of lithium-ion or sodium-ion insertion/extraction between cathodes and anodes and ion transport through electrolytes. However, compared with copper current collectors used in LIB anode materials, low-cost aluminum foil can be utilized as current collectors for both electrodes in SIBs to greatly reduce costs and weight. Overall, scientists aim to achieve a high specific energy density of 500 Wh kg−1 in battery packs by 2030, which is more than twice the value of 170–200 Wh kg−1 for current electric vehicle (EV) batteries, meaning that significant efforts need to be devoted to the development of key components, including positive and negative electrodes, electrolytes, designs and other technologies [3]. And among these factors, the development of advanced cathode and anode materials with higher energy and power densities may be the most critical [14, 15, 16, 17]. Here, various electrode materials for LIBs and SIBs such as metals [18, 19], metal oxides [20, 21, 22, 23, 24, 25, 26] and metal sulfides [27, 28, 29] have been proposed as high-capacity anode alternatives and have attracted significant attention due to their theoretical capacities being 2 to 3 times higher than that of commercial graphite anodes (372 mAh g−1). However, poor electronic conductivity, large volume change and undesirable side reactions in electrolytes during cycling can lead to fast capacity fading, poor rate performance and low Coulombic efficiency, severely limiting practical application. To address this, researchers have recently started to explore hollow nanostructures as electrode materials for high-performance LIBs and SIBs [2, 6, 30, 31, 32, 33] due to intriguing porous interiors that can offer large surface areas, low densities, microreactor environments and void spaces for the introduction of guest components such as lithium ions or sodium ions. In addition, many studies have demonstrated that the large surface area and open porous channels of hollow structural electrodes can provide large accessible active sites and shortened pathways for electrolyte infusion, Li/Na and electron diffusion and even Li/Na storage. In addition, the thin shells and void spaces of these hollow nanostructures can also relax structural strain associated with large volume change during Li+ and Na+ insertion/extraction. Furthermore, the use of carbonaceous material-supported composites is another popular and effective strategy to improve the Li/Na storage performances of high-capacity electrodes due to the soft and electrically conductive properties of these materials in which the presence of carbonaceous materials can accommodate large volume change and improve the electronic conductivity and structural stability of supported high-capacity components [34, 35, 36, 37, 38, 39, 40, 41].

Metal–organic frameworks (MOFs) are a type of crystalline materials constructed by using metal ions or metal-containing clusters (secondary building units, SBUs) with coordinated organic ligands [42, 43, 44, 45, 46, 47] and since being reported in the late 1990s by Yaghi et al. [48], MOFs have been proposed to be a promising category of porous nanomaterials with increasing interests from researchers. This is because MOFs possess impressive characteristics including large surface areas, uniform ordered pores, tunable pore sizes, low densities and controllable functional groups [49, 50, 51, 52, 53]. Here, MOFs can possess extremely large surface areas (up to 10,000 m2 g−1) exceeding those of traditional porous materials such as zeolites and carbons. Furthermore, numerous porous MOFs have been determined to possess pore sizes ranging from ~ 2 to 50 Å with MOF-associated porosity being more extensive in terms of their variety and multiplicity than other types of porous materials. Moreover, these pores within MOFs can also be functionalized by adjusting pore/window sizes. Because of these merits, MOFs have been used in a wide range of applications including gas storage and separation, catalysis, drug delivery, sensing and nonlinear optics [54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72]. And recently, MOF-derived approaches along with a variety of other synthetic approaches such as the Kirkendall effect, chemical etching, galvanic replacement and Ostwald ripening have been demonstrated to be effective templated strategies to fabricate porous metal-containing structures [44, 45, 46, 47], resulting in the application of MOFs and derivatives in the field of energy storage, especially in LIBs and SIBs, and attracting significant attention. Here, a few reviews have summarized the application of MOFs and derivatives in broad areas of clean energy, including batteries, supercapacitors, fuel cells, solar cells and hydrogen storage systems [73, 74, 75, 76, 77, 78]; however, monometal–organic framework-derived metal oxides and their composites are usually the major focus in these reviews. In addition, there are no specific reviews focusing on the synthesis and application of multi-metal–organic frameworks (MMOFs) and their derivatives for LIBs and SIBs. Based on this, the recent developments of MMOFs and their derived materials specifically for LIB and SIB applications are summarized and critically discussed in this review. This is because MMOFs have been demonstrated to be able to be used as direct electrodes or precursors to design multi-metallic electrode materials for LIBs and SIBs with richer redox reactions and enhanced electrochemical performances in which through in situ one-pot synthesis or ex situ multi-step ion-change reactions, uniform or hierarchical multi-components can be obtained through the control of different types of MOFs with two or more metal ions [79, 80, 81, 82, 83]. And as a special type of MOF-derived structure, MMOF-derived multi-metallic materials can not only exhibit conventional features such as well-inherited morphology and porosities from MOF precursors, but also be endowed with significant synergistic effects arising between two or more different metal components [84, 85, 86, 87, 88, 89, 90]. Overall, based on the effects on LIB/SIB applications, four categories of MMOF-derived multi-metallic electrodes are presented in this review, including MMOFs and their composites [91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103], MMOF-derived multi-metallic oxides and their composites [104, 105, 106, 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, 169, 170, 171, 172, 173, 174], MMOF-derived multi-metallic sulfides/selenides/phosphides/carbides and their composites [175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190] and MMOF-derived other materials (mainly alloys and lithium metal oxides) [191, 192, 193, 194, 195, 196, 197, 198, 199] (Scheme 1) as well as their electrochemical performances in LIBs and SIBs (Tables 1, 2, 3, 4). In addition, this review aims to strengthen the importance and guide the sustained exploration of MMOFs and their derivatives for high-performance LIBs and SIBs.
Scheme 1

Schematic illustration showing four main categories of multi-metal–organic frameworks (MMOFs)-derived materials for Li/Na-ion battery application with the mostly admitted structural or performance superiorities (the octahedron: reprinted with permissions from Ref. [97], Copyright 2016, Royal Society of Chemistry; the multilayer hollow sphere: reprinted with permissions from Ref. [145], Copyright 2015, American Chemical Society; the dodecahedron: reprinted with permissions from Ref. [181], Copyright 2016, Wiley-VCH; the cactus-like ball: Reprinted with permissions from Ref. [192], Copyright 2017, Wiley-VCH

Table 1

Electrochemical performances of representative MMOFs as electrodes for LIBs and SIBs

Composite

Ligand

Morphology

IRC

RRC/CN

CD

V

References

Mn/Fe–MOF

CN

Nanocube

~ 545

~ 296/100

200

0.01–3.0 (Li/Li+)

[92]

Na–Fe–MOF

CN

Cube

~ 144

~ 170/150

25

2.7–4.0 (Na/Na+)

[93]

K/Na–Mn/Fe-MOF

CN

Cube

~ 108

~ 91/100

40

2.0–4.2 (Na/Na+)

[94]

Na–Mn/Fe-MOF

CN

None

134

121/30

6

2.0–4.2 (Na/Na+)

[95]

Tb/W-MOF

CN

None

31

~ 27/10

10

2.5–4.3 (Li/Li+)

[96]

Co/Zn-MOF

BDC

Particle

1467

1211/100

100

0.01–3.0 (Li/Li+)

[97]

Mn/Co-MOF

BTC

Sheet

~ 880

901/150

100

0.01–3.0 (Li/Li+)

[98]

Fe/Co-MOF

TPDC

None

~ 930

~ 900/100

100

0.01–3.0 (Li/Li+)

[99]

BP–Ni/Co-MOF

BDC

Sheet

~ 600

~ 398/1000

5000

0.02–3.0 (Li/Li+)

[100]

SnO2/Cr-MOF

BDC

Octahedron

~ 780

510/100

79

0.02–2.5 (Li/Li+)

[101]

Fe3O4/Cu-MOF

BTC

Core–shell nanoparticle

~ 919

~ 994/100

100

0.01–3.0 (Li/Li+)

[102]

Li(Li0.17Ni0.20Co0.05Mn0.58)O2/Mn-MOF

DOBDC

Nanoparticle

324

~ 284/100

30

2.0–4.8 (Li/Li+)

[103]

IRC—initial reversible capacity (mAh g−1), RRC—retained reversible capacity (mAh g−1), CN—cycle number, CD—current density (mA g−1), V—voltage (V). All abbreviations for the ligands of MOFs are summarized in Appendix Table 5

Table 2

Electrochemical performances of representative MMOF-derived multi-metallic oxide materials as electrodes for LIBs and SIBs

Composite

Ligand

Morphology

IRC

RRC/CN

CD

V

References

ZnO–ZnFe2O4

CN

Nanoparticle

826

803/500

1000

0.01–3.0 (Li/Li+)

[104]

Fe2O3–CuO

CN

Cube

795

774/120

500

0.01–3.0 (Li/Li+)

[105]

MgFe2O4

CN

Microbox

930

~ 633/100

50

0.005–3.0 (Li/Li+)

[106]

MgFe2O4

CN

Hollow microbox

207

~ 135/150

50

0.005–3.0 (Na/Na+)

[107]

ZnO–ZnFe2O4

CN

Microcube

~ 1371

~ 837/200

1000

0.01–3.0 (Li/Li+)

[108]

ZnFe2O4–ZnO

CN

Nanosheet

~ 839

~ 537/500

500

0.01–3.0 (Li/Li+)

[109]

ZnO/ZnFe2O4

CN

Particle

~ 705

~ 704/200

200

0.01–3.0 (Li/Li+)

[110]

Fe2O3–NiO

CN

Cube-in-box

~ 1040

1100/300

200

0.01–3.0 (Li/Li+)

[111]

NiFe2O4

CN

Hollow nanocage

1152

1071/200

1000

0.01–3.0 (Li/Li+)

[112]

SnO2–Fe2O3

CN

Nanosheet and nanorod

~ 1500

~ 536/100

100

0.01–3.0 (Li/Li+)

[113]

Fe2O3–NiCo2O4

CN

Hollow nanocage

~ 903

~ 1080/100

100

0.01–3.0 (Li/Li+)

