Research Progress of Antimony⁃Based Anode for Sodium/Potassium Ion Batteries： Failure Analysis and Solutions

doi:10.19894/j.issn.1000-0518.230366

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (5): 616-636.DOI: 10.19894/j.issn.1000-0518.230366

• Review • Previous Articles

Research Progress of Antimony⁃Based Anode for Sodium/Potassium Ion Batteries： Failure Analysis and Solutions

Dong-Yu ZHANG¹^,², Chun-Li WANG¹, Yong CHENG¹(), Li-Min WANG¹^,²

^1.State Key Laboratory of Rare Earth Resource Utilization，Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Changchun 130022，China
^2.School of Applied Chemistry and Engineering，University of Science and Technology of China，Hefei 230026，China

Received:2023-11-21 Accepted:2024-03-31 Published:2024-05-01 Online:2024-06-03
Contact: Yong CHENG
About author:cyong@ciac.ac.cn
Supported by:
the Science and Technology Development Program of Jilin Province(YDZJ202101ZYTS185);the National Natural Science Foundation of China(21975250)

Abstract

Abstract:

Sodium/potassium-ion batteries are considered the most promising choice for large-scale energy storage applications in the post-lithium-ion battery era due to their abundant resource reserves. Among the numerous anode materials for sodium/potassium ion batteries， Sb-based anodes have attracted attention due to their high theoretical specific capacity. However， Sb-based materials have thorny problems in the energy storage process that hinder their practical application， such as， huge volume expansion causing the material to pulverize and separate from the current collector， causing battery failure； poor conductivity and slow electrochemical power； electrode-side reactions at the electrolyte interface， poor battery performance， etc. In order to solve these problems， researchers have explored aspects such as structural design， doping catalytic modification， and electrolyte interface control， hoping to take advantage of the high capacity of Sb-based materials. Therefore， this article summarizes the highlights of the research on “Sb-based anodes for sodium/potassium ion batteries” in the past ten years， discusses the failure mechanism of Sb-based materials in detail. And the corresponding solutions are systematically reviewed to provide a reference for the optimization strategy of high-performance Sb-based and other alloy-based anode materials.

Key words: Sodium/potassium-ion batteries, Sb-based anode, Failure analysis, Electrochemical performance optimization

CLC Number:

O646

Dong-Yu ZHANG, Chun-Li WANG, Yong CHENG, Li-Min WANG. Research Progress of Antimony⁃Based Anode for Sodium/Potassium Ion Batteries： Failure Analysis and Solutions[J]. Chinese Journal of Applied Chemistry, 2024, 41(5): 616-636.

Figures/Tables 13

Fig.1 （A） Failure mechanism of Sb-based alloy anode；（B） Solution to the failure problem of Sb-based alloy anode

Fig.2 （A） Operando evolution of the XRD pattern recorded and the corresponding voltage profile［18］；（B） PDF and NMR-derived mechanism of （de）sodiation of antimony from the first （de） sodiation during galvanostatic cycling at a rate of C/20［19］； TOF-SIMS depth profiles through （C） 100 nm Sb and （D） the Na signal across［13］

Fig.3 （A） Crystal structure of K and the structure evolution during the potassiation process；（B） DFT calculated equilibrium voltages for the potassiation process；（C） CV curves for the Sb@CSN electrode ［20］；（D） In situ XRD measurement of an Sb electrode for the first discharge and （E） formation energies of K x Sb obtained by the ionic substitution method［21］

Fig.4 （A） Contour plot of the operando XRD of Sb2S［26］；（B） Schematic drawing showing the rocket-launching-like nanoparticle growth along with phase evolution during potassiation process and corresponding （C） TEM and （D） SAED［27］ images

Fig.5 （A） Synthesis of monodisperse Sb nanocrystals with TEM image and （B） rate performance and （C） cycle performance［38］；（D） Schematics of the Sb thin film coated MCL and the interfacial stress during the sodiation and （E） patterned arrays of voids are created to buffer the stress accumulation［39］

Fig.6 （A） Schematic illustration of the preparation process of the Sb@C microspheres［53］；（B） Schematic illustration of the preparation process of Sb@Void@GDY NB［56］

Fig.7 （A） Schematic illustration for the preparation of carbon-coated Sb/MXene （CSM） hybrid［68］；（B） Schematic illustration for the preparation of Sb/Na-Ti3C2T x hybrid［69］

