Phosphorus Doping for Enhanced Lithium Storage Performances over Multiscale Porous SiGeSnSbPAl Composite Anode

Qin Hao , Zefang Ding , Cuiping Li , Fengxia Li , Li Li , Rumeng Bai , Junqiang Wei , Jinfeng Dong , Wenqing Ma , Caixia Xu , RuiQin Zhang

Transactions of Tianjin University ›› 2025, Vol. 31 ›› Issue (3) : 306 -319.

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Transactions of Tianjin University ›› 2025, Vol. 31 ›› Issue (3) : 306 -319. DOI: 10.1007/s12209-025-00439-z
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Phosphorus Doping for Enhanced Lithium Storage Performances over Multiscale Porous SiGeSnSbPAl Composite Anode

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Abstract

The development of high-performance lithium-ion batteries (LIBs) hinges on searching for advanced anode materials with large specific capacities as well as high cycling stability. However, traditional graphite anodes have not met the demand for higher energy storage owing to the deficiency of low lithium storage capacity. In the current work, we focus on designing one composite anode material with multiscale porous (MP) structure and phosphorus (P) doping. The coupling effects of three-dimensional (3D) interconnected skeleton, hollow pore channels, and P doping can facilitate the electrolyte diffusion and the mass transfer, as well as accommodate the volume changes during lithiation/delithiation processes. As expected, the as-prepared MP-SiGeSnSbPAl composite exhibits superior lithium storage performance, achieving a specific capacity of 827.9 mAh/g after 150 cycles at 200 mA/g and maintaining the high capacity of 456.7 mAh/g after 400 cycles at 1 A/g. Contrastively, the corresponding surplus capacities are only 590.3 and 225.7 mAh/g for the non-doped counterparts, respectively. In particular, MP-SiGeSnSbPAl displays much more stable cycling performances under the measurement of high areal mass loading of ~ 3 mg/cm2 and the full-cell tests with the lithium iron phosphate as the cathode. This work witnesses one scalable protocol for preparing multinary Si-based composite in terms of facile operation and high lithium storage performances.

Keywords

Porous structure / Phosphorus doping / Lithium-ion battery / Alloy anodes

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Qin Hao, Zefang Ding, Cuiping Li, Fengxia Li, Li Li, Rumeng Bai, Junqiang Wei, Jinfeng Dong, Wenqing Ma, Caixia Xu, RuiQin Zhang. Phosphorus Doping for Enhanced Lithium Storage Performances over Multiscale Porous SiGeSnSbPAl Composite Anode. Transactions of Tianjin University, 2025, 31(3): 306-319 DOI:10.1007/s12209-025-00439-z

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References

[1]

SuHP, LiXR, LiuCW, et al.. Scalable synthesis of micrometer-sized porous silicon/carbon composites for high-stability lithium-ion battery anodes. Chem Eng J, 2023, 451. 138394

[2]

LarkinRJ, WillenbergSC, RossN. Silicon-based anodes towards enhanced cycling efficiencies for next-generation lithium-ion batteries. Int J Electrochem Sc, 2023, 186. 100158

[3]

ChenTM, JinY, LvHY, et al.. Applications of lithium-ion batteries in grid-scale energy storage systems. Trans Tianjin Univ, 2020, 26: 208-217.

[4]

ChenBC, LiangM, WuQZ, et al.. Recent developments of antimony-based anodes for sodium and potassium-ion batteries. Trans Tianjin Univ, 2022, 28: 6-32.

[5]

ChenS, YangXY, ZhangJ, et al.. Aluminum-lithium alloy as a stable and reversible anode for lithium batteries. Electrochim Acta, 2021, 368. 137626

[6]

NiY, TuSB, ZhanRM, et al.. In situ formation of LiF-rich carbon interphase on silicon particles for cycle-stable battery anodes. Trans Tianjin Univ, 2023, 29: 101-109.

[7]

SultanaI, RahmanMM, GlushenkovAM, et al.. Nano germanium incorporated thin graphite nanoplatelets: a novel germanium based lithium-ion battery anode with enhanced electrochemical performance. Electrochim Acta, 2021, 391. 139001

[8]

SongT, ChengCHY, TownK, et al.. Electrochemical properties of Si-Ge heterostructures as an anode material for lithium ion batteries. Adv Funct Mater, 2014, 24: 1458-1464.

[9]

StokesK, FlynnG, GeaneyH, et al.. Axial Si-Ge heterostructure nanowires as lithium-ion battery anodes. Nano Lett, 2018, 18(9): 5569-5575.

[10]

LiangSZ, ChengYJ, ZhuJ, et al.. A chronicle review of nanosilicon (Sn, Sb, Ge)-based lithium/sodium-ion battery alloying anodes. Small Methods, 2020, 482000218.

[11]

GaoY, FanL, ZhouR, et al.. High-performance silicon-rich microparticle anodes for lithium-ion batteries enabled by internal stress mitigation. Nano-Micro Lett, 2023, 15222.

