锌离子电池用锰/钒基氧化物异质结构正极的研究进展

doi:10.19799/j.cnki.2095-4239.2023.0854

摘要/Abstract

摘要：

水系锌离子电池（AZIBs）由于其理论比容量高、安全性高、成本低、制造工艺简单和环境友好等特性在电化学储能领域展现出巨大应用潜力。锰/钒基氧化物因其价态丰富、结构优异、比容量高等优点成为最具潜力的锌离子电池正极材料。然而，它们的本征导电性差、锌离子扩散动力学缓慢、电化学过程中的溶解和结构塌陷等限制了其进一步发展和实际应用。缓解上述问题的一种有效方法是将锰/钒基氧化物与不同功能性的组分结合构筑异质结构。原因在于，获得的异质结构能够借助各组分的特点和具有显著物化特性的异质界面，实现多功能性和协同效应，从而实现高效的储锌性能。基于此，本综述总结了锰/钒基氧化物正极材料面临的主要挑战，重点介绍了近年来已报道锰/钒基氧化物异质结构的类型、特点、制备方法及储锌性能增强机制等。最后，本文对水系锌离子电池用异质结构正极材料未来的发展进行了展望，以期为高性能锌离子电池电极材料的开发提供新的思路。

关键词: 水系锌离子电池, 锰/钒基氧化物, 异质结构, 正极材料

Abstract:

Aqueous zinc-ion batteries (AZIBs) have significantly shown application potential in the field of electrochemical energy storage due to their high theoretical specific capacity, high safety, low cost, simple manufacturing process, and environmental friendliness. Manganese/vanadium-based oxides are considered to be efficient cathode materials for zinc-ion batteries owing to their rich valence states, excellent structure, and high specific capacity. However, their disadvantages such as poor intrinsic conductivity, slow diffusion kinetics of zinc ions, and dissolution and structural collapse in electrochemical processes limit their further development and practical application. An effective way to alleviate the above problems is to combine manganese/vanadium-based oxides with different functional components to construct heterostructures. These heterostructures can achieve versatility and a synergistic effect by virtue of the characteristics of each component; further, they have heterogeneous interfaces with significant physical and chemical properties, thus achieving efficient zinc storage performance. Based on these developments, this review summarizes the main challenges faced by manganese/vanadium-based oxide cathodes, and focuses on the types, characteristics, preparation methods, and enhancement mechanisms of zinc storage properties of manganese/vanadium-based oxide heterostructures that have been reported in recent years. Finally, this paper discusses the future development of heterogeneous materials for cathodes of aqueous zinc-ion batteries and provides new insights for the development of electrode materials for high-performance zinc-ion batteries.

Key words: aqueous zinc-ion batteries, manganese/vanadium-based oxides, heterogeneous structure, cathode materials

中图分类号:

TM 911

李万瑞, 李文俊, 王小青, 路胜利, 徐喜连. 锌离子电池用锰/钒基氧化物异质结构正极的研究进展[J]. 储能科学与技术, 2024, 13(5): 1496-1515.

Wanrui LI, Wenjun LI, Xiaoqing WANG, Shengli LU, Xilian XU. Research progress of manganese/vanadium-based oxide heterostructure cathodes for zinc-ion batteries[J]. Energy Storage Science and Technology, 2024, 13(5): 1496-1515.

图/表 12

图1

图2

表1

金属掺杂锰/钒基氧化物异质结构及其储锌性能"

