1.华南理工大学材料学院,广东 广州 510641
2.南方科技大学材料科学与工程系,广东省电驱动力能源材料重点实验室
3.南方科技大学创新创业学院,广东 深圳 518055
4.新宙邦科技 股份有限公司,广东 深圳 518118
张通(1999—),男,博士研究生,研究方向为高能量密度锂电池电解液设计,E-mail:12132094@mail.sustech.edu.cn;
邓永红,教授,研究方向为锂电池关键材料,E-mail:yhdeng08@163.com。
王朝阳,教授,研究方向为锂电池关键材料,E-mail:zhywang@scut.edu.cn
张光照,副研究员,研究方向为储能材料与器件,E-mail:zhanggz@sustech.edu.cn
收稿:2025-10-27,
修回:2025-12-26,
纸质出版:2026-04-28
移动端阅览
张通, 刘中波, 许晓雄, 等. 超高比能锂金属二次电池适配电解液的设计与应用研究进展[J]. 储能科学与技术, 2026, 15(4): 1511-1531.
ZHANG Tong, LIU Zhongbo, XU Xiaoxiong, et al. Advanced liquid electrolyte design for ultrahigh-specific-energy lithium-metal batteries[J]. Energy Storage Science and Technology, 2026, 15(4): 1511-1531.
张通, 刘中波, 许晓雄, 等. 超高比能锂金属二次电池适配电解液的设计与应用研究进展[J]. 储能科学与技术, 2026, 15(4): 1511-1531. DOI: 10.19799/j.cnki.2095-4239.2025.0965.
ZHANG Tong, LIU Zhongbo, XU Xiaoxiong, et al. Advanced liquid electrolyte design for ultrahigh-specific-energy lithium-metal batteries[J]. Energy Storage Science and Technology, 2026, 15(4): 1511-1531. DOI: 10.19799/j.cnki.2095-4239.2025.0965.
石墨基锂离子电池已接近理论能量密度极限,而锂金属电池作为下一代储能与电动汽车核心技术,有望突破该局限,实现超500 Wh/kg的能量密度,拓展应用场景。然而,超高比能锂金属电池的开发面临三大核心挑战:一是锂枝晶生长,充电时锂金属表面易形成枝晶,可能刺穿隔膜引发短路甚至起火;二是界面不稳定,锂金属与电解液反应生成的固态电解质界面膜(SEI)膜稳定性差,加剧活性锂损耗并缩短循环寿命;三是安全隐患,电解液具有易燃特性,在短路时易引发快速热失控。针对上述挑战,本综述聚焦液态电解质这一关键环节,从分子设计视角系统探讨先进液态电解质的构建策略。通过分析溶剂化结构调控、溶剂分子间相互作用优化等核心手段,阐明不同电解液设计(如高浓及局部高浓电解液、弱溶剂化电解液、竞争配位型电解液、多组分电解液、阻燃溶剂体系等)对抑制锂枝晶、稳定界面、提升安全性的作用机理并展望液态电解质未来研究方向,旨在推动超高比能锂金属电池的实际商业化。
Graphite-based lithium-ion batteries have nearly reached their theoretical energy density limit. By contrast
lithium-metal batteries (LMBs)
as core technology for next-generation energy storage and electric vehicles
are expected to surpass this limit
achieve energy densities over 500 Wh/kg
and broaden applications. However
the development of ultrahigh-specific-energy LMBs faces three core challenges: first
lithium dendrite growth—during charging
dendrites form on the lithium surface
potentially piercing the separator and causing short circuits or even fires; second
interfacial instability—the solid electrolyte interphase (SEI) formed between lithium metal and electrolyte is unstable
accelerating active lithium loss and shortening battery cycle life; third
safety risks—the flammable electrolyte can trigger rapid thermal runaway after short circuits. To address these issues
this review focuses on liquid electrolytes and systematically discusses advanced liquid electrolyte design strategies from a molecular perspective. By analyzing core approaches such as solvation structure regulation and solvent interaction optimization
it clarifies how different electrolyte designs (e.g.
weakly solvating electrolytes
competitive coordination electrolytes
and flame-retardant solvent systems) inhibit lithium dendrites
stabilize interfaces
and improve safety. Finally
future research directions for liquid electrolytes are proposed to accelerate the commercialization of ultrahigh-specific-energy LMBs.
HAN B, XU D W, CHI S S, et al. 500 Wh/kg class Li metal battery enabled by a self-organized core-shell composite anode[J]. Advanced Materials, 2020, 32(42): e2004793. DOI:10.1002/adma.202004793.