[114]

SnO2–Fe2O3–NiO

CN

Nanoparticle

~ 1300

~ 514/350

100

0.01–3.0 (Li/Li+)

[115]

NiCo2O4

mIM

Nanobox

906

1080/150

~ 328/30

500

0.01–3.0 (Li/Li+)

0.01–3.0 (Na/Na+)

[116]

~ 520

50

Co3O4@NiCo2O4

mIM

Sheets-in-cage

~ 782

~ 1083/100

100

0.01–3.0 (Li/Li+)

[117]

Co3O4–TiO2

mIM

Hollow polyhedron

535

642/200

500

0.01–3.0 (Li/Li+)

[118]

Mn2V2O7

mIM

Nanoparticle

~ 268

~ 868/180

500

0.005–3.0 (Li/Li+)

[119]

Co3V2O8

mIM

Nanoparticle

926

1177/200

200

0.01–2.5 (Li/Li+)

[120]

Ni3V2O8

mIM

Nanoparticle

~ 820

~ 940/400

1000

0.01–3.0 (Li/Li+)

[121]

Zn3V2O8

mIM

Porous sheet

830

~ 1228/200

300

0.01–3.0 (Li/Li+)

[122]

ZnCo2O4

mIM

Cuboid

1013

~ 1091/100

100

0.1–3.0 (Li/Li+)

[123]

Co3O4/ZnO

mIM

Nanosheet

~ 462

~ 442/1000

~ 220/1000

3000

0.01–3.0 (Li/Li+)

0.01–3.0 (Na/Na+)

[124]

~ 242

2000

SnO2–Co3O4

mIM

Nanofiber

~ 1000

~ 1287/300

500

0.005–3.0 (Li/Li+)

[125]

Co3O4/MoS2

mIM

Nanosheets on Octahedron

~ 912

~ 1200/100

100

0.01–3.0 (Li/Li+)

[126]

ZnO–ZnCo2O4

BDC

Nanosheet

987

870/200

1000

0.01–3.0 (Li/Li+)

[127]

NixFe3−xO4

BDC

Nanotube

1223

1184/200

250

0–3.0 (Li/Li+)

[128]

Co3V2O8

BDC

Microsphere

933

995/120

500

0.01–3.0 (Li/Li+)

[129]

Co3V2O8

BDC

Particle

934

~ 980/140

200

0.005–2.5 (Li/Li+)

[130]

Ni3V2O8

BDC

Spindle

~ 920

~ 822/100

200

0.005–3.0 (Li/Li+)

[131]

Co-Doped TiO2

BDC

Nanodisk

232

~ 170/100

100

0.01–3.0 (Na/Na+)

[132]

NixCo3−xO4

BTC

Hollow microsphere

~ 1139

~ 1110/100

100

0.005–3.0 (Li/Li+)

[133]

CuO/Cu2O@CeO2

BTC

Particle

~ 500

~ 593/100

200

0.005–3.0 (Li/Li+)

[134]

(Cu0.30Co0.7)Co2O4/CuO

BTC

Rectangular pyramid

324

~ 610/1000

1000

0.01–3.0 (Li/Li+)

[135]

CoxMn3−xO4

BTC

Nanoparticle

~ 739

~ 984/100

100

0.01–3.0 (Li/Li+)

[136]

CuO/TiO2

BTC

Octahedron

780

~ 692/200

100

0.01–3.0 (Li/Li+)

[137]

Ni0.3Co2.7O4

DOBDC

Nanorod

1189

1410/200

100

0.005–3.0 (Li/Li+)

[138]

Co3O4–CoFe2O4

DOBDC

Particle

918

~ 940/80

100

0.01–3.0 (Li/Li+)

[139]

ZnCo2O4

DOBDC

Particle

~ 2023

~ 1243/80

100

0.01–3.0 (Li/Li+)

[140]

Fe2O3–ZnO

TGA

Particle

1189

700/60

100

0.005–3.0 (Li/Li+)

[141]

Ni0.9Zn0.1O

PD

Nanosheet

~ 830

~ 750/160

400

0.01–3.0 (Li/Li+)

[142]

Co3O4@Co3V2O8

mIM

Triple-shelled nanobox

1186

~ 920/100

100

0.01–2.5 (Li/Li+)

[143]

ZnO/NiO

BDC

Yolk–shell sphere

~ 769

~ 1009/200

100

0.005–3.0 (Li/Li+)

[144]

CuO–NiO

BTC

Multilayer hollow sphere

856

1061/200

100

0.005–3.0 (Li/Li+)

[145]

Co3O4–TiO2

NTA

Core–shell nanorod

~ 850

~ 803/100

200

0.01–3.0 (Li/Li+)

[146]

TiO2@NiCo2O4@Co3O4

mIM

Triple-shelled nanocage

~ 1760

~ 852/200

100

0.01–3.0 (Li/Li+)

[147]

NiO–ZnCo2O4

mIM

Nanowire

~ 980

1002/100

100

0.01–3.0 (Li/Li+)

[148]

3NiO·2Ni3/2Co1/2ZnO4

mIM

Hollow dodecahedron

1263

~ 1337/100

200

0.01–3.0 (Li/Li+)

[149]

Te@ZnCo2O4

mIM

Nanofiber

839

956/100

100

0.01–3.0 (Li/Li+)

[150]

Co2NiV2O8

mIM

Nanoparticle

1282

~ 986/195

200

0.01–3.0 (Li/Li+)

[151]

Fe3O4–VOx@C

CN

Hollow microbox

~ 650

742/400

500

0.01–3.0 (Li/Li+)

[152]

ZnO–Co@N-doped C

CN

Nanosphere

~ 1135

~ 1086/100

100

0.01–3.0 (Li/Li+)

[153]

Sn@C–ZnO

mIM

Core–shell sheet

~ 718

~ 516/50

100

0.01–3.0 (Li/Li+)

[154]

ZnCo2O4/C

mIM

Nanoplate

~ 867

~ 1342/100

200

0.01–3.0 (Li/Li+)

[155]

ZnCo2O4–ZnO@C

mIM

Nanorod array

898

~ 1318/150

200

0–3.0 (Li/Li+)

[156]

MnO–ZnMn2O4@N-doped C

mIM

Yolk–shell nanorod

586

803/100

50

0.01–3.0 (Li/Li+)

[157]

ZnO/ZnFe2O4@N-doped C

mIM

Polyhedron

1180

~ 1000/100

200

0.01–3.0 (Li/Li+)

[158]

ZnO/ZnCo2O4/CuCo2O4@N-doped C

mIM

Polyhedron

1967

~ 1742/500

300

0.01–3.0 (Li/Li+)

[159]

ZnO–ZnFe2O4@C

BDC

Hollow octahedron

1047

1390/100

500

0.005–3.0 (Li/Li+)

[160]

ZnO–ZnFe2O4@C

BDC

Ball-in-ball nanosphere

1114

1283/100

100

0.01–3.0 (Li/Li+)

[161]

NiFe2O4@C

BDC

Hollow nanosphere

1050

1355/100

91.5

0.01–3.0 (Li/Li+)

[162]

SnO2/TiO2@C

BDC

Tablet

1177

~ 1045/100

100

0.01–3.0 (Li/Li+)

[163]

Zn2SnO4@C/Sn

BDC

Particle

~ 1514

~ 1140/100

100

0.01–3.0 (Li/Li+)

[164]

Co3O4/NiO@C

BTC

Multilayered microsphere

~ 642

~ 776/1000

1000

0.01–3.0 (Li/Li+)

[165]

ZnFe2O4@C

FA

Spindle

772

~ 650/400

1000

0.01–3.0 (Li/Li+)

[166]

ZnCo2O4@N-doped C

CTAB

Nanoparticle

~ 1080

~ 903/100

1000

0.01–3.0 (Li/Li+)

[167]

MoxW1−xO2−xCu@P-doped C

BTC

Octahedron

770

911/250

500

0.01–3.0 (Li/Li+)

[168]

FeTiO3@CNTs

BDC

Nanotube

~ 418

~ 414/200

100

0.01–3.0 (Na/Na+)

[169]

NiCo2O4/CNT

mIM

Microsphere

~ 1197

~ 1673/200

1000

0.001–3.0 (Li/Li+)

[170]

Ni@ZnO/CNF

mIM

Polyhedron on nanofiber

1100

1051/100

100

0.01–3.0 (Li/Li+)

[171]

NiCo2O4@graphene

mIM

Nanorod

858

~ 858/50

500

0.01–3.0 (Li/Li+)

[172]

MnO2–Co3O4–graphene

mIM

Nanocage

~ 800

~ 554/400

500

0.01–3.0 (Li/Li+)

[173]

MoO2–Cu@C–graphene

BTC

Nano-octahedron

~ 938

~ 1115/100

100

0.01–3.0 (Li/Li+)

[174]

IRC—initial reversible capacity (mAh g−1), RRC—retained reversible capacity (mAh g−1), CN—cycle number, CD—current density (mA g−1), V—voltage (V). All abbreviations for the ligands of MOFs are summarized in Appendix Table 5

Table 3

Electrochemical performances of representative MMOF-derived multi-metallic sulfide/selenide/phosphide/carbide materials as electrodes for LIBs and SIBs

Composite

Ligand

Morphology

IRC

RRC/CN

CD

V

References

Co3S4@C@MoS2

mIM

Dodecahedron

~ 741

~ 673/200

200

0.05–3.0 (Li/Li+)

[175]

ZnS–Sb2S3@C

mIM

Core–shell polyhedron

1029

~ 630/120

100

0.01–1.8 (Na/Na+)

[176]

FeS@TiO2@C

BDC

Nanotube

~ 406/150

1000

0.01–3.0 (Na/Na+)

[177]

NiCo2S4@N-doped C

CN

Hollow cube

503

~ 480/100

100

1.0–3.0 (Li/Li+)

[178]

ZnCoS@Co9S8/N-doped C

mIM

Hollow core–shell polyhedron

~ 750

~ 1814/500

500

0.01–3.0 (Li/Li+)

[179]