Cathodes	Voltage/V	Capacity (mAh/g@A/g)	Cycling performance (cycles@A/g)	Electrolyte	Ref.
Ag-V₂O₅	0.2~1.6	200@0.2, 96@1	80(700@3)	3 mol/L Zn(CF₃SO₃)₂	[76]
Ag-V₂O₅	0.2~1.6	426@0.1, 326.1@5	270(2000@5)	2 mol/L Zn(CF₃SO₃)₂	[77]
Al-VOH	0.2~1.6	380@0.05, 245@4	236.5(3000@4)	3 mol/L Zn(CF₃SO₃)₂	[78]
Mg-MnO₂	1.0~1.8	370@0.6, 172@6	95(10000@1.5)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[79]
δ-Ca_0.25V₂O₅·nH₂O/ δ-Zn_0.25V₂O₅·nH₂O	0.6~1.6	340@0.2C, 289@1C	68(3000@80C)	1 mol/L ZnSO₄	[80]
FeVO	0.2~1.6	214.4@0.5, 201.6@3	221.6(650@1)	3 mol/L Zn(CF₃SO₃)₂	[81]
Li₃(V₆O₁₆)	0.3~1.8	350@0.1, 189.8@1	189.8(1000@1)	3 mol/L Zn(CF₃SO₃)₂	[82]
Na₆V₁₀O₂₈	0.2~1.9	279.5@0.1, 60@2	143(2000@2)	3 mol/L Zn(CF₃SO₃)₂	[74]
NH₄V₄O₁₀	0.4~1.4	361.6@1, 252.8@10	255.5(1000@10)	2 mol/L ZnSO₄	[83]
δ-Ni_0.25V₂O₅	0.3~1.7	402@0.2, 218.3@5	214(1200@5)	3 mol/L ZnSO₄	[84]
Mg_0.34V₂O₅·0.84H₂O	0.1~1.8	353@0.1, 264@1	84(2000@5)	3 mol/L Zn(CF₃SO₃)₂	[54]
Na_0.33V₂O₅	0.2~1.6	367.1@0.1, 96.4@2	218.4(1000@1)	3 mol/L Zn(CF₃SO₃)₂	[85]
Zn_0.3V₂O₅·1.5H₂O	0.3~1.6	426@0.2, 265.2@10	214(20000@10)	3 mol/L Zn(CF₃SO₃)₂	[86]
Cu_0.06MnO₂·1.7H₂O	0.8~1.9	493.3@0.1, 350@0.5	363.7(150@0.5)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[87]
Bi_0.09MnO₂·1.5H₂O	0.8~1.9	175.5@0.1, 116.1@1	114.5(1100@1)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[87]
Cu-Mn₃O₄	0.8~1.9	250@0.1, 45@1	110(900@0.6)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[88]
KMgVOH	0.2~1.5	423@0.1, 318@4	222(2000@4)	3 mol/L Zn(CF₃SO₃)₂	[89]
Al_2.65V₆O₁₃·2.07H₂O	0.2~1.4	571.7@1, 205.7@5	183.5(2000@5)	3 mol/L Zn(CF₃SO₃)₂	[90]
AlMO	0.8~1.8	311.2@0.1, 145.2@5	125.3(15000@4)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[91]
Na₆[V₁₀O₂₈]·nH₂O	0.2~1.5	228.5@0.1, 84.6@10	119.4(3000@10)	2 mol/L Zn(CF₃SO₃)₂	[92]
NaV₈O₂₀·xH₂O	0.4~1.4	417@0.1, 111@80	214(1600@10)	3 mol/L Zn(CF₃SO₃)₂	[93]
δ-K_0.49V₂O₅	0.3~1.5	361@0.2, 150@5	154(2000@5)	3 mol/L Zn(CF₃SO₃)₂	[94]
Ag_0.33V₂O₅	0.1~1.6	311@0.1, 107@5	144(500@2)	3 mol/L Zn(CF₃SO₃)₂	[95]
Cu_0.95V₂O₅	0.2~1.6	405@0.1, 195@5	200(1000@5)	3 mol/L Zn(CF₃SO₃)₂	[96]
HNaV₆O₁₆·4H₂O	0.2~1.6	444@0.5, 328@5	307(1000@5)	3 mol/L Zn(CF₃SO₃)₂	[97]

表1

图3

图4

表2

目前已报道的锰/钒基氧化物/碳材料异质结构正极及其储锌性能"