谢欢欢, 梁晓瑜, 董桂枝, 等. 航空运输锂电池的风险管理应用[J]. 电池, 2024, 54(1): 98-102. DOI:10.19535/j.1001-1579.2024.01.022.XIE H H, LIANG X Y, DONG G Z, et al. Application of risk management on the lithium battery by air transportation[J]. Battery Bimonthly, 2024, 54(1): 98-102. DOI:10.19535/j.1001-1579.2024.01.022.
WU C S, LOU J T, ZHANG J, et al. Current status and future directions of all-solid-state batteries with lithium metal anodes, sulfide electrolytes, and layered transition metal oxide cathodes[J]. Nano Energy, 2021, 87: 106081. DOI:10.1016/j.nanoen. 2021.106081.
XIAO J. How lithium dendrites form in liquid batteries[J]. Science, 2019, 366(6464): 426-427. DOI:10.1126/science.aay8672.
ADENUSI H, CHASS G A, PASSERINI S, et al. Lithium batteries and the solid electrolyte interphase (SEI)—Progress and outlook[J]. Advanced Energy Materials, 2023, 13(10): 2203307. DOI:10.1002/aenm.202203307.
WANG Y K, LI Z M, HOU Y P, et al. Emerging electrolytes with fluorinated solvents for rechargeable lithium-based batteries[J]. Chemical Society Reviews, 2023, 52(8): 2713-2763.
SPOTTE-SMITH E W C, PETROCELLI T B, PATEL H D, et al. Elementary decomposition mechanisms of lithium hexafluorophosphate in battery electrolytes and interphases[J]. ACS Energy Letters, 2023, 8(1): 347-355. DOI:10.1021/acsenergylett.2c02351.
SUN J L, YAO Y J, CUI X L, et al. Improving low-temperature tolerance of a lithium-ion battery by a localized high-concentration electrolyte based on the weak solvation effect[J]. Battery Energy, 2025, 4(5): e20240106. DOI:10.1002/bte2.202 40106.
YAMADA Y, WANG J H, KO S, et al. Advances and issues in developing salt-concentrated battery electrolytes[J]. Nature Energy, 2019, 4(4): 269-280. DOI:10.1038/s41560-019-0336-z.
WANG J H, YAMADA Y, SODEYAMA K, et al. Superconcentrated electrolytes for a high-voltage lithium-ion battery[J]. Nature Communications, 2016, 7: 12032. DOI:10.1038/ncomms12032.
JIAO S H, REN X D, CAO R G, et al. Stable cycling of high-voltage lithium metal batteries in ether electrolytes[J]. Nature Energy, 2018, 3(9): 739-746. DOI:10.1038/s41560-018-0199-8.
CHEN Y W, LI M H, LIU Y, et al. Origin of dendrite-free lithium deposition in concentrated electrolytes[J]. Nature Communications, 2023, 14: 2655. DOI:10.1038/s41467-023- 38387-8.
EFAW C M, WU Q S, GAO N, et al. Localized high-concentration electrolytes get more localized through micelle-like structures[J]. Nature Materials, 2023, 22(12): 1531-1539. DOI:10.1038/s41563-023-01700-3.
WAN C, HU M Y, BORODIN O, et al. Natural abundance 17 O, 6 Li NMR and molecular modeling studies of the solvation structures of lithium bis(fluorosulfonyl)imide/1,2-dimethoxyethane liquid electrolytes[J ] . Journal of Power Sources, 2016, 307: 231-243. DOI:10.1016/j.jpowsour.2015.12.120.
LIU W, LI J X, LI W T, et al. Inhibition of transition metals dissolution in cobalt-free cathode with ultrathin robust interphase in concentrated electrolyte[J]. Nature Communications, 2020, 11: 3629. DOI:10.1038/s41467-020-17396-x.
LOULI A J, ELDESOKY A, WEBER R, et al. Diagnosing and correcting anode-free cell failure via electrolyte and morphological analysis[J ] . Nature Energy, 2020, 5(9): 693-702. DOI:10.1038/s41560-020-066 8-8.
ZENG Z Q, MURUGESAN V, HAN K S, et al. Non-flammable electrolytes with high salt-to-solvent ratios for Li-ion and Li-metal batteries[J]. Nature Energy, 2018, 3(8): 674-681. DOI:10.1038/s41560-018-0196-y.
WANG Z C, HAN R, ZHANG H Y, et al. An intrinsically nonflammable electrolyte for prominent-safety lithium metal batteries with high energy density and cycling stability[J]. Advanced Functional Materials, 2023, 33(24): 2215065. DOI:10.1002/adfm.202215065.
