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化学进展 2021, Vol. 33 Issue (11): 2002-2023 DOI: 10.7536/PC200876 前一篇   后一篇

• 综述 •

金属-有机框架材料衍生转换型负极在碱金属离子电池中的应用

刘志超1, 穆洪亮1, 李艳1, 冯柳2,*(), 王东1,3,*(), 温广武1,3   

  1. 1 山东理工大学材料科学与工程学院 淄博 255000
    2 山东理工大学分析测试中心 淄博 255000
    3 山东理工大学工程陶瓷研究院 淄博 255000
  • 收稿日期:2020-08-29 修回日期:2020-11-11 出版日期:2020-12-28 发布日期:2020-12-28
  • 通讯作者: 冯柳, 王东
  • 基金资助:
    山东省自然科学基金资助项目(ZR2020QE066); 中国博士后科学基金面上项目(2020M672081); 浮法玻璃新技术国家重点实验室开放课题(2020KF08)
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Application of Metal-Organic Frameworks-Derived Conversion-Type Anodes in Alkali Metal-Ion Batteries

Zhichao Liu1, Hongliang Mu1, Yan Li1, Liu Feng2(), Dong Wang1,3(), Guangwu Wen1,3   

  1. 1 School of Materials Science and Engineering, Shandong University of Technology,Zibo 255000, China
    2 Analysis and Testing Center, Shandong University of Technology,Zibo 255000, China
    3 Institute of Engineering Ceramics, Shandong University of Technology,Zibo 255000, China
  • Received:2020-08-29 Revised:2020-11-11 Online:2020-12-28 Published:2020-12-28
  • Contact: Liu Feng, Dong Wang
  • Supported by:
    Natural Science Foundation of Shandong Province(ZR2020QE066); fellowship of China Postdoctoral Science Foundation(2020M672081); Opening Project of State Key Laboratory of Advanced Technology for Float Glass(2020KF08)

碱金属离子电池是指以Li+、Na+、K+离子为载体的二次电池,其能量密度高、使用寿命长,在电子设备、清洁能源存储中应用广泛。负极是影响电池性能的关键因素,迫切需要开发高比容量和强结构稳定性的负极。基于转换反应的金属化合物负极理论容量高、安全性好、资源丰富,然而其导电性较差,体积效应大,会损害倍率和循环性能。利用金属有机框架材料(MOFs)可以有效解决上述问题,由MOFs衍生的金属化合物优势明显:(1)孔道丰富,离子迁移快;(2)比表面大,活性位点多;(3)结构和组成可调。本文对MOFs衍生转换型负极及其在碱金属离子电池上的应用进行了系统性梳理,综述了MOFs衍生各类化合物的研究进展,总结了由MOFs制备转化型负极的性能提升策略及机理,以及应用于电池负极的优势与挑战,并对研究新趋向进行展望。

关键词： 碱金属离子电池, 负极, 金属化合物, 转换型材料, 金属有机框架衍生物

Alkali metal-ion batteries refer to secondary batteries with Li+, Na+, and K+ ions as carriers. They possess high energy density and long service life, and are widely applicated in electronic equipment and clean energy storage. Since the negative electrode plays a critical role on the electrochemical performance, it is urgent to develop high-performance negative electrode with high specific capacity and strong structural stability. It has been accepted that metal compounds anodes based on conversion-type mechanism feature with high theoretical specific capacity, good safety, and abundant resources. However, metal compounds suffer from poor electronic conductivity and obvious volume variation during charge/discharge processes, which damage the rate capabilities and cyclic performance. Using metal-organic frameworks(MOFs) as templates to fabricate metal compounds can effectively solve the above problems. MOFs-derived metal compounds possess distinct advantages when used as anodes for alkali metal-ion batteries:(1) abundant pore structures, which promote fast ion migration;(2) large specific surface area and enormous electrochemically active sites;(3) tunable structure and chemical composition. Herein, this review systematically combs the MOFs-derived conversion-type anodes and their applications in alkali metal-ion batteries. Firstly, three kinds of alkali metal-ion batteries are introduced briefly, and the research progress of various metal compounds derived from MOFs are reviewed. Then, the performance improvement strategies and mechanisms accompanied with MOFs-engaged strategy are summarized. At last, the advantages and challenges of the MOFs-derived conversion-type anodes in alkali metal-ion batteries are concluded, and the perspective of this research area is prospected.