Cathodes	Voltage/V	Capacity (mAh/g@A/g)	Cycling performance (cycles@A/g)	Electrolyte	Ref.
VOH-rG	0.2～1.6	466@0.1, 190@20	267(5000@10)	2 mol/L Zn(CF₃SO₃)₂	[98]
δ-MnO₂-C NA/CC	0.8～1.8	346.7@0.5, 187.8@4	147(50000@4)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[99]
$α$ -V₂O₅@C	0.3～1.9	448@0.15, 170@10	176(1500@10)	3 mol/L Zn(CF₃SO₃)₂	[100]
Cu_0.26V₂O₅@C	0.3～1.6	330@0.2, 163.8@2	175(500@2)	3 mol/L Zn(CF₃SO₃)₂	[101]
Ni_0.006Ca_0.0045VO₂@C	0.3～1.8	433.8@0.1, 158.8@5	74(4000@5)	2 mol/L ZnSO₄	[102]
VO₂@C	0.2～1.4	281@0.2, 202@5	195(1000@5)	3 mol/L Zn(CF₃SO₃)₂	[103]
Mn₃O₄@HCFs	0.9～1.85	215.8@0.3, 115.7@2	225(1300@0.4)	2 mol/L ZnSO₄+0.15 mol/L MnSO₄	[104]
MnO₂@CNTs/CNHs	1.0～1.9	343@0.3, 191.3@3	162.3(500@3)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[105]
NiMn₂O₄@C	1.0～1.85	139.7@0.05, 98.5@1.2	128.8(850@0.4)	2 mol/L ZnSO₄+0.15 mol/L MnSO₄	[106]
B-V₂O₃@C	0.2～1.4	422@0.2, 349@2.5	84(2000@5)	2 mol/L Zn(CF₃SO₃)₂	[107]
V₂O₃@C	0.3～1.5	350@0.1, 250@2	161(4000@5)	3 mol/L Zn(CF₃SO₃)₂	[108]
V₂O₃-C	0.2～1.8	415@0.1, 349@1	260(100@0.1)	3 mol/L Zn(CF₃SO₃)₂	[109]
H-VO₂@CC	0.1～1.3	350@0.1, 192@4	150(4500@4)	3 mol/L Zn(CF₃SO₃)₂	[110]
V₂O₅@void@V₂O₅@CFs	0.1～1.8	499@0.5, 387@16	455(100@4)	3 mol/L Zn(CF₃SO₃)₂	[111]
V₂O₅@CFC	0.005～2.0	293@0.05, 91@4	154(1000@0.5)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[112]
MnO@C	0.3～1.8	456@0.05, 160@2	128(2000@2)	2 mol/L ZnSO₄+0.2 mol/L MnSO₄	[113]
MnO@C	0.8～1.8	210@0.1, 111@1	120.2(4500@1)	3 mol/L ZnSO₄+0.1 mol/L MnSO₄	[114]
V₂O₅@CNT	0.2～1.7	312@1, 232@10	261(2000@1)	1 mol/L ZnSO₄	[115]
α-MnO₂@CNT	1.0～1.8	308.5@0.97C, 69.5@97.4C	163(1000@32.5C)	2 mol/L ZnSO₄+0.2 mol/L MnSO₄	[116]
Zn _x MnO₂@CNTs	0.8～1.8	400@0.1, 148@3	300(100@1)	3 mol/L ZnSO₄+0.1 mol/L MnSO₄	[55]
CNTs@Mn₃O₄	0.8～1.8	310@0.1, 116@2	123(500@1)	3 mol/L ZnSO₄+0.1 mol/L MnSO₄	[117]
CuV₂O₆@RCNTs	0.3～1.5	353@0.1, 121.5@5	174.7(1400@5)	3 mol/L Zn(CF₃SO₃)₂	[118]
KV₃O₈·0.75H₂O@SWCNT	0.3～1.3	379@0.1, 206@5	200(10000@5)	4 mol/L Zn(CF₃SO₃)₂	[119]
MnO₂@MNH-CNT	1.0～1.8	236@0.4, 108@1.6	140(100@0.4)	1 mol/L ZnSO₄	[120]
V₂O₅@CNT	0.2～1.6	375@0.5, 279@10	168.5(500@10)	2 mol/L ZnSO₄	[121]
ZnMn₂O₄@CNT	0.4～1.8	220.3@0.1, 136.5@1	74.7(2000@3)	1 mol/L ZnSO₄+0.1 mol/L MnSO₄	[122]
α-MnO₂@CNT HMs	1.0～1.85	296@0.2, 80@3	82.9(10000@3)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[123]
α-V₂O₅@CNT	0.2～1.8	480@0.5, 353@15	158(1000@30)	3 mol/L Zn(CF₃SO₃)₂	[124]
S-ZnMn₂O₄/CNTs	0.8～1.8	175.1@0.5, 128.4@1	91.7(800@1.5)	2 mol/L ZnSO₄+0.2 mol/L MnSO₄	[125]
RGO@VO₂	0.3～1.3	276@0.1, 120@35	240(1000@4)	3 mol/L Zn(CF₃SO₃)₂	[126]
CuV₂O₆@RGO	0.3～1.6	427@0.1, 241@5	285(200@2)	3 mol/L Zn(CF₃SO₃)₂	[127]
MnO₂@G	1.0～1.9	317@0.1, 112@7.5	186(2000@2)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[128]
β-MnO₂@GO	1.05～1.8	312.4@0.25C, 94.9@10C	129.6(2000@4C)	3 mol/L ZnSO₄+0.2 mol/L MnSO₄	[129]
γ-MnO₂@G	0.8～1.8	301@0.5, 95.8@10	64(300@1)	2 mol/L ZnSO₄+0.4 mol/L MnSO₄	[130]
MnO₂@rGO	1.0～1.9	332.2@0.3, 172.3@6	165.4(500@6)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[131]
Na/MnO₂@GCF	1.0～1.8	381.8@0.1, 94.8@3	188(1000@1)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[132]
P-MnO_2-_x @VMG	1.0～1.8	302.8@0.5, 150.1@10	185.8(1000@2)	2 mol/L ZnSO₄+0.2 mol/L MnSO₄	[133]
ZnMn₂O₄@NG	0.8～1.8	221@0.1, 110@1	74(2500@1)	1 mol/L ZnSO₄+0.05 mol/L MnSO₄	[134]
rGO@HM-ZnMn₂O₄	0.8～1.8	188@0.3, 59@2	72.7(650@1)	1 mol/L ZnSO₄+0.05 mol/L MnSO₄	[135]
δ-Na _x V₂O₅·nH₂O@G	0.2～1.6	433.5@0.1, 244.1@5	215(1000@2)	3 mol/L Zn(CF₃SO₃)₂	[66]
H₁₁Al₂V₆O_23.2@G	0.4～1.4	305.4@1, 180.6@10	131.7(400@2)	2 mol/L ZnSO₄	[136]
Na_1.1V₃O_7.9@rGO	0.4～1.4	220@0.3, 72@2	84.8(500@1)	1 mol/L Zn(CF₃SO₃)₂	[137]
O_d-VO₂@rG	0.2～1.4	376@0.1, 116@20	186(5000@10)	2 mol/L Zn(CF₃SO₃)₂	[138]
O_v-PVO@G	0.2～1.6	583.1@0.2, 372.3@20	448.3(3000@10)	3 mol/L Zn(CF₃SO₃)₂	[139]
V₂O₅@EGO	0.2～1.6	462@0.2, 334@5	187(3000@5)	3 mol/L Zn(CF₃SO₃)₂	[140]
V₂O₅/VG/CC	0.2～1.6	370@0.2, 216@50	278(5000@2)	3 mol/L ZnSO₄	[141]
Na₅V₁₂O₃₂@G	0.2～1.6	220@0.3, 104.2@5	105(4400@5)	2 mol/L Zn(CF₃SO₃)₂	[142]
VO₂(B)/GO	0.3～1.7	423@0.5, 371@3	227(2750@15)	3 mol/L Zn(CF₃SO₃)₂	[143]