CUI Z Z, JIA Z Z, RUAN D G, et al. Molecular anchoring of free solvents for high-voltage and high-safety lithium metal batteries[J]. Nature Communications, 2024, 15: 2033. DOI:10.1038/s41 467-024-46186-y.
WU H Z, LUO S H, LI L, et al. A high-capacity dual-ion full battery based on nitrogen-doped carbon nanosphere anode and concentrated electrolyte[J]. Battery Energy, 2023, 2(4): 20230009. DOI:10.1002/bte2.20230009.
FU J L, JI X, CHEN J, et al. Lithium nitrate regulated sulfone electrolytes for lithium metal batteries[J]. Angewandte Chemie International Edition, 2020, 59(49): 22194-22201. DOI:10.1002/anie.202009575.
MCOWEN D W, SEO D M, BORODIN O, et al. Concentrated electrolytes: Decrypting electrolyte properties and reassessing Al corrosion mechanisms[J]. Energy & Environmental Science, 2014, 7(1): 416-426.
BAO W, YAO W L, LI Y X, et al. Insights into lithium inventory quantification of LiNi 0.5 Mn 1.5 O 4 -graphite full cells[J ] . Energy & Environmental Science, 2024, 17(12): 4263-4272. DOI:10.1039/d4ee00842a.
ZHANG J G, XU W, XIAO J, et al. Lithium metal anodes with nonaqueous electrolytes[J]. Chemical Reviews, 2020, 120(24): 13312-13348.
ZHANG G Z, DENG X L, LI J W, et al. A bifunctional fluorinated ether co-solvent for dendrite-free and long-term lithium metal batteries[J]. Nano Energy, 2022, 95: 107014. DOI:10.1016/j.nanoen.2022.107014.
CHEN S R, ZHENG J M, YU L, et al. High-efficiency lithium metal batteries with fire-retardant electrolytes[J]. Joule, 2018, 2(8): 1548-1558. DOI:10.1016/j.joule.2018.05.002.
CHEN S R, ZHENG J M, MEI D H, et al. High-voltage lithium-metal batteries enabled by localized high-concentration electrolytes[J]. Advanced Materials, 2018, 30(21): 1706102. DOI:10.1002/adma.201706102.
LIU Y C, LIN Y S, YANG Z L, et al. Stable harsh-temperature lithium metal batteries enabled by tailoring solvation structure in ether electrolytes[J]. ACS Nano, 2023, 17(20): 19625-19639.
LI X P, LI M H, LIU Y, et al. Fast interfacial defluorination kinetics enables stable cycling of low-temperature lithium metal batteries[J]. Journal of the American Chemical Society, 2024, 146(25): 17023-17031.
FU H, YE X, ZHANG Y X, et al. Toward ultralow temperature lithium metal batteries: Advancing the feasibility of 1,3-dioxolane based localized high-concentration electrolytes via lithium nitrate[J ] . Advanced Energy Materials, 2024, 14(39): 2401961. DOI:10.1002/aenm.202401961.
TRAN T N, CAO X, XU Y B, et al. Enhancing cycling stability of lithium metal batteries by a bifunctional fluorinated ether[J]. Advanced Functional Materials, 2024, 34(42): 2407012. DOI:10.1002/adfm.202407012.
ZHAO Z F, WANG A X, CHEN A S, et al. Leveraging ion pairing and transport in localized high-concentration electrolytes for reversible lithium metal anodes at low temperatures[J]. Angewandte Chemie International Edition, 2024, 63(45): e202412239. DOI:10.1002/anie.202412239.
PHAN A L, NAN B, LE P M L, et al. Lightweight electrolyte design for Li/sulfurized polyacrylonitrile (SPAN) batteries[J]. Advanced Materials, 2024, 36(35):2406594. DOI:10.1002/adma.20240 65 94.
MENG Y F, ZHOU D, LIU R L, et al. Designing phosphazene-derivative electrolyte matrices to enable high-voltage lithium metal batteries for extreme working conditions[J]. Nature Energy, 2023, 8(9): 1023-1033. DOI:10.1038/s41560-023-01339-z.
KIM M, AN J, SHIN S J, et al. Anti-corrosive electrolyte design for extending the calendar life of lithium metal batteries[J]. Energy & Environmental Science, 2024, 17(16): 6079-6090.