Ni3S2–Co9S8@N-doped C

BTC

Hollow sphere

425

~ 414/100

100

0.005–3.0 (Na/Na+)

[180]

Co0.4Zn0.19S@N/S-doped C–CNT

mIM

Dodecahedron

1057

941/250

100

0.005–3.0 (Li/Li+)

[181]

ZnxCo1−xS@C–CNT

mIM

Starfish-like morphology

~ 1000

~ 635/1000

1200

0.01–3.0 (Li/Li+)

[182]

CoSe2/(NiCo)Se2

mIM

Box-in-box hollow nanocube

~ 526

~ 497/80

200

0.001–3.0 (Na/Na+)

[183]

NixCo1−xSe2/C

mIM

Polyhedron

~ 1500

~ 1667/600

2000

0.01–3.0 (Li/Li+)

[184]

Co–Zn–Se@C

DOBDC

Microrod

~ 1020

949/500

1000

0.005–3.0 (Li/Li+)

[185]

ZnSe/CoSe@N-doped C–CNT

mIM

Polyhedron

~ 670

~ 768/1000

1000

0.02–3.0 (Li/Li+)

[186]

Ni1.5CoSe5@N–doped C–graphene

CN

Nanocube

~ 470

~ 360/80

500

0.01–2.8 (Na/Na+)

[187]

FexNi2−xP/P-doped C

BDC

Nanorod

~ 788

~ 775/400

100

0.01–3.0 (Li/Li+)

[188]

C–FeP@CoP@graphene

CN

Core–shell microcube

~ 551

~ 456/200

100

0.01–3.0 (Na/Na+)

[189]

Co3ZnC@N-doped C–CNT

mIM

Polyhedron

~ 580

~ 404

585/1500

~ 386/750

2000

0.01–3.0 (Li/Li+)

0.01–3.0 (Na/Na+)

[190]

1000

IRC—initial reversible capacity (mAh g−1), RRC—retained reversible capacity (mAh g−1), CN—cycle number, CD—current density (mA g−1), V—voltage (V). All abbreviations for the ligands of MOFs are summarized in Appendix Table 5

Table 4

Electrochemical performances of representative MMOF-derived other multi-metallic materials as electrodes for LIBs and SIBs

Composite

Ligand

Morphology

IRC

RRC/CN

CD

V

References

Fe–Co@C

BTC

Nanoparticle

483

550/180

100

0.01–3.0 (Li/Li+)

[191]

Ni–Sn–P@C–CNT

BTC

Microsphere

933

704/200

100

0–3.0 (Li/Li+)

[192]

Sn–Co@N-doped C

mIM

Microbox

945

818/100

100

0.01–3.0 (Li/Li+)

[193]

Ni–Sb@C

BTC

Hollow microsphere

~ 678

~ 487/100

100

0.01–2.6 (Li/Li+)

[194]

Sn–In–Ni

CN

Nanoparticle

~ 1200

~ 618/200

100

0.01–2.0 (Li/Li+)

[195]

Co–Zn@N-doped C

mIM

Nanocage

~ 510

702/400

200

0.01–3.0 (Li/Li+)

[196]

LiNi0.5Mn1.5O4

BDC

Octahedral particle

~ 121

~ 101/500

20,000

3.5–5.0 (Li/Li+)

[197]

Li4Ti5O12@C

BDC

Tablet

253

~ 277/700

500

0.01–3.0 (Li/Li+)

[198]

Li2ZnTi3O8@N-doped C

mIM

Nanoparticle

~ 251

~ 271/200

500

0.02–3.0 (Li/Li+)

[199]

IRC—initial reversible capacity (mAh g−1), RRC—retained reversible capacity (mAh g−1), CN—cycle number, CD—current density (mA g−1), V—voltage (V). All abbreviations for the ligands of MOFs are summarized in Appendix Table 5

2 Design Principles/Strategies and Application Merits

MOFs with controllable morphology and porous structures can be fabricated based on coordination interactions between inorganic SBUs (metal ions or clusters) and single/multiple organic ligands in which commonly used metal centers of SBUs for the synthesis of MOFs include but are not limited to transition metals such as Zn, Cu, Co, Cd, Ti and main group metals of Mg, Ca, Al as well as lanthanide metals, with realizable coordination geometry including tetrahedral, trigonal bipyramidal, square, pyramidal and octahedral [66]. As for organic linkers (bridging ligands), carboxylates or other organic anions such as phosphonate, sulfonate and N-heterocyclic compounds can be adopted to allow for the support of large separations between metal centers to create permanent porosity and maintain structural robustness and diversity [74, 75, 76, 77]. In addition, the reversible formation of coordination bonds can allow for the rearrangement of SBUs and organic ligands during polymerization/coordination to further fabricate highly ordered framework structures [66]. Moreover, the structure and property of MOFs can be easily tailored by adjusting the metal species, geometry, pore size and functionality of pre-designed units in which the versatility of metallic SBUs, organic linkers and their many combinations in all possible directions allows for diverse physical and chemical properties in MOFs. Therefore, the synthesis of novel MOF structures needs to take into consideration various factors, including reactant material concentrations, solvent properties (referring to the solubility of reactants), pH values, reaction temperatures and reaction times.

Synthesis approaches for MOFs have been well developed with several methods being regularly used. These methods include [47, 70, 71, 72, 76, 77, 81, 82, 83, 200]: (1) the precipitation method, which is one of the most common and widely used methods for the synthesis of MOFs and is based on the direct mixing of highly concentrated solutions containing metal ions and bridging ligands; (2) the conventional heating methods, which allow for crystal engineering through hydro/solvothermal methods that is the most challenging issue among numerous parameters affecting MOF formation; (3) the microwave and ultrasound driven synthesis, in which the reaction of metal ions and ligands is facilitated through the assistance of microwaves and ultrasounds. Here, growth mechanisms resulting in different product morphology, sizes and porosity can be dramatically influenced by gradients in concentration and temperature within the reaction vessel; (4) the electrochemical synthesis, which provides advantages over the conventional synthesis in the control of crystal growth, including the modulation of metal cation concentrations in solution through changes in current intensity or the possibility of controlling metal oxidation states; and (5) the ionic liquid-assisted synthesis, in which due to interesting physicochemical properties such as tunable solubility and negligible vapor pressure, ionic liquids can behave as reactants, structure directing agents, functional inclusions or templates during MOF synthesis. And as a result of these versatile and flexible synthesis methods, the design and preparation of MOFs containing two or more metal components are possible as well as the endowment of more unique properties and applications in resulting MMOFs [50, 79, 80, 201].

Originating from regular MOF synthetic approaches, several strategies have also been explored to fabricate MMOFs [81]. Here, in situ one-pot reactions through the simultaneously mixing of a variety of metal species with organic ligands based on the aforementioned five approaches have been reported to be viable for the synthesis of MMOFs, in which the chemical composition and phase uniformity of obtained MMOF materials can be finely tuned by adjusting molar ratios of metal species, temperatures and precursor concentrations [92, 93, 94, 95, 96, 97, 98, 99, 100, 108, 109, 110, 111, 112, 113, 114, 115, 116, 119, 120, 121, 122, 124, 126, 127, 128, 129, 130, 131, 132, 133, 135, 136, 138, 139, 140, 141, 142, 144, 148, 149, 151, 153, 155, 158, 160, 161, 162, 164, 165, 166, 167, 171, 178, 179, 180, 181, 182, 185, 186, 188, 190, 191]. Another efficient strategy to synthesize tunable MMOFs is the trans-metalation reaction involving a secondary step of ion-exchange reactions between preformed monometal–organic frameworks and another metal ion precursor to yield MMOF structures with mixed metal centers, resulting in new and distinct chemical functionalities [104, 105, 106, 107, 118, 123, 134, 145, 159, 192]. In addition, because the ion-exchange reaction preferentially occurs on the exterior surface of preformed monometal–organic frameworks, this approach can result in versatile core–shell/yolk–shell MMOF structures. And similar to the trans-metalation method, a combination of preformed monometal–organic frameworks with additives of other metal-based components such as metal oxide loadings or coatings [91, 101, 102, 137, 143, 147, 169], metal salts [125, 163, 172, 177, 193], Mo/W-based polyoxometalates [168, 174] or Li-containing compounds [103, 198, 199] can also be selected to fabricate MMOFs and be an effective method to prepare composites of metal oxides or Li-containing compounds loaded into MOF pores [101, 102, 103]. The multi-step seed-mediated growth method is another effective approach to fabricate MMOFs with core–shell/yolk–shell structures in which through repetitive seeding and growing cycles or through the simply adjustment of used seed amounts, core–shell/yolk–shell MMOF structures composed of multiple shells with desirable metal compositions and/or particle sizes can be obtained [154, 156, 157, 173, 196]. Here, the introduction of predefined seeds, common metal oxides, can suppress nucleation and preferentially enable the uniform growth of MOF shells over metal oxide seeds. Overall for MMOFs, uniformly dispersed two or more metal centers coordinated with single or multiple organic ligands can generally be synthesized based on in situ one-pot reactions, whereas trans-metalation reactions and multi-step seed-mediated growth techniques generally lead to core–shell/yolk–shell MMOF structures. And as compared with monometal–organic frameworks, the pore size distributions and surface area properties of MMOFs can be adjusted through the modulation of the molar ratio of different metal components. In addition, the introduction of other metal components can also effectively improve the structural stability and electric conductivity of MMOFs.

Based on derivation from various MMOF precursors, multi-metallic oxides, sulfides, selenides and phosphides can also be obtained through corresponding oxidation, sulfidation, selenization and phosphorization processes under suitable temperatures and gas atmospheres. And similar to transformations from monometal–organic frameworks to monometallic derivatives, the inheritance of MMOF precursor morphology and porosity can also be achieved for multi-metallic derivatives. This is especially true for diverse core–shell MMOFs, which can be obtained through ex situ multi-step ion-change reactions between preformed monometal–organic frameworks and other metal ion precursors, and can be used as simple and effective sacrificial templates for the preparation of multi-metallic core–shell structures upon calcination. Aside from the inheritance of multi-metal derivative materials based on the metal centers of MMOF precursors, organic ligands of MMOF precursors can usually also be retained as porous carbon during the controllable carbonization of MMOFs in inert gas [175, 176, 177, 178, 179, 180, 181, 182, 191, 192, 193, 194]. In comparison with carbon composites prepared through other synthetic approaches, the in situ formation of porous carbon from MMOF precursors can result in homogeneous carbon composites with uniform distributions of multi-metal relative components in carbon matrixes.