表2

图5

表3

图6

表4

图7

图8

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Cathodes	Voltage/V	Capacity (mAh/g @A/g)	Cycling performance (cycles@A/g)	Electrolyte	Ref.
V₂O₅@PEDOT	0.2~1.4	370.5@0.5, 175@50	310.1(1000@5)	3 mol/L Zn(CF₃SO₃)₂	[151]
O_d-V₂O₅@PEDOT	0.3~1.6	449@0.2, 358@10	318(6000@10)	3 mol/L Zn(CF₃SO₃)₂	[152]
NH₄V₃O₈@PEDOT	0.4~1.6	356.8@0.05, 163.6@10	160.6(5000@10)	3 mol/L ZnCF₃SO₃	[153]
VO@PEDOT	0.3~1.4	390@0.3, 100@20	170(1000@5)	3 mol/L ZnSO₄	[56]
V₂O₅@PEDOT/CC	0.2~1.6	360@0.1, 232@20	223.6(1000@5)	2.5 mol/L Zn(CF₃SO₃)₂	[154]
Na_0.76V₆O₁₅@PEDOT	0.3~1.5	355@0.05, 165@4	168(2600@4)	3 mol/L ZnSO₄+3 mol/L Zn(CF₃SO₃)₂	[155]
(NH₄)₂V₆O₁₆·1.5H₂O@PEDOT	0.2~1.8	344@0.5, 155@20	209(1000@10)	2.5 mol/L Zn(CF₃SO₃)₂	[150]
V₂O₅@PPy	0.3~1.6	441@0.1, 291@5	304(2000@5)	3 mol/L Zn(CF₃SO₃)₂	[156]
Mn₂O₃@PPy	0.8~1.8	337.9@0.1, 77.6@3.2	73.5(3000@3)	3 mol/L ZnSO₄+0.5 mol/L MnSO₄	[144]
MnO₂/Mn₂O₃@PPy	1.0~1.85	289.8@0.2, 199.8@3	253(1000@1)	2 mol/L ZnSO₄+0.2 mol/L MnSO₄	[146]
Fe/α-MnO₂@PPy	0.8~1.9	270@0.1, 73@1	280(100@0.1)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[157]
β-MnO₂@PPy	0.8~1.8	361.8@0.2, 69.9@1.5	361.8(160@0.2)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[158]
MnO _x @PPy	0.4~1.9	302@0.15, 159.9@3	113.7(1000@6)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[159]
V₂O₅·nH₂O@PPy	0.2~1.5	383@0.1, 281@2	203(2000@4)	3 mol/L Zn(CF₃SO₃)₂	[160]
V₂O₅@PPy	0.3~1.5	374@0.2, 241@5	220(2000@10)	3 mol/L Zn(CF₃SO₃)₂	[149]
PANI@MnO₂/CC	0.8~1.8	286@0.5, 177@4	158(9000@4)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[161]
MnO₂@PANI	1.0~1.8	280@0.2, 110@3	125(5000@2)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[24]
MnVO@PANI	0.3~1.6	462@0.1, 290@5	246.5(10000@5)	3 mol/L Zn(CF₃SO₃)₂	[162]
Mg/PANI/V₂O₅·nH₂O	0.2~1.6	424@0.5, 158@6	78(1000@10)	3 mol/L Zn(CF₃SO₃)₂	[163]
V₂O₅·H₂O@PANI	0.4~1.6	346@0.3, 186@5	223(800@3)	3 mol/L Zn(TfO)₂+6 mol/L LiTFSI	[64]
V₂O_5-_x @PANI	0.4~1.6	283@1, 234@16	201(1000@1)	2 mol/L ZnSO₄	[145]
SP@PDA-d-δ-MnO₂	1.0~1.8	483@0.2, 80.3@2	73.3(500@1)	2 mol/L ZnSO₄	[164]
VO-DP	0.2~1.6	473@0.05, 144@10	117.5(15000@10)	2 mol/L Zn(OTF)₂	[165]