WU Z C, LI R H, ZHANG S Q, et al. Deciphering and modulating energetics of solvation structure enables aggressive high-voltage chemistry of Li metal batteries[J]. Chem, 2023, 9(3): 650-664. DOI:10.1016/j.chempr.2022.10.027.
LEE K, KWON S H, KIM J, et al. Fluorinated cyclic ether diluent for high-voltage lithium metal batteries[J]. ACS Energy Letters, 2024, 9(5): 2201-2211.
CAO X, REN X D, ZOU L F, et al. Monolithic solid-electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization[J]. Nature Energy, 2019, 4(9): 796-805. DOI:10.1038/s41560-019-0464-5.
ZENG H P, YU K, LI J W, et al. Beyond LiF: Tailoring Li 2 O-dominated solid electrolyte interphase for stable lithium metal batteries[J ] . ACS Nano, 2024, 18(3): 1969-1981.
LIU X, MARIANI A, DIEMANT T, et al. Reinforcing the electrode/electrolyte interphases of lithium metal batteries employing locally concentrated ionic liquid electrolytes[J]. Advanced Materials, 2024, 36(1): 2309062. DOI:10.1002/adma.202309062.
ZHU C N, SUN C C, LI R H, et al. Anion-diluent pairing for stable high-energy Li metal batteries[J]. ACS Energy Letters, 2022, 7(4): 1338-1347.
HAI F, YI Y K, XIAO Z C, et al. A low-cost, fluorine-free localized highly concentrated electrolyte toward ultra-high loading lithium metal batteries[J]. Advanced Energy Materials, 2024, 14(17): 2304253. DOI:10.1002/aenm.202304253.
HE R, DENG K R, MO D Z, et al. Active diluent-anion synergy strategy regulating nonflammable electrolytes for high-efficiency Li metal batteries[J]. Angewandte Chemie International Edition, 2024, 63(7): e202317176. DOI:10.1002/anie.202317176.
CHEN J E, ZHANG H, FANG M M, et al. Design of localized high-concentration electrolytes via donor number[J ] . ACS Energy Letters, 2023, 8(4): 1723-1734. DOI:10.1021/acsenergylett.3c00004.
LI G X, KOVERGA V, NGUYEN A, et al. Enhancing lithium-metal battery longevity through minimized coordinating diluent[J]. Nature Energy, 2024, 9(7): 817-827. DOI:10.1038/s41560-024-01519-5.
ZHOU J H, WANG H M, YANG Y Q, et al. Advanced liquid electrolyte design for high-voltage and high-safety lithium metal batteries[J]. Advanced Energy Materials, 2025, 15(34): 2502654. DOI:10.1002/aenm.202502654.
HOLOUBEK J, LIU H D, WU Z H, et al. Tailoring electrolyte solvation for Li metal batteries cycled at ultra-low temperature[J]. Nature Energy, 2021, 6(3): 303-313. DOI:10.1038/s41560-021-00783-z.
LI Z, RAO H, ATWI R, et al. Non-polar ether-based electrolyte solutions for stable high-voltage non-aqueous lithium metal batteries[J]. Nature Communications, 2023, 14: 868. DOI:10.1038/s41467-023-36647-1.
ZHANG X J, ZHAO D N, QUAN Y, et al. A solid-liquid hybrid electrolyte with weak-solvated solvent to reduce Li + transfer barrier at electrode and solid electrolyte interphase[J ] . Battery Energy, 2025, 4(6): e70042. DOI:10.1002/bte2.20250029.
ZHANG G Z, CHANG J, WANG L G, et al. A monofluoride ether-based electrolyte solution for fast-charging and low-temperature non-aqueous lithium metal batteries[J]. Nature Communications, 2023, 14: 1081. DOI:10.1038/s41467-023-36793-6.
PARK E, PARK J, LEE K, et al. Exploiting the steric effect and low dielectric constant of 1,2-dimethoxypropane for 4.3 V lithium metal batteries[J]. ACS Energy Letters, 2023, 8(1): 179-188. DOI:10.1021/acsenergylett.2c02003.
LI A M, BORODIN O, POLLARD T P, et al. Methylation enables the use of fluorine-free ether electrolytes in high-voltage lithium metal batteries[J]. Nature Chemistry, 2024, 16(6): 922-929. DOI:10.1038/s41557-024-01497-x.
CHEN Y L, YU Z A, RUDNICKI P, et al. Steric effect tuned ion solvation enabling stable cycling of high-voltage lithium metal battery[J]. Journal of the American Chemical Society, 2021, 143(44): 18703-18713. DOI:10.1021/jacs.1c09006.