The widespread application of MOFs and their derivatives (including metal oxides/sulfides/selenides and their carbon composites) for energy storage systems is a result of corresponding structural merits. This is because the chemical composition and phase uniformity of MOFs can be finely tuned by adjusting metal species, molar ratios, synthetic temperatures and reaction concentrations. In addition, the tunable composition and structure of MOFs can provide more active Li/Na storage sites to allow for enhanced lithium/sodium transformation and electrolyte infiltration. Moreover, the porous characteristics of MOF structures including pore size/volume and pore functionalization can be controlled through the adjustment of metal centers and organic ligands during synthesis, which can also functionalize small molecules in the as-synthesized MOFs. These properties are vital to the improvement of Li/Na storage properties because uniform pores can lead to more uniform local volume change during Li/Na insertion and extraction processes, allowing associated mechanical stress to be more homogenous and easier to accommodate in electrodes. Furthermore, MOF-derived materials such as metal oxides/sulfides/selenides and their carbonaceous composites possess inherited structural and porous characteristics that can lead to improved electrochemical properties.

Aside from the merits of MOFs and their derivatives for Li/Na storage, MMOFs have also attracted increasing attention due to several advantages and principles in terms of the design of MMOFs and their derived materials for electrochemical energy storage applications. Here, the most promising merit of MMOF-based approaches is that MMOF-templated growth processes can lead to the formation of more homogenous pores in their derived metal-containing products as compared with other synthetic approaches for porous structures, such as the Kirkendall effect, chemical etching, galvanic replacement and Ostwald ripening. In addition, the pore size, volume and functionalization of MMOFs can also be controlled through the adjustment of the molar ratios of two or more metal components and organic ligands. This also allows for the improvement of Li/Na storage properties because uniform pores can lead to more uniform local volume change during Li/Na insertion and extraction processes, also allowing associated mechanical stress to be more homogenous and easier to accommodate in electrodes. Moreover, MMOF-derived materials can usually exhibit hydrophobic pores due to the use of organic MOF precursors, which is an intriguing merit that can facilitate the infusion of organic electrolytes into electrode pores, which cannot be achieved for the metal oxides/sulfides/selenides and their carbonaceous composites obtained through other synthetic approaches [72]. MMOFs have also proven to be effective templates for the generation of hierarchical porosity, which can provide versatile functionalities to enhance electrochemical performances [22].

In general, the obtained macropores in MMOFs can accelerate the kinetic processes of electrolyte infusion and ion diffusion in electrodes, whereas mesopores can store electrolytes and prevent over-flooding due to capillary forces. More importantly, ion or charge transfer can be facilitated by meso-/micropores, which can also function as more active sites for additional Li/Na storage. MMOFs with core–shell or yolk–shell structure are also easier to design due to the heterogeneous thermal properties of MMOF precursors, which are highly desirable in electrochemical energy storage. This is because permeable thin shells can provide reduced pathways for electron/ion diffusion, resulting in better rate capabilities. In addition, the hierarchical hollow interiors can provide extra free space to alleviate structural strain and accommodate large volume expansion associated with repeated Li/Na insertion and extraction, leading to long-term electrode stability. And aside from MOF-derived porous characteristics, MMOF-derived multi-metallic materials and their carbonaceous composites can also exhibit special structural properties and intriguing electrochemical performances through suitable electrode designs for LIBs and SIBs. Moreover, the choice of two or more metal-related materials can provide richer redox chemistries and stepwise Li/Na storage potentials as a result of synergistic effects between the two or more different metal components at different stages for Li/Na insertion and extraction. And due to the different potentials of Li/Na storage in the multi-metal components of multi-metallic materials, inactive components can act as buffering materials to accommodate large volume expansion induced by Li/Na insertion and extraction in active components to allow for improved structural stability of electrodes during repetitive cycling [84, 85, 86, 87, 88, 89, 90, 138, 145, 181], suggesting that the structural merits of multi-metallic species with controllable compositions and phase uniformity can provide long-term structural stabilization in MMOFs and their derived multi-metallic electrodes.

The introduction of guest molecules is one of the most frequently adopted strategies to induce conductivity in otherwise non-conducting coordination polymers in which the choice of two and more metal-related materials requires matched electronic structures for each other, allowing MMOF-derived multi-metallic materials to possess low activation energy for electron transfer between cations and improving the electronic/ionic conductivity of electrodes to further boost the kinetics of ion/charge transfer [22]. As for carbon-supported MMOF-derived composites, these carbonaceous materials (including carbon coatings and carbon nanotubes) usually arise from the in situ decomposition or catalytic formation of various organic ligand precursors [175, 176, 177, 178, 179, 180, 181, 182, 191, 192, 193, 194] to result in more intimate contact with metal-based components as compared with other carbon composites, allowing for increased structural stability and improved electronic conductivity. Here, researchers report that these enhancements as induced by these carbonaceous materials are displayed more prominently in MMOF-derived carbon composites and that based on similar reasons, MMOF-derived multi-metallic materials with yolk–shell/core–shell morphology can also exhibit enhanced functionalities and improved electrochemical performances [102, 143, 144, 145, 146, 147, 154, 157, 176, 179, 183].

3 Applications of MMOFs in LIBs and SIBs

MOFs with controllable functional ligands can provide high-performance Li/Na storage due to high porosity, huge surface areas and tunable structures and pore sizes [73, 74, 75, 76, 77, 78]. In addition, metal cations in MOFs can act as active sites for redox reactions and open crystal frameworks can offer convenient pathways for effective and reversible Li/Na insertion and extraction. Here, the highly tailored porous nature of MOFs can allow for the adsorption of electrolytes to enhance the transport of Li+/Na+ and the high surface area of MOFs can shorten Li+/Na+ diffusion lengths, provide more active sites and reduce electrolyte resistances. In addition, the nanosized building blocks of MOFs with increased exposed atoms are also beneficial for electrolyte migration and Li+/Na+ diffusion [74, 75, 76, 77]. Thus far, researchers have proposed two main Li/Na storage mechanisms for MOFs used directly as electrodes for LIBs and SIBs [202] in which one is a conversion mechanism with metal ions in MOFs being reduced by Li+/Na+ to generate metals at the early stage, followed by the reversible conversion between metals and metal ions (alloying reaction). This mechanism is comparable to the conversion mechanism of well-known transition metal oxide/sulfide anodes for LIBs and SIBs in which reversible conversion reactions between transition metal oxides/sulfides and metal, and Li/Na oxides and sulfides occur [9]. The other proposed Li/Na storage mechanism is an insertion mechanism involving Li+/Na+ insertion into MOF pores without direct metal valence change and is comparable to the insertion mechanism of carbonaceous materials and titanium-based oxide electrodes. Here, researchers report that superior Li/Na storage performances and enhanced cycling properties can be achieved for MOF electrodes based on the conversion mechanism [74] in which for MOF electrodes with the conversion mechanism, variable-valence metal ions and/or organic ligands rich in functional groups can strongly interact with Li+/Na+ to improve electrochemical properties.

Compared with monometallic systems, MMOF materials possess more flexible morphology and/or dimension control. For example, Wang et al. [91] reported that the design of a ZIF-8 seed layer on a ZnO template enabled the uniform growth of various MMOF materials (Zn/Co-ZIF) with different dimensions (1D, 2D and 3D) (Fig. 1a). Furthermore, multi-metal centers in MMOF electrodes can provide richer redox chemistries, facilitate interlayer diffusions and improve electronic conductivity and structural stability, resulting in enlarged reversible capacities and high rate capabilities. In addition, the pore size distribution and surface area properties of MMOFs can be adjusted through the modulation of the molar ratios of metal components, resulting in enhanced Li+/Na+ transfer and alleviated volume change during cycling. And as a result of this, this section will concentrate on MMOF electrodes for LIBs and SIBs with enhanced properties and new structural designs that have been reported in recent years [91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103] and provide a summary of their electrochemical performances (Table 1).
Fig. 1

Bimetallic core–shell Zn/Co-ZIF. a Schematic of the growth of bimetallic Zn/Co-ZIF core–shell structures by using ZnO nanowires as a template under different precursor addition sequences. Reprinted with permissions from Ref. [91], copyright 2018, Wiley-VCH. Bimetallic Co/Zn-MOF. b Schematic of the preparation process. c TEM image. d Cycling performance at 100 mA g−1. e Rate capability. Reprinted with permissions from Ref. [97], copyright 2016, Royal Society of Chemistry

As a typical crystalline MOF, Prussian blue (PB) and Prussian blue analogues (PBAs) with a formula of M 3 II [MIII(CN)6]2·nH2O (M = Fe, W, Mn, Ni, Co, Zn, etc.) can be easily obtained at room temperature in water/ethanol systems and are among the most popular MOFs for LIB and SIB electrodes. This is because based on the reversible redox reaction of FeIII/FeII or WV/WIV, several Fe/W-involved multi-metallic PBA structures with variable-valence Fe/W centers can be used as electrodes based on the conversion mechanism for Li/Na storage [92, 93, 94, 95, 96]. In addition, Zn/Co-BDC MOFs [97], cobalt-doped Mn/Co-BTC MOFs [98] and Fe/Co-TPDC MOFs [99] have also been synthesized and used as anodes based on the insertion Li storage mechanism. Here, Zn/Co-BDC MOF particles [97] can be obtained from MOF-5 modified by Co(II) and can exhibit excellent electrochemical properties in terms of enhanced cycling performance in which a reversible capacity of 1211 mAh g−1 can be retained after 100 cycles at 100 mA g−1 and high rate properties can be achieved if used as an anode material for LIBs (Fig. 1b–e). Cobalt-doped Mn/Co-BTC anodes [98] can also achieve a high reversible capacity of 901 mAh g−1 after 150 cycles at 100 mA g−1 because Co-doping can improve both electronic conductivity and structural integrity to enhance cyclic performances. Moreover, researchers report that a 2D few-layer black phosphorus/NiCo-MOF (BP/NiCo-MOF) hybrid as a LIB anode can display enhanced electrochemical properties including a high reversible capacity of 853 mAh g−1 at 0.5 A g−1, long cycle lifespans and an excellent high-rate capability of 398 mAh g−1 retained at 5 A g−1 after 1000 cycles [100].

