金属磷化物钠离子电池负极材料研究进展

王海花; 金倩倩; 舒珂维

doi:10.13801/j.cnki.fhclxb.20220120.009

金属磷化物钠离子电池负极材料研究进展

doi: 10.13801/j.cnki.fhclxb.20220120.009

陕西科技大学　化学与化工学院, 西安 710021

基金项目: 国家自然科学基金面上项目(21978164；22078189)；陕西省创新团队项目(2018TD-015)；陕西省杰出青年基金项目(2021JC-46)

详细信息

通讯作者:
王海花，博士，教授，博士生导师，研究方向为高性能及功能复合材料等　E-mail：whh@sust.edu.cn

中图分类号: O646
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出版历程
- 收稿日期: 2021-11-22
- 修回日期: 2021-12-24
- 录用日期: 2022-01-11
- 网络出版日期: 2022-01-20
- 刊出日期: 2022-06-01

Research progress on metal phosphides anode materials for sodium ion batteries

College of Chemistry and Chemical Engineering, Shaanxi University of Science & Technology, Xi’an 710021, China

摘要

摘要: 钠离子电池(SIBs)因其成本低、安全性高等优势引起了愈加广泛的关注与研究。在已报道的SIBs负极材料中，磷由于理论容量极高被认为是最具应用前景的负极材料之一。然而磷的电导率低，且在充放电过程中会发生体积膨胀，极大地影响了其倍率性能和循环稳定性。将磷与锗、锡、铜等金属结合形成金属磷化物可有效提高其导电性，并显著改善磷基负极材料的倍率性能和循环性能。本文主要综述了金属磷化物及其与碳纳米管、石墨烯等复合材料作为SIBs负极的最新研究进展，总结了目前金属磷化物SIBs负极材料存在的问题，比如实际容量偏低、储钠机制研究不够深入等；提出了相应的解决方法和手段，例如复合材料设计和构筑、表面修饰、尺寸形貌调控和先进原位表征手段等；并对金属磷化物SIBs负极材料的发展前景进行了展望。
- 钠离子电池 /
- 金属磷化物 /
- 负极材料 /
- 复合材料 /
- 电化学性能
Abstract: Sodium ion batteries (SIBs) have attracted more and more attention because of their low cost and high safety. Due to the extremely high theoretical capacity, phosphorus-based material has been considered as one of the most promising anode materials for SIBs. However, phosphorus has shortcomings such as low conductivity and large volume expansion during sodiation-desodiation cycles, which significantly deteriorate its rate performance and cycle stability. Constructing metal phosphides by combining P with germanium, tin, copper or other metals can not only enhance their conductivity, but also significantly improve the reversibility and cycle performance of phosphorus-based anode materials. In this review, recent progress on metal phosphides and their composites with carbon nanotubes and graphene for SIBs anode materials were summarized. Furthermore, the current issues of metal phosphides anodes for SIBs were discussed, such as low practical capacity, poor cycle performance and so no. Meanwhile, various approaches and techniques to address these issues were proposed, including design and construction of composite materials, surface modification, regulation of size and morphology, advanced in-situ characterizations, etc. Finally, future perspectives of metal phosphides anode materials for SIBs were also presented.
- sodium-ion batteries /
- metal phosphides /
- anode materials /
- composite /
- electrochemical performance

HTML全文

图 1 CuP₂@石墨烯(GNs)合成过程示意图^[27](a)和Cu₂P₇-黑磷(BP)(CuP₅)和CuP₅/多壁碳纳米管(MWCNTs)合成过程示意图^[28](b)

Figure 1. Schematic of synthesis process of CuP₂@graphene (GNs)^[27] (a) and Cu₂P₇-balck phosphorus (BP) (CuP₅) and CuP₅/multiwalled carbon nanotubes (MWCNTs)^[28](b)

RP—Red phosphorus

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图 2 (a) NiP₃/Na电池在0.0~2.5 V的电压范围内以C/3的倍率第一次放电时的不同阶段的原位XRD图谱^[29]；(b) Ni₂P@CNT、Ni₂P@酸处理的碳纳米管(ACNT)和Ni₂P@ACNT(CTAB)合成过程示意图；(c) Ni₂P@ACNT(CTAB)储钠机制示意图^[30]

Figure 2. (a) XRD patterns collected at various stages of the first discharge of a NiP₃/Na cell cycled between 0.0 and 2.5 V at a C/3 rate^[29]; (b) Schematic illustration of the synthesis process of Ni₂P@CNT, Ni₂P@acid treated carbon nanotubes (ACNT) and Ni₂P@ACNT(CTAB); (c) Sodiation schematics of Ni₂P@ACNT(CTAB)^[30]

CATB—Cetyltrimethyl ammonium bromid

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图 3 多孔纳米片组装花状Ni₅P₄(PNAF-NP)颗粒的SEM图像^[31]((a)、(b))、Ni₁₂P₅@C/GNs复合材料合成过程示意图^[32](c)

Figure 3. SEM images of Porous nanosheets assemble flower-like Ni₅P₄ (PNAF-NP) particle^[31]((a), (b)), schematic illustration of the synthesis process of Ni₁₂P₅@C/GNs^[32](c)

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图 4 Ge₂P₃复合材料合成过程示意图^[35](a)；GeP₃、GeP₃@还原氧化石墨烯(rGO)、GeP₃/C和GeP₃/C@rGO合成路线示意图(GeP₃/C和GeP₃/C@rGO中的线表示碳基体)及循环性能和相应的库伦效率^[36](b)；GeP₅/乙炔黑(AB)/部分还原氧化石墨烯(p-rGO)复合材料合成过程示意图^[40](c)；FL-GP/rGO合成过程示意图^[41](d)；多孔磷化锗(MGeP_x)的SEM图像及其与其他磷化物在不同电流密度下的比容量比较^[42](e)