Fig.8 （A， B， C） Synthesis， morphology， and structure analyses of the Sb（Sn）@C sample［72］；（D） Illustration of the crystal structure of Bi2S3 and Sb2S3 and （E） the synthesis procedures of （Bi，Sb）2S3 nanotubes［76］； Schematic illustration for the preparation of （F） BiSb@TCS［77］ and （G） rGO@Sb-Ni framework［79］

Fig.9 （A） Schematic drawing of hollow interwoven structured Sb/TiO2；（B） Illustration of nanoconfined galvanic replacement from a Ti template to hollow Sb/Ti x intermediates， TEM images of （C） hollow structured Sb/Ti x and （D） yolk-shell Ti@Sb/Ti x and （E） XRD［80］

Fig.10 （A） Schematic illustration of the synthesis process of Sb@N，S-CNFs［91］；（B） Schematic illustration of the synthesis process of u-Sb@CNF［92］；（C） Schematic illustration of the fabrication process of SbNS-G film and （D） Typical digital photograph and （E） SEM image［95］

Fig.11 （A） Illustration of electrode/SEI evolution in ECPC （up） and EGDE-based （down） electrolytes； XPS spectra of Sb electrodes after cycling three times in （B） 1 mol/L KFSI/ECPC and （C） 1 mol/L KFSI/EGDE electrolytes［99］；（D， E） Schematic diagram of electrolyte exchange experiment［100］；（F， G） Raman spectra of electrolyte［101］

Table 1 Comparison of the modification method and Na+ storage performances for the different Sb?based materials

Classify	Electrode material	Initial coulombic efficiency	Cycling performance （current density\|cycle number\|capacity）	Rate performance （current density\|capacity）	Ref.
Nanoscale	Sb NCs	-	2.64 A/g\|100\|~600 mA·h/g	13.2 A/g\|~500 mA·h/g	［38］
Nanoscale	Sb HNSs	79%	0.05 A/g\|50\|622.2 mA·h/g	1.6 A/g\|315 mA·h/g	［48］
Structural design	Sb@Void@GDY	45.6%	0.1 A/g\|200\|593 mA·h/g	10 A/g\|294 mA·h/g	［56］
	Sb NPs	63.2%	0.1 A/g\|200\|569.1 mA·h/g	5 A/g\|277.8 mA·h/g	［46］
	HNP?Sb	-	0.33 A/g\|200\|541 mA·h/g	5 A/g\|335 mA·h/g	［50］
	P?Sb	61.8%	0.05 A/g\|120\|517 mA·h/g	3 A/g\|300 mA·h/g	［49］
	Sb@C?5	50.6%	0.1 A/g\|240\|407 mA·h/g	20A/g\|310 mA·h/g	［54］
Composite	Sb/C_CHI	69.4%	0.5 A/g\|100\|372 mA·h/g	32 A/g\|138 mA·h/g	［55］
	Sb@C	46%	0.18 A/g\|300\|456 mA·h/g	4.8 A/g\|190 mA·h/g	［53］
	2D Sb/AC	68.5%	0.1 A/g\|200\|440 mA·h/g	5 A/g\|357 mA·h/g	［52］
	Sb/MXene	-	0.1 A/g\|100\|450 mA·h/g	4 A/g\|365 mA·h/g	［66］
	Sb₂O₃/MXene	59.2%	0.1 A/g\|100\|472 mA·h/g	2 A/g\|295 mA·h/g	［65］
	Sb/TiO₂	-	0.1 A/g\|100\|475 mA·h/g	2 A/g\|377 mA·h/g	［80］
	Sb@TiO₂_-x	-	2.64 A/g\|1 000\|300 mA·h/g	13.2 A/g\|312 mA·h/g	［81］
Sb?M	NiSb	86%	0.1 A/g\|100\|521 mA·h/g	2 A/g\|350 mA·h/g	［34］
	SnSb	65.8%	0.1 A/g\|100\|430 mA·h/g	10 A/g\|191 mA·h/g	［73］
	Sb（Sn）@C	70%	2 A/g\|100\|529 mA·h/g	5 A/g\|480 mA·h/g	［72］
	BiSb	-	0.5 A/g\|1 000\|328 mA·h/g	10 A/g\|319 mA·h/g	［75］
Heteroatom doping	Sb@（N，S?C）	-	0.1 A/g\|150\|621.1 mA·h/g	10 A/g\|374.7 mA·h/g	［84］
	Sb@NCs	63%	0.1 A/g\|250\|359.8 mA·h/g	2 A/g\|240 mA·h/g	［86］
	Sb₂S₃/SGS	-	2 A/g\|900\|524.4 mA·h/g	5 A/g\|591.6 mA·h/g	［60］
	Sb/Sb₂O₃?NC	63.3%	0.1 A/g\|200\|391.6 mA·h/g	1 A/g\|252.9 mA·h/g	［85］
Integrated electrode	Sb@N，S?CNFs	56.7%	0.2 A/g\|200\|348.7 mA·h/g	4 A/g\|219 mA·h/g	［91］
Integrated electrode	Sb&Sb₂O₃@C/CC	50.8%	0.1 A/g\|250\|115.6 mA·h/g	0.6 A/g\|98.4 mA·h/g	［93］