[12]

LiuS, FengJK, BianXF, et al.. The morphology-controlled synthesis of a nanoporous-antimony anode for high-performance sodium-ion batteries. Energ Environ Sci, 2016, 9(4): 1229-1236.

[13]

HaoXH, QiMY, LiXJ, et al.. Study on the Microstructure and Properties of AlCrFeMoSix High Entropy Alloys. J Liaocheng Univ (Nat Sci Ed), 2024, 37(1): 62-69

[14]

LinTC, DawsonA, KingSC, et al.. Understanding stabilization in nanoporous intermetallic alloy anodes for Li-ion batteries using operando transmission X-ray microscopy. ACS Nano, 2020, 14(11): 14820-14830.

[15]

CaoZJ, LiuHT, HuangWL, et al.. Hydrogen bonding-assisted synthesis of silica/oxidized mesocarbon microbeads encapsulated in amorphous carbon as stable. Trans Tianjin Univ, 2019, 39: 805-813

[16]

XuH, LiS, ChenXL, et al.. Surpassing lithium metal rechargeable batteries with self-supporting Li-Sn-Sb foil anode. Nano Energy, 2020, 74. 104815

[17]

RodriguezJR, QiZM, WangHY, et al.. Ge2Sb2Se5 glass as high-capacity promising lithium-ion battery anode. Nano Energy, 2020, 68. 104326

[18]

XiongBQ, ZhouXW, XuGL, et al.. Boosting superior lithium storage performance of alloy-based anode materials via ultraconformal Sb coating-derived favorable solid-electrolyte interphase. Adv Energy Mater, 2019, 1041903186.

[19]

ZhangQP, WangX, JianTZ, et al.. Free-standing multiscale porous high entropy NiFeCoZn alloy as the highly active bifunctional electrocatalyst for alkaline water splitting. Chinese J Chem, 2024, 42(13): 1465-1473.

[20]

WangXY, JianTZ, YangYT, et al.. Enhancing zinc storage performance of Mn3O4 cathode through Ag-doping and -crosslinking dual-modification strategy. Trans Nonferrous Met Soc China, 2024, 34(11): 3693-3706.

[21]

LiYX, YangHX, ZhangQP, et al.. In-situ building of multiscale porous NiFeZn/NiZn-Ni heterojunction for superior overall water splitting. Trans Nonferrous Met Soc China, 2024, 34(9): 2972-2986.

[22]

ChenSJ, NieL, ShiHS, et al.. Ultrafast carbonized wood of electrode-scaled aligned-porous structure for high-performance lithium batteries. Trans Tianjin Univ, 2023, 29: 387-394.

[23]

LiuS, FengJK, BianXF, et al.. Nanoporous germanium as high-capacity lithium-ion battery anode. Nano Energy, 2015, 13: 651-657.

[24]

PengMX, QiuYC, ZhangMX, et al.. Improved electrochemical performance of SiO-based anode by N, P binary doped carbon coating. Appl Surf Sci, 2020, 507. 145060

[25]

HanXY, MengXD, ChenS, et al.. P-doping a porous carbon host promotes the lithium storage performance of red phosphorus. ACS Appl Mater Interfaces, 2023, 15: 11713-11722.

[26]

ZhangJM, ZhouXY, TangJJ, et al.. Phosphoric acid induced homogeneous crosslinked phosphorus doped porous Si nanoparticles with superior lithium storage performance. Appl Surf Sci, 2020, 509. 144873

[27]

GeXL, LiZQ, YinLW, et al.. Metal-organic frameworks derived porous core/shellCoP@C polyhedrons anchored on 3D reduced graphene oxide networks as anode for sodium-ion battery. Nano Energy, 2017, 32: 117-124.

[28]

NiSB, MaJJ, LvXH, et al.. The fine electrochemical performance of porous Cu3P/Cu and the high energy density of Cu3P as anode for Li-ion batteries. J Mater Chem A, 2014, 220506.

[29]

WeiYQ, YaoRZ, ZhaoYH, et al.. Triggering the phase conversion of GeP from monoclinic to cubic by Zn substitution toward a high-rate Ge1-xZnxP solid solution anode for Li-ion batteries. Adv Energy Mater, 2023, 132202884.

[30]

WeiYQ, WenYW, OuMY, et al.. Fusing semiconductor and nonmetal into a high conductive wide-range solid solution alloy for Li-ion batteries. Energy Storage Mater, 2021, 42: 502-512.

[31]

NiuAM, LiXH, LvHR, et al.. Research progress of anode binder for lithium ion battery. J Liaocheng Univ (Nat Sci Ed), 2025, 38(1): 51-58

[32]

PolatDB, KelesO, AmineK. Well-aligned, ordered, nanocolumnar, Cu-Si thin film as anode material for lithium-ion batteries. J Power Sources, 2014, 270: 238-247.

[33]

GuoS, LiHX, BaiHM. Ti/Si/Ti sandwich-like thin film as the anode of lithium-ion batteries. J Power Sources, 2014, 248: 1141-1148.