Aside from application as direct electrodes for LIBs and SIBs, MOF architectures can also be used as supports to load metal oxide related electrode materials [101, 102, 103]. For example, the Cr-MOF and the Cu-MOF can be used as matrixes to load SnO2 and Fe3O4 to generate SnO2@Cr-MOF [101] and Fe3O4@Cu-MOF [102] for application in Li storage and have resulted in enhanced electrochemical properties. In addition, a composite of layered Li(Li0.17Ni0.20Co0.05Mn0.58)O2 modified with the Mn-based MOF was used as a cathode and resulted in a large initial capacity of 324 mAh g−1 at 30 mA g−1 and good cyclability in which ~ 284 mAh g−1 was retained after 100 cycles. Overall, these results indicate that modified Mn-based MOF layers with open metal sites and large surface areas can strengthen bonding interactions between transition metals and oxygen and provide rich ion diffusion channels, resulting in alleviated oxygen evolutions, enhanced stability of host lattices and facilitated lithium-ion migrations [103].

Overall, MOF structures are unstable to various atmospheres and moistures, meaning that the chemical stability of MOFs suffers from severer challenges in the complex electrochemical environments of LIBs and SIBs. Therefore, thermally, chemically and structurally stable MOFs are required to obtain optimal cycling performances for LIBs and SIBs in practical applications. In addition, the electronic conductivity of MOFs is also important to achieve practical specific capacities and high rate performances. Based on this, more efforts need to be devoted to the exploration of MMOF electrodes with high electronic conductivities and improved stability despite the promising results reported already in the literature.

4 MMOF Derivatives and Their Applications in LIBs and SIBs

4.1 Multi-metallic Oxides

Aside from direct application as electrodes, MMOFs have also been widely explored as precursors to fabricate multi-metallic derivatives, especially multi-metallic oxides, as electrodes for LIBs and SIBs. Here, researchers have reported that high capacities can be achieved in monometallic oxide electrodes for LIBs and SIBs; however, the pulverization of these electrodes as a result of huge volume changes during repetitive lithiation/delithiation can lead to rapid capacity decay and poor cycling stability [20, 21]. To resolve this issue, researchers have proposed that an effective resolution is the design of multi-metallic oxide electrodes [22, 23, 24, 84, 85, 90]. This is because the coupling of multiple metal species in dual or multi-metallic systems can lead to richer redox reactions and improved electronic conductivities as compared with corresponding monometallic systems. In addition, multi-metallic components can also facilitate stepwise Li/Na storage, which is a Li/Na insertion and extraction reaction occurring at different voltages for two or more components, in which volume change in one active component within a corresponding voltage range can be buffered by the inactive component at this voltage. This phenomenon is similar to what occurs in well-known Sn–Sb alloy systems for stepwise Li storage and can allow for the effective control of electrode volume change and enhanced cycling performance. Overall, the regular Li/Na storage mechanism of bimetal oxides (AxB3−xO4, A/B = Co, Ni, Fe, Cu, Zn, Mn, etc., A ≠ B) can be described as follows:
$$ {\text{A}}_{x} {\text{B}}_{3 - x} {\text{O}}_{4} + 8{\text{Li}}^{ + } + 8{\text{e}}^{ - } \leftrightarrow x{\text{A}} + \left( {3 - x} \right){\text{B}} + 4{\text{Li}}_{2} {\text{O}} $$
(1)
$$ {\text{A}}_{x} {\text{B}}_{3 - x} {\text{O}}_{4} + 8{\text{Na}}^{ + } + 8{\text{e}}^{ - } \leftrightarrow x{\text{A}} + \left( {3 - x} \right){\text{B}} + 4{\text{Na}}_{2} {\text{O}} $$
(2)

And due to this mechanism, multi-metallic oxides can exhibit higher electronic conductivities and improved electrochemical activities as compared with monometallic ones. However, the fabrication of multi-metallic oxides remains challenging due to the difficulty of achieving uniform metal species distribution and morphology [24]. Here, researchers have reported that MMOF-derived approaches are effective strategies to synthesize multi-metallic oxides with inherited porous characteristics with many studies being conducted on MMOF-derived multi-metallic oxides and composites as electrode materials for LIBs and SIBs [104, 105, 106, 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, 169, 170, 171, 172, 173, 174]. In this review, however, more recent MMOF-derived multi-metallic oxide electrodes possessing superior electrochemical properties will be presented (Table 2).

Besides direct usage as MMOF electrodes, Prussian blue (PB) and Prussian blue analogues (PBAs) are popular MOF precursors to derive multi-metallic oxides. Here, multi-metallic oxides can be synthesized from PB or PBA precursors by using two different approaches, in which one is a direct templated reaction between PB (Fe3[Fe(CN)6]2·nH2O) and different substances. And based on this templated reaction between Prussian blue (PB) precursors and different substances [ZnAc2, Cu(NO3)2 or MgAc2], several Fe-involved dual-metallic oxides have been fabricated as anodes for LIBs and SIBs [104, 105, 106, 107]. For example, Yang et al. synthesized a porous ZnO–ZnFe2O4 nanoparticle electrode [104] using the direct template reaction between PB and ZnAc2 and reported that if used as a LIB anode, this electrode can exhibit good Li storage performances with an initial charge capacity of 826 mAh g−1 and a retained capacity of 803 mAh g−1 after 500 cycles at 1 A g−1. Here, these researchers attributed the excellent performances to the porous structure of the combined nanoparticles, which can provide more transportation channels for lithium ions and effectively buffer volume expansion during cycling, resulting in enhanced properties for the ZnO–ZnFe2O4 anode. The other method to fabricate multi-metallic oxides is a direct transformation from as-synthesized multi-metallic PBA precursors [108, 109, 110, 111, 112, 113, 114, 115] in which more reports on PBA-derived dual-metallic oxide electrodes for LIBs and SIBs are based on as-synthesized bimetal PBA structures consisting of Fe ions and other metal ions [108, 109, 110, 111, 112, 113]. For example, among reported PBA-derived Fe/Zn-based dual-metallic oxide electrodes [108, 109, 110], Hou et al. obtained mesoporous molecular two-component-activated ZnO–ZnFe2O4 (ZZFO) sub-microcubes [108] through a self-sacrificing templated synthetic process using Zn3[Fe(CN)6]2 cubes and reported attractive Li storage properties in which as compared with single-phase ZnFe2O4 anodes, superior Li storage properties (initial charge capacity of ~ 1371 mAh g−1 and a retained capacity of ~ 837 mAh g−1 after 200 cycles at 1 A g−1) can be achieved for the ZZFO anode. Here, these researchers ascribed these performances to the unique microstructural characteristics of the ZZFO anode and the synergistic effects between the two active components (ZnO and ZnFe2O4). Furthermore, Fe-involved trimetallic oxides derived from PB or PBA precursors have also been reported as electrodes for LIBs and SIBs [114, 115] in which Huang et al. [114] successfully synthesized a Fe2O3@NiCo2O4 porous nanocage composite through the stepwise growth and subsequent annealing of PBAs. Here, theses researchers reported significantly enhanced specific capacities with an initial charge capacity of ~ 903 mAh g−1 and cycling performances with ~ 1080 mAh g−1 retained after 100 cycles at 100 mA g−1. Aside from Prussian blue (PB) and Prussian blue analogues (PBA), other MMOF precursors, obtained through the coordination of multi-metal ions with ligands such as 2-methylimidazolate (2-mIM), 1,4-benzenedicarboxylic acid (BDC) and 1,3,5-benzenetricarboxylic acid (BTC) [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], can also generate a variety of hollow/porous multi-metallic oxides through thermal treatment to deliver interesting electrochemical properties as electrodes for LIBs and SIBs. For example, Li et al. [138] conducted a one-step microwave-assisted synthesis of Co/Ni dual-metallic MOF-74 nanorods to obtain derived nanoparticle (~ 20–40 nm in size)-integrated mesoporous Co–Ni–O (Ni0.3Co2.7O4) nanorods (Fig. 2a–d). Here, the researchers used the obtained Co–Ni–O nanorods as a LIB anode and reported a larger-than-theoretical reversible capacity of 1410 mAh g−1 after 200 repetitive cycles at 100 mA g−1 with excellent high-rate capabilities in which large reversible capacities of 812 and 656 mAh g−1 were retained after 500 cycles at large currents of 2 and 5 A g−1, respectively (Fig. 2e, f). In this study, the superior electrochemical performances were attributed to the interconnected nanoparticle-integrated mesoporous rod-shaped structure and the synergistic effects between the two active metal oxide components.
Fig. 2

Mesoporous Co–Ni–O nanorods with a Co/Ni molar ratio of 9:1. a Schematic showing the one-step microwave-assisted synthesis of a bimetal–organic framework precursor and the formation of mesoporous Co–Ni–O nanorods for Li storage applications. b SEM image. c and d TEM images. e Cycling performances compared with Co–Ni–O–B (Co:Ni = 2:1) and Co3O4 at 100 mA g−1 (0.1 C). f High-rate cycling performances.