Contents

1 Introduction

2 Alkali metal-ion batteries

2.1 Lithium-ion batteries

2.2 Sodium-ion batteries

2.3 Potassium-ion batteries

3 Metal compounds

3.1 Metal oxides

3.2 Metal sulfides

3.3 Metal selenides

3.4 Metal phosphides

3.5 Other metal compounds

4 Performance improvement strategies for MOFs-derived conversion-type anodes

4.1 Nanostructure engineering

4.2 Heterostructure engineering

4.3 Hybridization with carbon

5 Conclusion and outlook

Key words: alkali metal-ion batteries, anodes, metal compounds, conversion-type materials, MOFs derivatives
()
图1 (a)Li、Na、K 3种元素的性质对比图;文献报道的(b)LIBs[14,17,32⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓~46]、(c)SIBs[23,26,37,47⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓~61]、(d)PIBs[19,24,25,62⇓⇓⇓⇓⇓⇓⇓⇓~71]负极材料在100 mA·g-1下的电化学性能
Fig. 1 (a) Comparison of the properties of Li, Na, and K; the electrochemical performance of anode materials for(b) LIBs[14,17,32⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓~46],(c) SIBs[23,26,37,47⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓⇓~61] and(d) PIBs[19,24,25,62⇓⇓⇓⇓⇓⇓⇓⇓~71] at 100 mA·g-1 reported in the literatures
图2 MOFs衍生金属氧化物:纺锤状多孔α-Fe2O3的(a)TEM图和(b)倍率性能[89];(c)NCO@NCS复合材料的制备示意图[34]
Fig. 2 MOFs-derived metal oxides: (a)TEM image and (b)rate performance of spindle-like porous α-Fe2O3[89], Copyright 2012 American Chemical Society;(c) schematic diagram of the preparation process of NCO@NCS[34] Copyright 2019, American Chemical Society
表1 MOFs衍生转换型负极的电化学性能
Table 1 Electrochemical performance of MOFs-derived conversion-type anodes
Samples Raw materials Applications MLa)(mg·
cm-2)		 Initial D/Cb) capacities
(mAh·g-1);ICEc)		 Electrolyte RCd) (current density,
cycle numbers)		 ref
α-Fe2O3 FeCl3·6H2O
Terephthalic acid		 LIBs 1 1372/970;69% 1 mol·L-1 LiPF6
(EC∶DMC)		 911 mAh·g-1
(0.2 A·g-1,50)		 89
Co3O4 Co(NO3)2·6H2O
Terephthalic acid		 LIBs - 1286.1/879.5;68% 1 mol·L-1 LiPF6
(EC∶DMC:EMC)		 913 mAh·g-1
(0.2 A·g-1,60)		 90
Co3V2O8 Cu(Ac)2·H2O
Trimesic acid
Ce(NO3)2·6H2O		 LIBs - 1582/933;58.9% 1 mol·L-1 LiPF6
(EC∶DMC)		 995 mAh·g-1
(0.5 A·g-1,120)		 92
C@FeS2 FeCl3·6H2O
Terephthalic acid
Sulfur		 LIBs 1.5 1394/1115;80% 1 mol·L-1 LiPF6
(EC∶DMC:DEC)		 1074 mAh·g-1
(0.1 A·g-1,100)		 46
CuCo2S4@C Co(NO3)2·6H2O
2-methylimidazole
CuSO4
Thioacetamide		 LIBs 1 1715/1413;82.4% 1 mol·L-1 LiPF6
(EC∶DEC)		 1100.8 mAh·g-1
(0.1 A·g-1,200)		 113
CoSe/Co@NC Co(NO3)2·6H2O
2-methylimidazole
Selenium
Dicyandiamide		 LIBs 0.8 576/421;73.1% 1 mol·L-1 LiPF6
(EC∶DMC)		 630 mAh·g-1
(0.2 A·g-1,100)		 123
C@Ni-Co-Se Ni(Ac)2·4H2O
Co(Ac)2·4H2O
trimesic acid
Selenium		 LIBs - 821/634;77% 1 mol·L-1 LiPF6
(EC∶DMC)		 2061 mAh·g-1
(0.5 A·g-1,300)		 128
FePx@P Red phosphorus
Fe(NO3)2·9H2O
trimesic acid
NaH2PO2		 LIBs - 2682/1623;60.5% 1 mol·L-1 LiPF6
(EC∶DEC)		 1283.9 mAh·g-1
(0.1 A·g-1,80)		 32
MoC/C Molybdenum hexacarbonyl
trimesic acid		 LIBs 1.2 990.8/647.3;65.3% 1 mol·L-1 LiPF6
(EC∶DEC)		 647.3 mAh·g-1
(0.2 A·g-1,400)		 140
MnO/C Mn(Ac)2
trimesic acid		 SIBs - 560/233;41.6% 1 mol·L-1 NaClO4
(EC∶PC;
5%FEC)		 260 mAh·g-1
(0.05A·g-1,100)		 100
NiCo2O4/NiO/C Cobalt acetylacetonate Nickel acetylacetonate
PAN
Ni(NO3)2·6H2O
Co(NO3)2·6H2O
2-methylimidazole		 SIBs 1.12 798.6/466.7;58.44% 1 mol·L-1 NaClO4
(PC:2%FEC)		 210 mAh·g-1
(0.1 A·g-1,200)		 57
MnS-(ZnCo)S/NC