[34]

ChenY, ZouYM, ShenXP, et al.. Ge nanoparticles uniformly immobilized on 3D interconnected porous graphene frameworks as anodes for high-performance lithium-ion batteries. J Energy Chem, 2022, 69: 161-173.

[35]

YanY, LiuY, ZhangY, et al.. Sn modified nanoporous Ge for improved lithium storage performance. J Colloid Interface Sci, 2021, 602: 563-572.

[36]

ZhouJ, HuangP, HaoQ, et al.. Ag nanoparticles anchored on nanoporous Ge skeleton as high-performance anode for lithium-ion batteries. Chin J Chem, 2021, 39(10): 2881-2888.

[37]

McnultyD, GeaneyH, RamasseQ, et al.. Long Cycle Life, Highly ordered SnO2/GeO2 nanocomposite inverse opal anode materials for Li-ion batteries. Adv Funct Mater, 2020, 30512005073.

[38]

JiaBE, HuEH, HuZY, et al.. Laminated tin-aluminum anodes to build practical aqueous aluminum batteries. Energy Storage Mater, 2024, 65. 103141

[39]

WeiYQ, YaoRZ, LiuXH, et al.. Understanding the configurational entropy evolution in metal-phosphorus solid solution for highly reversible Li-ion batteries. Adv Mater, 2023, 1092300271

[40]

DuXY, ZhangHY, LanXX, et al.. Sn alloy and graphite addition to enhance initial coulombic efficiency and cycling stability of SiO anodes for Li-ion batteries. Energy Environ Mater, 2021, 5(1): 353-359.

[41]

XinY, NieSQ, PanS, et al.. Electrospinning fabrication of Sb-SnSb/TiO2@CNFs composite nanofibers as high-performance anodes for lithium-ion batteries. J Colloid Interf Sci, 2023, 630: 403-414.

[42]

WangYT, YuRH, LuoTT, et al.. Solid solution of Bi and Sb for robust lithium storage enabled by consecutive alloying reaction. Small, 2021, 17382102915.

[43]

KilianS, MccarthyK, StokesK, et al.. Direct growth of Si, Ge, and Si-Ge heterostructure nanowires using electroplated Zn: an inexpensive seeding technique for Li-ion alloying anodes. Small, 2021, 17102005443.

[44]

LiY, WuF, LiY, et al.. Multilevel gradient-ordered silicon anode with unprecedented sodium storage. Adv Mater, 2024, 3672310270.

[45]

AnW, GaoB, MeiS, et al.. Scalable synthesis of ant-nest-like bulk porous silicon for high-performance lithium-ion battery anodes. Nat Commun, 2019, 1011447.

[46]

PidaparthyS, LuoM, RodriguesM-TF, et al.. Physicochemical heterogeneity in silicon anodes from cycled lithium-ion cells. ACS Appl Mater Interfaces, 2022, 14(34): 38660-38668.

[47]

WeiY, HeJ, ZhangJ, et al.. Seamlessly merging the capacity of P into Sb at same voltage with maintained superior cycle stability and low-temperature performance for Li-ion batteries. Energy Environ Mater, 2023, 62. e12336

[48]

ZhangS, ZhengY, HuangX, et al.. Structural engineering of hierarchical micro-nanostructured Ge-C framework by controlling the nucleation for ultralong-life Li storage. Adv Energy Mater, 2019, 9191900081.

[49]

WangL, YuJ, LiS, et al.. Recent advances in interface engineering of silicon anodes for enhanced lithium-ion battery performance. Energy Storage Mater, 2024, 66. 103243

[50]

ChoeHS, KimSJ, KimMC, et al.. Synthesis of Ge/C composites as anodes using glucose as a reductant and carbon source for lithium-ion batteries. RSC Adv, 2016, 6: 72926-72932.

[51]

ZhaoM, ZhaoD, HanX, et al.. Ge nanoparticles embedded in spherical ordered mesoporous carbon as anode material for high performance lithium ion batteries. Electrochim Acta, 2018, 287: 21-28.

[52]

YanYH, LiuY, ZhangYG, et al.. Sn modified nanoporous Ge for improved lithium storage performance. J Colloid Interf Sci, 2021, 602: 563-572.

[53]

XiaoW, ZhouJ, YuL, et al.. Electrolytic formation of crystalline silicon/germanium alloy nanotubes and hollow particles with enhanced lithium-storage properties. Angew Chem, 2016, 128: 7553-7557.

[54]

MaJ. Research progress of crosstalk behavior in lithium batteries. J Liaocheng Univ (Nat Sci Ed), 2024, 38(1): 34-42

[55]

WangL, ZhuLM, ZhangWF, et al.. Revealing the unique process of alloying reaction in Ni-CoSb/C nanosphere anode for high-performance lithium storage. J Colloid Interf Sci, 2021, 586: 730-740.

[56]

LuoH, ZhangXM, WangZY, et al.. Vanadium-tailored silicon composite with furthered ion diffusion behaviors for longevity lithium-ion storage. ACS Appl Mater Inter, 2023, 15(3): 4166-4174.

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