Table 2 Comparison of the modification method and K+ storage performances for the different Sb?based materials

Classify	Electrode material	Initial coulombic efficiency	Cycling performance （current density\|cycle number\|capacity）	Rate performance （current density\|capacity）	Ref.
Nanoscale	SBS/C	-	0.5 A/g\|200\|404 mA·h/g	2 A/g\|~160 mA·h/g	［47］
Structural design	Sb@C?3DP	76.2%	0.05 A/g\|150\|516 mA·h/g	1 A/g\|286 mA·h/g	［58］
Structural design	NP?Sb	71%	0.1 A/g\|50\|510 mA·h/g	0.5 A/g\|265 mA·h/g	［51］
Composite	Sb?G?C	46.84%	0.1 A/g\|100\|204.95 mA·h/g	1 A/g\|120.8 mA·h/g	［90］
	Sb/MXene	76.7%	0.1 A/g\|100\|435.9 mA·h/g	1 A/g\|323 mA·h/g	［68］
	Sb@MCMB	65.7%	0.1 A/g\|80\|497.5 mA·h/g	5 A/g\|293.9 mA·h/g	［57］
	Sb₂S₃@C	58.4%	0.05 A/g\|50\|293 mA·h/g	1 A/g\|163 mA·h/g	［27］
	Sb/Na?Ti₃C₂T _x	65.6%	0.1 A/g\|450\|392.2 mA·h/g	2 A/g\|127 mA·h/g	［69］
	Ti₃C₂?Sb₂S₃	43.3%	0.1 A/g\|100\|349 mAh/g	2 A/g\|102 mA·h/g	［26］
	Sb₂S₃@MXene	53.4%	0.5 A/g\|100\|341.1 mA·h/g	2 A/g\|119 mA·h/g	［67］
Sb?M	（Bi，Sb）₂S₃	51.9%	0.5 A/g\|1 000\|353 mA·h/g	1 A/g\|300 mA·h/g	［76］
	BiSb@TCS	64.8%	2 A/g\|5 700\|181 mA·h/g	6 A/g\|119.3 mA·h/g	［77］
	（Sb_0.99Ni_0.01）₂Se₃@C	-	0.1 A/g\|100\|410 mA·h/g	10 A/g\|140 mA·h/g	［25］
	（Bi?Sb）₂S₃@N?C	66.3%	0.1 A/g\|220\|667 mA·h/g	2 A/g\|251 mA·h/g	［35］
	Sb₂S₃?SNG	69.7%	0.05 A/g\|100\|537 mA·h/g	1 A/g\|340 mA·h/g	［22］
	Sb₂Se₃@rGO@NC	-	0.05 A/g\|100\|216 mA·h/g	5 A/g\|＜100 mA·h/g	［82］
	Sb₂S₅/CoNC	70.37%	0.5 A/g\|150\|468.5 mA·h/g	8 A/g\|137 mA·h/g	［89］
Integrated electrode	u?Sb@CNFs	48.3%	1 A/g\|2 000\|225 mA·h/g	5 A/g\|154 mA·h/g	［92］
Integrated electrode	Sb@Cu₁₅Si₄	-	0.2 A/g\|1 250\|250.2 mA·h/g	4 A/g\|104.9 mA·h/g	［94］

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Research Progress of Antimony⁃Based Anode for Sodium/Potassium Ion Batteries： Failure Analysis and Solutions

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