Reprinted with permissions from Ref. [138], copyright 2016, Wiley-VCH

Metal oxide electrodes with core–shell or yolk–shell morphology can provide void spacing to buffer the large volume change of electrodes during repetitive Li/Na insertion and extraction. And because of core–shell/yolk–shell morphology, many MMOF-derived multi-metallic oxides can exhibit improved electrochemical performances as electrodes for LIBs and SIBs [143, 144, 145, 146]. For example, Guo et al. [145] used microwave irradiation to obtain Cu–Ni-BTC precursors through the control of cation exchange between Cu ions and preformed Ni-MOFs and reported that the intermediate product of Cu–Ni-BTC can be subsequently converted into multilayer hollow CuO@NiO microspheres after calcination (Fig. 3a). Here, the CuO@NiO microspheres exhibited a three-layer ball-in-ball hollow morphology with an interconnected nanoparticle-integrated multi-shell structure (Fig. 3b) in which the Ni content increased from the exterior first ball to the core third ball because more Ni ions on the exterior surface were substituted by Cu ions as compared with interior Ni ions in the Cu–Ni-BTC MOF. These researchers also reported that the MMOF-derived synthesis approach led to dual-modal pores in the CuO@NiO product in which hydrophobic inter-particle mesopores can provide large electrochemically active surface areas and more active sites for Li storage, and large macroporous void spaces (~ 100–200 nm in size) can facilitate electrolyte infusion and ion/electron transport. In addition, these mesopores and macropores can also buffer large electrode volume change during cycling. Furthermore, because lithium insertion occurs at a higher voltage of ~ 1.2–1.1 V for CuO and a lower voltage of ~ 0.7–0.6 V for NiO, these stepwise electrochemical reactions coincided with the structural design of CuO@NiO in the composite, and as a result, superior Li storage performances in terms of large capacities and enhanced cycling performances (reversible capacities of 856 mAh g−1 for the first cycle and 1061 mAh g−1 retained after 200 cycles at 100 mA g−1) were achieved for the multilayer CuO@NiO microsphere anode (Fig. 3c). Geng et al. [146] also derived a 1D Co3O4@TiO2 core–shell structure composed of a Co3O4 particle-interconnected inner core and a TiO2 outer shell from Co-MOFs with polydopamine and TiO2 layers. Here, the researchers reported that the unique core–shell characteristics of the Co3O4@TiO2 composite can enhance electronic conductivity, lithium ion mobility and structural stability during cycling in which the Co3O4@TiO2 core–shell anode material achieved excellent cyclability (high initial capacity of ~ 850 mAh g−1 and a retained capacity of ~ 803 mAh g−1 after 100 cycles at 200 mA g−1) and good high-rate performances (~ 520 mAh g−1 at 1000 mA g−1). Moreover, Co-involved trimetallic oxide electrodes can also be derived from ZIF-based precursors and used as anode materials for LIBs to allow for good electrochemical properties [147, 148, 149, 150, 151]. For example, Song et al. [149] synthesized a 3NiO·2Ni3/2Co1/2ZnO4 electrode with hollow dodecahedron morphology from Zn/Co-ZIFs precursors and reported excellent electrochemical properties (reversible capacities of 1263 mAh g−1 for the first cycle and ~ 1337 mAh g−1 after 100 cycles at 200 mA g−1).
Fig. 3

Multilayer hollow CuO@NiO microspheres. a Schematic showing the cationic exchange process of the MOF precursor and its conversion to a multilayer hollow structure. b TEM image. c Cycling performances at 100 mA g−1.

Reprinted with permissions from Ref. [145], copyright 2015, American Chemical Society

To achieve structural advantages and synergistic effects, multi-metallic oxide composites with carbonaceous materials have also attracted significant attention because these composites can improve physical and chemical properties in which through the introduction of carbon matrixes, improved conductivity can be attained. In addition, the presence of carbon materials can effectively buffer volume change and avoid electrode pulverization during cycling, resulting in better cycling performances. As a result, various carbonaceous materials such as porous carbon layers, carbon nanotubes (CNTs), carbon nanofibers (CNFs), graphene and corresponding derivatives have been explored with MMOF-derived multi-metallic oxides for LIBs and SIBs [152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174]. For example, Zou et al. [160] selected Fe III-modified MOF-5 octahedra as the precursor and self-sacrificing template to produce porous ZnO/ZnFe2O4/C octahedra composed of ZnO and ZnFe2O4 ultrafine nanocrystals (less than 5 nm in size) embedded into the framework of 3D interconnected porous carbon. And as a result, the porous ZnO/ZnFe2O4/C hollow octahedra showed excellent electrochemical Li storage properties (high capacity, high power and long life) in which excellent cycling performances (1390 mAh g−1 after 100 cycles at 500 mA g−1) and rate capabilities (934, 887 and 842 mAh g−1 at 1, 2 and 5 A g−1, respectively) can be achieved. Here, the researchers attributed these performances to the superfine nanocrystals and the elastic carbon network as well as the hollow structure and high porosity. In addition, multi-metallic oxides trapped in N-doped carbon composites can also be derived from MOF precursors containing N-containing organic ligands [153, 157, 158, 159]. For example, Qiu et al. [168] synthesized a Mo0.8W0.2O2–Cu@P-doped carbon nanohybrid through the controlled pyrolysis of multi-metallic Mo/W/Cu-MOF composed of Mo- and W-based polyoxometalate in the framework of the Cu-BTC MOF. Here, the obtained nanohybrid electrode provided an initial charge capacity of 770 mAh g−1 that was retained at 911 mAh g−1 after 250 cycles at 500 mA g−1 along with exceptionally long cycle lifespans (2000 cycles) and slow capacity losses (0.043% per cycle) at a large current density of 5 A g−1. These researchers concluded in this study that the synergistic multi-doping effects in the composite of Mo0.8W0.2O2 nanocrystallites homogeneously dispersed in Cu and P co-doped carbon nano-octahedrons can greatly accelerate charge transfer, enhance lithium diffusion kinetics and improve structural stability. Aside from these electrode materials, it is worth mentioning that only few reports exist for multi-metallic oxide electrodes with CNTs, CNFs or graphene [169, 170, 171, 172, 173, 174] derived from MMOF precursors, and therefore, more efforts need to be devoted to the effective combination of MOF or MMOF precursors with additional CNTs, CNFs or graphene and their transformation into multi-metallic oxides with CNT/CNF/graphene composite electrodes for enhanced Li/Na storage.

4.2 Multi-metallic Sulfides/Selenides/Phosphides/Carbides

In addition to metal oxide electrodes, metal sulfides/selenides/phosphides with unique physical and chemical properties have also been investigated as promising electrode materials for LIBs and SIBs in which Li/Na storage can be achieved through the reversible conversion reaction:
$$ {\text{M}}^{n + } \left( {\text{X}} \right) + n{\text{e}}^{ - } + n{\text{Li}}^{ + } / {\text{Na}}^{ + } \leftrightarrow {\text{M}}^{0} + n{\text{Li/Na}}\left( {\text{X}} \right)\quad \left( {{\text{X}} = {\text{S}},{\text{Se}},{\text{P}}} \right) $$

And to improve poor cycling stability caused by large volume change and the resulting electrode pulverization during repeated Li/Na insertion and extraction, the design of porous metal sulfide/selenide/phosphide electrodes along with carbonaceous material supports has been shown to be the most effective strategy, allowing for alleviated structural strain during cycling and further enhanced cyclability [28, 29]. In addition, the synergistic effects between two or more different metal components in multi-metallic sulfide/selenide/phosphide electrodes can also effectively alleviate volume expansion of electrodes during cycling. However, few studies have focused on MMOF-derived multi-metallic sulfides/selenides/phosphides [175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189], possibly due to complex synthesis processes and difficulty in morphology and porosity control. (Electrochemical performances for MMOF-derived multi-metallic sulfides/selenides/phosphides reported in the literature are summarized in Table 3.)

Multi-metallic sulfides/selenides/phosphides can be obtained with carbonaceous supports through MMOF-derived approaches because sulfidation/selenization/phosphorization processes are often performed with sulfur/selenium/phosphor powder in inert atmospheres. Based on MMOF precursors consisting of N-containing organic ligands such as cyanides or 2-methylimidazole, LIB electrodes of multi-metallic sulfides trapped in N-doped carbon [178, 179, 181] can be obtained with nitrogen doping directly derived from N-containing organic ligands. Besides, the multi-metallic sulfide@N-doped carbon (Ni3S2–Co9S8@N-doped C) electrodes [180] can also be fabricated from Ni–Co-BTC MOF precursors with the assistance of N-containing polyvinylpyrrolidone (PVP). In addition, directly mixed precursors of MMOFs with carbon nanotubes (CNTs) as well as in situ CNT growth during the derivation of MOFs through the decomposition of hydrocarbon gas with metal catalysts have also been reported to be effective approaches to introduce CNTs into multi-metallic sulfide-carbon composites, allowing for enhanced Li/Na storage performances due to improved electronic conductivity and structural stability based on the effects of carbon and CNTs [181, 182]. For example, Wang et al. [181] derived dual-metallic sulfide products with carbon and CNTs (Co–Zn–S@N–S–C–CNT) from dual-metallic MOFs (Co/Zn-ZIF) through a two-step reaction involving chemical vapor reduction/deposition and sulfidation (Fig. 4a–d) in which the Co–Zn–S@N–S–C–CNT product consisted of small CNTs rooted in the mesoporous CoS2/Zn0.975Co0.025S dodecahedron with a N and S co-doped carbon overlayer (Fig. 4d). And applied as a LIB anode, this Co–Zn–S@N–S–C–CNT composite reportedly exhibited highly reversible and large capacities (941 mAh g−1 after repetitive 250 cycles at 100 mA g−1) and improved rate capabilities (734, 591 and 505 mAh g−1 retained after 500 cycles at large current densities of 1, 2 and 5 A g−1, respectively) as compared with monometallic CoS2@N–S–C–CNT products (Fig. 4e, f). Here, the researchers ascribed the excellent Li storage performances to the porous structure derived from the MMOF precursors, the presence of N and S co-doped carbon matrixes and CNT networks and the synergistic effect between the two metal species. Moreover, extruded small CNTs from the products can further enhance electronic conductivity and structure stability through the bridging of neighboring metal sulfide particles and by acting as “spacers” to prevent agglomeration during cycling. Park et al. [183] also fabricated multi-metallic selenide void@CoSe2@void@(NiCo)Se2 (Co/(NiCo)Se2) without carbon supports from cube-shaped ZIF-67/Ni–Co layered double hydroxides with a yolk–shell structure and reported that the Co/(NiCo)Se2 composite exhibited unique box-in-box hollow nanocube morphology that provided enhanced intimate electrolyte penetration and rapid mass/ion transport along with shortened ion diffusion lengths. In addition, the large voids between shells can also alleviate electrode volume expansion during cycling. And if applied as a SIB electrode, the Co/(NiCo)Se2 electrode can deliver a high initial discharge capacity (661 mAh g−1 at 0.2 A g−1) and good cycling stability. Furthermore, Zn-, Co- and Ni-based multi-metallic selenides with carbon and CNTs/graphene have also been reported based on MMOFs and have been adopted for LIB and SIB applications [184, 185, 186, 187].
Fig. 4