Mn(NO3)2
Co(NO3)2·6H2O
Zn(NO3)2·6H2O
trimesic acid
Sulfur		 SIBs 1-1.5 770.7/-;69.1% 1 mol·L-1 NaClO4
(PC:10%FEC)		 353 mAh·g-1
(1 A·g-1,400)		 114
C@ReS2 Potassium ferricyanide NH4ReO4
Thiourea		 SIBs 1.5-2 540/400;74% 1 mol·L-1 NaClO4
(EC∶DEC;
2%FEC)		 290 mAh·g-1
(0.2A·g-1,200)		 115
Ni3S2@C Ni(NO3)2·6H2O
terephthalic acid
Thioacetamide
PPy		 SIBs - 987.7/512.6;51.9% 1 mol·L-1 NaClO4
(EC∶DEC;
5%FEC)		 432.8 mAh·g-1
(0.2 A·g-1,100)		 81
CNT/CoSe2/NC CNTs
Co(NO3)2·6H2O
2-methylimidazole
Selenium		 SIBs 1.2 686/-;67.3% 1 mol·L-1 NaClO4
(EC∶DMC;
5%FEC)		 404 mAh·g-1
(0.2 A·g-1,120)		 124
CoSe2/NC/TiO2 Co(NO3)2·6H2O
2-methylimidazole
Tetrabutyl titanate		 SIBs 0.88 -/-;76% 1 mol·L-1 NaClO4
(EC∶DMC;
5% FEC)		 374 mAh·g-1
(0.2 A·g-1,200)		 126
RGO/CoP/C-FeP Co(Ac)2·4H2O
PAB
NaH2PO2		 SIBs - 968/551.4; 56.9% 1 mol·L-1 NaClO4
(PC;5% FEC)		 456.2 mAh·g-1
(0.1 A·g-1,200)		 135
ZnSe-FeSe2@RGO Ferric acetylacetonate
Zn(NO3)2·6H2O
Phthalic acid
RGO		 PIBs - 527/405;77% 0.8 mol·L-1 KPF6
(EC∶DMC)		 363 mAh·g-1
(0.05 A·g-1,100)		 87
NC/MoS2 Zn(CH3COO)2
2-methylimidazole
(NH4)2MoS4
N2H4·H2O		 PIBs 1 1121/773.5;69% 0.8 mol·L-1 KPF6
(DMC)		 1239 mAh·g-1
(0.1 A·g-1,100)		 116
CNT/Fe-Mn-Se Mn(NO3)2
K3[Fe(CN)6]
CNTs
Selenium		 PIBs 1.5 1611/762;47.3% 0.8 mol·L-1 KPF6
(EC∶DEC)		 411 mAh·g-1
(0.8 A·g-1,70)		 125
Co0.85Se@
CNFs		 Co(NO3)2·6H2O
PAN
2-methylimidazole
Selenium		 PIBs 1.9 613/308;50.2% 0.8 mol·L-1 KPF6
(EC∶DEC)		 353 mAh·g-1
(0.2 A·g-1,100)		 170
图3 MOFs衍生的金属硫化物:CoS2-C@CNT的制备示意图[111]
Fig. 3 MOFs-derived metal sulfides: schematic diagram of the preparation process of CoS2/C@CNT[111].Copyright 2018, American Chemical Society
图4 MOFs衍生金属硒化物:Bi2Se3@C复合材料(a)制备示意图和(b)倍率性能图[122]