Cathodes	Voltage/V	Capacity (mAh/g@A/g)	Cycling performance (cycles@A/g)	Electrolyte	Ref.
VO₂@V₂O₅	0.2~1.6	435.4@0.2, 167.5@10	126.8(1500@10)	3 mol/L Zn(CF₃SO₃)₂	[168]
VO₂@V₂O₅	0.2~1.6	401@0.1, 178@5	167(2000@5)	2 mol/L ZnSO₄	[169]
V₃O₇@V₆O₁₃	0.2~1.4	445@0.1, 376@2	259(1000@1)	3 mol/L Zn(CF₃SO₃)₂	[166]
V₂O₅@NaV₆O₁₅	0.4~1.4	399@0.1, 275.8@1	164(2000@5)	3 mol/L ZnSO₄	[170]
V₂O₅@NaV₆O₁₅	0.2~1.8	390@0.3, 253.8@5	264(3000@5)	2 mol/L Zn(CF₃SO₃)₂	[171]
Al₂O₃@(NH₄)₂V₄O₉	0.2~1.6	269@0.5, 200@5	173(3000@5)	3 mol/L Zn(CF₃SO₃)₂	[172]
(NH₄)₂Co₂V₁₀O₂₈·16H₂O/ (NH₄)₂V₁₀O₂₅·8H₂O	0.2~1.8	367.7@0.1, 214@1	201.3(1000@1)	3 mol/L ZnSO₄	[173]
Zn₃V₃O₈@ZnO@NC	0.2~1.6	216.3@0.5, 183@3	120.5(2000@5)	3 mol/L Zn(CF₃SO₃)₂	[174]
ZnMn₂O₄@Mn₂O₃	0.8~1.9	82.6@0.5, 42.1@3.2	111.9(300@0.5)	1 mol/L ZnSO₄	[175]
ZnMn₂O₄@MnOOH	0.8~1.85	336.7@0.1, 98.5@5	81.9(1000@1)	2 mol/L ZnSO₄+0.2 mol/L MnSO₄	[176]
CeO₂/MnO _x @C	0.8~1.8	365@0.05, 70@2	130(800@0.5)	3 mol/L Zn(CF₃SO₃)₂+0.1 mol/L MnSO₄	[177]
Sn _x MnO₂@SnO₂	0.8~1.8	316.1@0.3, 179.4@2	153.4(2000@2)	2 mol/L ZnSO₄+0.1 mol/L MnSO₄	[178]
ZnMn₂O₄@Mn₂O₃	0.8~1.8	247.4@0.1, 120.2@5	108(2000@3)	2 mol/L Zn(CF₃SO₃)₂+0.1 mol/L MnSO₄	[167]
V₂O₃/V₃O₅/Zn₂VO₄@NC	0.2~1.5	358@0.2, 95.8@5	100.1(3000@5)	2 mol/L ZnSO₄	[179]

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