Co–Zn–S@N–S–C–CNT rhombic dodecahedra consisting of small carbon nanotubes rooted in the mesoporous CoS2/Zn0.975Co0.025S dodecahedron with a N and S co-doped carbon overlayer. a Schematic showing the bimetallic ZIF-derived synthesis approach. b SEM image of Co/Zn-ZIF. c TEM image of the intermediate product of Co/Co3ZnC@N–C–CNT. d TEM image of Co–Zn–S@N–S–C–CNT. e Cycling performances compared with CoS2@N–S–C–CNT at 100 mA g−1 (0.1 C). f High-rate cycling performances

Reprinted with permissions from Ref. [181], copyright 2016, Wiley-VCH

A few multi-metallic phosphides derived from MMOF precursors have also been reported and used as electrodes for LIBs and SIBs [188, 189]. For example, Yin et al. [189] obtained an intermediate product of GO@Co(OH)2@PB from Prussian blue (PB) precursors in the presence of graphene oxide (GO) nanosheets and through a subsequent phosphorization process, fabricated unique core–shell porous FeP@CoP phosphide microcubes interconnected by reduced graphene oxide nanosheets (RGO@CoP@FeP) and applied this as an anode material for SIBs. As a result, these researchers reported improved reversible capacities (initial charge capacity of ~ 551 mAh g−1 at 100 mA g−1), cycling stability (~ 456 mAh g−1 retained after 200 cycles) and rate capabilities and attributed these enhanced electrochemical performances to the synergistic effect between the unique porous core–shell structure and the multi-metallic phosphide components, in which the core–shell structure can shorten Na+ diffusion pathways and provide enough buffer space for volume change whereas the interconnected RGO nanosheets and carbon layers wrapped around the FeP core can improve the electronic conductivity of the electrode and enhance charge transfer kinetics. In another study, Chen et al. [190] synthesized a multi-metallic carbide from the direct decomposition of MMOFs for LIBs in which the hierarchical Co3ZnC/CNT-NCCPs composite with ultrafine Co3ZnC nanoparticles embedded in N-doped carbon or located at the tips of the in situ formed CNTs was fabricated through the direct pyrolysis of Co/Zn-ZIF (Fig. 5a). Here, the researchers reported that the hierarchical structure along with the existence of N-doped carbon and CNTs in the composite can alleviate volume variation and Co3ZnC nanoparticle aggregation during cycling and provide fast electron transportation (Fig. 5b–d). As a result, the composite as a LIB anode delivered a high reversible capacity (~ 800 mAh g−1 at 0.5 A g−1), outstanding high-rate capacity (408 mAh g−1 at 5.0 A g−1) and long-term cycling performance (585 mAh g−1 after 1500 cycles at 2.0 A g−1) (Fig. 5e, f). In addition, these researchers also reported that this Co3ZnC/CNT-NCCPs composite can exhibit excellent electrochemical performances (~ 494 mAh g−1 retained after 200 cycles at 0.2 A g−1) as a SIB anode (Fig. 5g, h).
Fig. 5

Hierarchical Co3ZnC/CNT-NCCP concave-polyhedron composite with Co3ZnC nanoparticles embedded in CNTs and N-doped carbon. a Schematic of the synthesis process. b and c SEM images. d TEM image. e Cycling performances at 0.5 A g−1 and f rate performances at various rates from 0.5 to 5.0 A g−1 as a LIB anode. g Cycling performances at 0.2 A g−1 and h rate capabilities at various current densities from 0.2 to 2.0 A g−1 as a SIB anode.

Reprinted with permissions from Ref. [190], copyright 2016, American Chemical Society

Overall, compared with widely reported MMOF-derived multi-metallic oxide electrodes, more attention should be paid to MMOF-derived multi-metallic sulfides/selenides/phosphides/carbides in the future in which the harsh synthesis processes and resulting morphological changes along with the structural collapses in the transformation process need to be resolved. Here, researchers propose that MOFs with good chemical and thermal stability such as ZIFs and MILs can be selected as MMOF precursors to preserve structural integrity during sulfidation, phosphorization, selenization or other transformation processes with suitable experimental conditions. However, facile and available transformation strategies under ambient temperatures and pressures, such as liquid-phase sulfidation, need to be further explored to fabricate well-inherited products with unbroken architectures [203, 204].

4.3 Alloys and Others

Aside from MMOF-derived multi-metallic oxide/sulfide/selenide/phosphide/carbide electrodes, other MMOF-derived alloys such as Li-based compounds and their carbonaceous composites have also been reported as electrodes for LIBs and SIBs [191, 192, 193, 194, 195, 196, 197, 198, 199]. (Their electrochemical performances are summarized in Table 4.) For example, researchers have reported that Sn/Sb-based alloy compounds (MxSn or MxSb, M = Co, Ni, Cu, Fe, Ti, etc.) are promising alloy electrodes for LIBs and SIBs due to large specific capacities and high Coulombic efficiencies. In addition, these Sn/Sb-based alloy compounds can generate less active metals (M) after initial lithiation to buffer Sn/Sb volume expansion during subsequent lithiation to result in enhanced structural stability and cycling performance. Moreover, the introduction of carbonaceous materials can further improve the electronic conductivity and structural stability of these alloy compounds. Currently, however, only a few MMOF-derived Sn/Sb-based alloy compounds [192, 193, 194, 195] have been reported as electrodes for LIBs and SIBs with most involving alloy composites with carbonaceous materials such as carbon, N-doped carbon or CNTs [192, 193, 194]. For example, Dai et al. [192] obtained alloy-involved porous composites (Ni–Sn@C–CNT, Ni–Sn–P@C–CNT, Ni–Sn@C and Ni–Sn–P@C, Fig. 6a) derived from Ni–Sn-BTC MMOF precursors and reported that the main product of Ni–Sn–P@C–CNT exhibited unique ball-cactus-like microsphere morphology of carbon-coated NiP2/Ni3Sn4 with deep-rooted CNTs, which were grown based on the in situ catalysis effect of Ni–Sn alloy (Fig. 6b, c). And as a result, the Ni–Sn–P@C–CNT composite delivered a larger reversible capacity of 704 mAh g−1 after 200 cycles at 100 mA g−1 and excellent high-rate cycling performances with a stable capacity of 504 mAh g−1 retained after 800 cycles at 1 A g−1 as compared with benchmark products of Ni–Sn@C–CNT and Ni–Sn–P@C (Fig. 6d, e). Here, the researchers attributed these enhanced electrochemical properties to the unique 3D mesoporous structure along with the dual active components showing synergistic electrochemical activities within different voltage windows as well as the effects of carbon coating and deep-rooted CNTs. Researchers also report that Sn/Sb-based alloy composites can be fabricated from precursors of MOFs with SnCl4 or SbCl3 [193, 194]. For example, Shi et al. [193] synthesized a Sn–Co@N–C microbox with Sn–Co nanoalloys embedded in porous N-doped carbon using ZIF-67 as the template and carbon source. In addition, Chen et al. [195] synthesized a ternary nanoporous Sn–In–Ni alloy network through a facile reduction process of as-prepared Sn(IV)–In(III)–Ni(II)–Co(III) cyanogel precursors as an anode material for LIBs. And as compared with Sn–Ni and In electrodes, this nanoporous Sn–In–Ni ternary alloy network demonstrated improved Li storage performances (~ 618 mAh g−1 after 200 cycles at 100 mA g−1), which the researchers attributed to the unique self-assembled 3D nanoporous network and the contained multiple functional components. Huang et al. [196] also fabricated porous dual-metallic Co/Zn embedded N-doped carbon (Co–Zn/N–C) polyhedral nanocages through the annealing of ZIF-8@ZIF-67 under inert atmosphere and reported excellent cyclic stability (702 mAh g−1 after 400 cycles at 200 mA g−1) and good rate capabilities (444 mAh g−1 obtained at 2 A g−1). Here, the researchers attributed the improved electrochemical performances to the synergistic effects of metallic Zn and Co as well as to the unique porous hollow structure with N doping that can resist volume change, enhance electronic conductivity and strengthen the electrochemical activity of Li storage. Furthermore, a Li-involved trimetallic LiNi0.5Mn1.5O4 material with octahedron morphology was also obtained from a BDC-based MOF precursor for use as a LIB cathode [197], and a carbon-coated Li4Ti5O12 composite with tablet-like morphology [198] and a nitrogen-doped carbon-coated Li2ZnTi3O8 composite [199] were also obtained from MMOF precursors for used as LIB anode materials.
Fig. 6

Ball-cactus-like microspheres of Ni–Sn–P@C–CNT with carbon-coated NiP2/Ni3Sn4 and deep-rooted CNTs. a Schematic showing the growth process of Ni–Sn–P@C–CNT and the benchmark Ni–Sn–P@C. b, c SEM images of Ni–Sn–P@C–CNT. d Cycling performances of Ni–Sn–P@C–CNT, Ni–Sn@C–CNT and Ni–Sn–P@C composites at 100 mA g−1. e Rate capabilities of Ni–Sn–P@C–CNT and Ni–Sn–P@C at different current densities