Figure 4. Illustrated preparation process of the Ge₂P₃composite^[35] (a); Schematic illustration of the synthesis routes for bare GeP₃, GeP₃@reduced graphene oxide (rGO), GeP₃/C, and GeP₃/C@rGO (Lines in GeP₃/C and GeP₃/C@rGO represent the carbon matrix) and their long-term cyclability and corresponding coulombic efficiency^[36] (b); Schematic illustration of the synthesis process for the GeP₅/acetylene black (AB)/partially reduced graphene oxide (p-rGO) composite^[40] (c); Synthesis process for FL-GP/rGO^[41] (d); SEM images for porous germanium phosphate (MGeP_x) and comparison of the specific capacities at various current densities for MGeP_x with other phosphides^[42] (e)

HEMM—High-energy mechanical ball milling; p-rGO—Partially reduced graphene oxide

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图 5 (a) Sn₄P₃-P(Sn:P=1:3)@GNs(SPPG)的机械化学合成过程原理图；(b)不同的电流密度下，SPPG的循环性能和相应的库仑效率；(c) SPPG中的钠嵌入/脱出机制示意图^[46]

Figure 5. (a) Schematic of the mechanochemical synthesis process of Sn₄P₃-P(Sn:P=1:3)@GNs(SPPG); (b) Long-term cyclability and corresponding coulombic efficiencies of SPPG at different current rates; (c) Schematic illustration on the de-/sodiation mechanism in SPPG^[46]

HEBM—High energy ball milling

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图 6 SnP₃/C复合材料的钠化和脱钠过程示意图(外层表示碳)^[50]

Figure 6. Schematic illustration for the sodiation and desodiation of SnP₃/C composite (Outer layer denotes carbon)^[50]

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图 7 Zn₃P₂(a) 和ZnP₂(b) 的充放电曲线(电流密度：0.05 A·g⁻¹)；(c) ZnP₂-C在钠嵌入/脱出过程中的结晶相变反应机制示意图^[51]

Figure 7. Discharge-charge curves of Zn₃P₂(a) and ZnP₂ (b) (Current density: 0.05 A·g⁻¹); (c) Crystallographic phase-change reaction mechanism of ZnP₂-C during sodiation/desodiation^[51]

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表 1 SnP_x的性能比较

Table 1. Comparison of properties of SnP_x

Sample	Sn/P	Theoretical specific capacity/(mA·h·g⁻¹)	Composite	ICE/%	Cycling stability/(mA·h· g⁻¹/cycles/A·g⁻¹)	Ref.
Sn₄P₃	1.33	1132	SPPG	75.1	>550/1000/1	[46]
			Sn₄P₃@HC	69.5	430/100/0.1	[47]
			Sn₄P₃@CNF	31.0	297.6/1750/1	[48]
SnP	1	1209	SnP NCs	>60	600/200/0.1	[49]
SnP₃	0.33	1616	SnP₃/C	71.2	810/150/0.15	[50]
Notes: ICE—Initial coulombic efficiency; HC—Hard carbon; CNF—Carbon nanofibers; NCs—Nanocrystallines.

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表 2 金属磷化物负极材料电化学性能

Table 2. Electrochemical performance of metal phosphides for SIBs

Sample	Voltage range/V	ICE/%	Charging potential/V	Cycling Stability/ (mA·h·g⁻¹)/cycles/(A·g⁻¹)	Rate performance/ (mA·h·g⁻¹)/(A·g⁻¹)	Ref.
Cu₃P/C	0.01-2.5	50	0.4	120/120/0.0366	130/0.363	[25]
CuP₂@GNs	−	83	0.5-0.9	640/50/0.5	508/5	[27]
CuP₅/MWCNTs	−	84	0.4	1170/200/-	580/5	[28]
NiP₃	0.0-2.5	−	0.2	900/15/0.1C	−	[29]
Ni₂P@ACNT(CTAB)	0.01-3	35.2	0.6	150.1/100/0.1	104.8/4	[30]
PNAF-NP	0.01-3	88.49	0.2	456.34/300/0.2	432.23/5	[31]
Ni₁₂P₅@C/GNs	0.1-3	45.5	0.8	164.8/500/0.1	105.6/2	[32]
FeP@NPC	0.01-3	49	0.5	391/1000/0.1	250.2/5	[33]
FeP₄	0.05-2.0	84.0	0.6	1000/30/0.089	~920/3.578	[34]
Ge₂P₃	−	88	0.6	890/100/-	275/5	[35]
GeP₃/C@rGO	0.01-2.5	57.8	0.7	823/400/0.2	435.4/5	[36]
Monolayer GeP₃	−	−	−	1295.42(theoretical)	−	[38]
GeP₅/AB/p-rGO	0.01-2.8	~60	0.5	400/50/0.5	175/5	[40]
FL-GP/rGO	0.01-2.5	57	0.5	504.2/70/0.1 230/250/1	250/2	[41]
MGeP_x	0.01-2	65.28	0.4	704/100/0.24 278/200/1.2	117/12	[42]
SPPG	0.005-2	75.1	0.5	>550/1000/1	315/10	[46]
SnP NCs	0.005-1.5	>60	0.46	600/200/0.1	396/2.5	[49]
SnP₃/C	0-2.0	71.2	0.5	810/150/0.15	400/2.56	[50]
ZnP₂-C	0-2.0	65.8	0.6	883/130/0.05	350/2.7	[51]
Notes: PNAF-NP—Porous nanosheets assemble flower-like Ni₅P₄; NPC—N, P-codoped carbon nanofifiber; FL-GP—Few-layer GeP.

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