Fig.4 MOFs-derived metal selenides: (a) schematic diagram of the preparation process and (b) rate performance of Bi2Se3@C[122]. Copyright 2020, American Chemical Society
图5 MOFs衍生金属磷化物:(a)CoP/C复合材料的制备示意图与(b)储锂循环性能[133]
Fig. 5 MOFs-derived metal phosphide: (a)schematic diagram of the preparation process of CoP/C and (b) cyclic performance for lithium storage[133]. Copyright 2018 American Chemical Society
图6 MOFs衍生其他化合物材料:MoO2/Mo2C/C复合材料的制备示意图[141]
Fig. 6 MOFs-derived other metal compounds: schematic diagram of the preparation process of MoO2/Mo2C/C[141]. Copyright 2016, American Chemical Society
图7 MOFs衍生低维纳米材料:CoSe2@NC-NR/CNT的制备示意图[146]
Fig. 7 MOFs-derived low-dimensional nanomaterials: schematic diagram of the preparation process of CoSe2@NC-NR/CNT[146]. Copyright 2018, American Chemical Society
图8 MOFs衍生中空结构的金属化合物:(a~c)不同层数核壳Fe2O3六面体TEM图与(d)不同层数的储锂循环性能[153];(e)SEM图与(f)蛋黄壳结构的NiO制备原理图[155]
Fig. 8 MOFs-derived metal compounds with hollow structures: (a~c)TEM images of core-shell Fe2O3 hexahedrons with different layers and (d) cyclic performance for lithium storage[153], Copyright 2013, American Chemical Society; (e)SEM image and (f) schematic diagram of the preparation process of NiO with yolk-shell structure[155], Copyright 2015, American Chemical Society
图9 MOFs衍生异质结构:核-壳ZnSe@CoSe2/NC的制备示意图[162]
Fig. 9 MOFs-derived heterostructure: schematic diagram of the preparation of core-shell ZnSe@CoSe2/NC[162]. Copyright 2020, American Chemical Society
图10 MOFs衍生碳基复合材料:ZnxMnO@C复合材料的(a)制备流程示意图、(b)TEM图和(c)循环性能图[165]
Fig. 10 MOFs-derived carbon-based composites: (a)schematic diagram of the preparation process composite, (b)TEM images, and (c)cyclic performance of ZnxMnO@C[165]. Copyright 2018, Royal Society of Chemistry
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