Reprinted with permissions from Ref. [192], copyright 2017, Wiley-VCH

5 Summary and Outlook

The development and control of electrode materials with optimal structures and compositions are the crucial issues in the fields of LIBs and SIBs to achieve highly effective electrochemical energy conversion and storage [16]. Based on this, the majority of recent research on MMOFs for LIB and SIB applications has been dedicated to MMOF-derived multi-metallic materials (multi-metallic oxides/sulfides/phosphides/selenides/carbides/alloys, etc.) and their carbon-based composites by using MOFs as precursors or sacrificial templates. This is because as induced by MOF-templated precursors, MMOF-derived multi-metallic materials and their carbonaceous composites can exhibit well-inherited morphology and porous characteristics or facile designable yolk/core–shell hollow structures. In addition, the homogenous pores of these MMOF-derived materials possess hydrophobic characteristics, which can provide more active sites and shortened pathways for Li/Na diffusion and can enhance reversible Li/Na storage in organic electrolytes. Moreover, MMOF-derived multi-metallic materials and their carbon-based composites can provide richer redox chemistries, make use of the advantages of different components and offer synergistic effects through the reinforcement or modification of each other, resulting in enhanced structural stability and cyclability. This is especially the case in Li/Na reactions with multi-metallic components at different voltages and can lead to alleviated volume expansion during cycling due to stepwise Li/Na storage, in which inactive components can act as buffering materials during Li/Na insertion and extraction involving active components [84, 85, 86, 87, 88, 89, 90, 138, 145, 181]. Lastly, MMOF-derived multi-metallic materials can provide more structural and compositional tuning and can therefore improve the electronic/ionic conductivity of electrodes to further boost charge transfer and ion diffusion kinetics [22].

MMOF-derived multi-metallic oxides have also been widely investigated as electrode materials for LIBs and SIBs due to high theoretical capacities, environmental friendliness and high chemical stability, in which facile synthesis processes (mostly through simple pyrolysis in air) of MMOFs can endow derived multi-metallic oxides with tunable physical/channel structures and high surface areas inherited from MMOF precursors. As a result, MMOF-derived multi-metallic oxides possess more active Li/Na storage sites and abundant Li/Na diffusion pathways with facilitated electrolyte infusion to enhance reversible capacities and cycling performances. Despite these promising characteristics, however, MMOF-derived multi-metallic oxides also possess poor intrinsic electrical conductivities as well as rapid capacity decay with repetitive Li/Na insertion and extraction and poor rate properties. Here, researchers report that various types of carbonaceous materials such as porous carbon layers, carbon nanotubes, carbon nanofibers, graphene and derivatives can be implemented to improve electrical conductivity, buffer volume expansion and avoid electrode pulverization during cycling in MMOF-derived multi-metallic oxides. Furthermore, the Li/Na storage potential for metal species in MMOF-derived multi-metallic oxides needs to be considered because multi-metallic species with obviously different Li/Na storage potentials can enhance synergistic effects and further alleviate volume variation in electrodes during cycling. As for MMOF-derived multi-metallic sulfides/selenides/phosphides/carbides and other related materials, enhanced electrical conductivity can originate from carbonaceous material combinations and synergistic effects between two different metal species. In addition, synthesis approaches for multi-metallic sulfides/selenides/phosphides/carbides and other related materials from MMOF precursors need to be optimized to fabricate well-inherited products with unbroken architectures. Furthermore, of these MMOF-derived multi-metallic sulfides/selenides/phosphides/carbides and other related materials, high electrical conductivity, theoretical capacity and initial Coulombic efficiency can usually be achieved for sulfides/selenides/phosphides/carbides, whereas MMOF-derived alloys and Li-based compounds can allow for high thermal stability, large specific capacity and high safety.

Overall, promising results have been achieved for various MOF-derived multi-metallic electrodes for LIBs/SIBs; however, various challenges remain, including the following:
  1. 1.

    Investigations on MMOFs with multiple-type metal species and derived multi-metallic compounds/composites are still comparatively scarce due to the difficulty in the synthesis of MMOFs and the uniform control of species distribution and morphology in their derivatives. And although numerous MOFs (more than 20,000) have been reported with a variety of metal clusters and organic linkers [48, 49, 50, 51, 52, 53, 54], only a small fraction of existing MOF structures obtained through conventional synthetic methods have been explored to fabricate MMOFs as electrodes or precursors to obtain multi-metallic derivative electrodes for LIBs and SIBs. Therefore, the design of novel MMOFs through the optimization of multi-functional linkage characteristics between organic ligands and multi-metal ions for optimal electrochemical properties is highly desirable. Here, effective Li/Na storage in MMOFs mainly depends on corresponding nanostructure design, in which MMOF particle size, active surface areas, pore size distribution, crystallinity and availability of functional groups can all affect conductivity. In addition, low molecular weight ligands (desirable for high storage capacity) and robust frameworks with open channels (facilitating rapid Li/Na transport) are also key requirements for novel MMOF materials. Moreover, additional Li/Na storage per unit for MMOFs based on multi-electron or multiple redox centers can effectively increase reversible capacities, but requires enhanced rigidity and robustness in MMOFs with variable-valence metal ions and/or multiple redox organic ligands. MMOF structures with tunable structures can also improve electronic conductivity [74, 75, 76, 77]. And compared with Li storage, MMOF-related electrode materials for Na storage require more open frameworks to achieve sufficient Na mobility due to the larger size of Na ions. Therefore, further investigations should search for more MOF structures or strategies to design MMOFs with versatile morphology, porous characteristics and/or advantageous functional groups. In addition, the introduction of guest compounds into monometal–organic framework pores also needs to be explored as an effective strategy to fabricate multi-metallic compounds [101, 102, 103, 163, 193, 198]. Aside from crystalline MOF structures, amorphous MOFs also possess attractive properties not found in crystalline materials [205, 206, 207, 208, 209] in which due to less packed solids, amorphous structures can provide better transport of ionic species and improve electrode reaction kinetics during electrochemical reactions [76]; therefore, more attention should also be paid to amorphous MMOFs and their derived electrodes for application in LIBs and SIBs.

     
  2. 2.

    Li/Na storage mechanisms based on variable-valence metal ions, organic ligands and porous structures in MMOFs need to be further explored and more efforts need to be devoted to the in-depth exploration of accurate active sites for extra Li/Na storage. In addition, the poor electronic conductivity of MMOFs is another significant limitation affecting practical application in LIBs and SIBs, especially in terms of high rate performances [92, 93, 94, 95, 96, 97, 98, 99]. Furthermore, multi-metallic electrodes with carbonaceous composites are needed to achieve improved electronic conductivity, Li/Na diffusion and structural integrity to enhance Li/Na storage properties and cycling performances. And aside from porous carbon directly derived from organic linkers of MMOF precursors, a variety of carbonaceous materials including CNTs, CNFs, graphene oxide, graphene and graphene aerogels can be used to fabricate composites with MMOFs or their derivative electrodes to maximize the advantages of MOFs and carbonaceous materials. The catalytic effects of metals from MOFs can promote the in situ formation of CNTs, graphene-like carbon coatings and carbons with doped elements such as nitrogen and sulfur [181, 192]. N/S-doped carbon can also be obtained from N-containing organic ligands or from conversion processes of MMOFs to metal sulfides in the presence of sulfur [157, 158, 159, 178, 179, 181, 186, 187, 190].

     
  3. 3.

    The in-depth understanding of the transformation process from MMOF precursors to multi-metallic derivatives in terms of elemental distribution, porosity generation, morphology conversion and compositional control is needed. In comparison with MMOF-derived multi-metallic oxide electrodes, MMOF-derived multi-metallic sulfide/phosphide/selenide/nitride/carbide electrodes also need to be explored further in the future. This is because the harsh synthesis processes, and resulting morphological changes and structural collapses in the transformation process from MMOFs to multi-metallic sulfide/phosphide/selenide/nitride/carbide derivatives remain a major challenge. Here, researchers have suggested that MOF precursors with good chemical and thermal stability as well as facile and available transformation processes under ambient temperatures and pressures can be adopted to achieve well-inherited derivatives with unbroken architectures [203, 204].

     
  4. 4.

    Large irreversible capacity losses in the first cycle are often observed for MMOFs and their derivatives mainly due to the available large surface area for undesirable electrochemical side reactions. Here, researchers suggest that this problem can be solved through surface coatings or prelithiation to achieve satisfactory Coulombic efficiencies toward practical application [5, 6]. Moreover, the establishment of mathematical models and theoretical simulations is also essential to guide the design and facile, large-scale and low-cost fabrication of MMOFs and their derivatives with superior electrochemical performances [22].

     
  5. 5.

    Currently, studies have mainly focused on the application of MMOF-based materials as electrodes for LIBs and SIBs. However, the development of MMOF-based materials for application as electrolytes, separators, lithium metal oxide cathodes and lithium–sulfur or lithium–oxygen batteries is scarce and requires more sustained and dedicated research. In addition, organic porous materials such as porous covalent organic materials (COMs) with similarly framed structures as MOFs have also been rapidly developed due to their high porosity, thermal stability, controllable structures as well as multi-functionality. And as sub-branches of COM materials, covalent organic frameworks (COFs), conjugated microporous polymers (CMPs), porous polymer networks (PPNs) and other porous organic composites [210, 211, 212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 224] can also be used as candidates of electrode materials or precursors to support metal-based components for high-performance LIBs and SIBs.

     

MMOFs and their derived multi-metallic materials are promising electrodes for LIBs and SIBs due to their excellent electrochemical properties, with significant advances being anticipated in terms of the in-depth understanding of the structure–function relationship and the conversion process from MMOF to MMOF derivatives. And overall, versatile MMOF-based materials will become an intriguing material platform to resolve current bottlenecks for LIBs and SIBs.

Notes

Acknowledgements

Funding was provided by Shanghai Municipal Education Commission (CN) Grant No. (2019-01-07-00-09-E00021) and Science and Technology Commission of Shanghai Municipality Grant No. (17010500300).

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© Shanghai University and Periodicals Agency of Shanghai University 2019

Authors and Affiliations

  1. 1.Department of Chemical Engineering, School of Environmental and Chemical EngineeringShanghai UniversityShanghaiChina

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