YANG Q, ZHOU X Z, HUANG T T, et al. Latent solvent-induced inorganic-rich interfacial chemistry to achieve stable potassium-ion batteries in low-concentration electrolyte[J]. Angewandte Chemie International Edition, 2025, 64(12): e202422259. DOI:10.1002/anie.202422259.
POMPIZII L, LIU M L, PARK D, et al. Non-fluorinated asymmetric ether electrolytes with controlled solvation structure for high-voltage lithium metal batteries[J]. ACS Energy Letters, 2025, 10(8): 3900-3906. DOI:10.1021/acsenergylett.5c01943.
ZHAO Y, ZHOU T H, MENSI M, et al. Electrolyte engineering via ether solvent fluorination for developing stable non-aqueous lithium metal batteries[J ] . Nature Communications, 2023, 14: 299. DOI:10.1038/s41467-023-35934-1.
CHOI I R, CHEN Y L, SHAH A, et al. Asymmetric ether solvents for high-rate lithium metal batteries[J]. Nature Energy, 2025, 10(3): 365-379. DOI:10.1038/s41560-025-01716-w.
WU L Q, LI Z, FAN Z Y, et al. Unveiling the role of fluorination in hexacyclic coordinated ether electrolytes for high-voltage lithium metal batteries[J]. Journal of the American Chemical Society, 2024, 146(9): 5964-5976. DOI:10.1021/jacs.3c11798.
YU Z A, RUDNICKI P E, ZHANG Z W, et al. Rational solvent molecule tuning for high-performance lithium metal battery electrolytes[J]. Nature Energy, 2022, 7(1): 94-106. DOI:10.1038/s41560-021-00962-y.
TAN C Q, SHEN Z Y, ZHANG S C, et al. Methylation design on weakly solvating ethers for wide-temperature Li-SPAN battery[J]. Advanced Functional Materials, 2025, 35(44): 2509658. DOI:10.1002/adfm.202509658.
RUAN D G, WANG Y R, GUO J S, et al. Oscillating lithium ion-acceptor fluorine-donor electrolytes for practical fast-charging high-energy lithium metal pouch cells[J]. Energy & Environmental Science, 2025, 18(12): 6224-6236.
ZHANG G Z, ZHANG T, LIU Y Q, et al. Molecular design of asymmetric difluorinated ether electrolytes for stable operation of high-voltage lithium metal batteries[J]. Angewandte Chemie International Edition, 2025, 64(38): e202506056. DOI:10.1002/anie.202506056.
ZHANG J M, LI Q P, ZENG Y P, et al. Weakly solvating cyclic ether electrolyte for high-voltage lithium metal batteries[J]. ACS Energy Letters, 2023, 8(4): 1752-1761. DOI:10.1021/acsenergylett.3c00181.
ZHAO Y, ZHOU T H, BASTER D, et al. Targeted functionalization of cyclic ether solvents for controlled reactivity in high-voltage lithium metal batteries[J]. ACS Energy Letters, 2023, 8(7): 3180-3187.
YU Z A, WANG H S, KONG X, et al. Molecular design for electrolyte solvents enabling energy-dense and long-cycling lithium metal batteries[J]. Nature Energy, 2020, 5(7): 526-533. DOI:10.1038/s41560-020-0634-5.
XIE J, SUN S Y, CHEN X, et al. Fluorinating the solid electrolyte interphase by rational molecular design for practical lithium-metal batteries[J]. Angewandte Chemie International Edition, 2022, 61(29): e202204776. DOI:10.1002/anie.202204776.
ZHANG G Z, ZHANG T, ZHANG Z, et al. High-energy and fast-charging lithium metal batteries enabled by tuning Li + -solvation via electron-withdrawing and lithiophobicity functionality[J ] . Nature Communications, 2025, 16: 4722. DOI:10.1038/s41467-025-5996 7-w.
XU R Z, HU A J, WANG Z, et al. Tailoring anion-dominant solvation environment by steric-hindrance effect and competitive coordination for fast charging and stable cycling lithium metal batteries[J]. Journal of Energy Chemistry, 2025, 105: 35-43. DOI:10.1016/j.jechem.2025.01.038.
MAO J J, IOCOZZIA J, HUANG J Y, et al. Graphene aerogels for efficient energy storage and conversion[J]. Energy & Environmental Science, 2018, 11(4): 772-799.
QU Z T, XUE P C, HU X, et al. Strongly and weakly solvating solvents co-coordinated electrolyte for stable lithium metal batteries[J]. ACS Energy Letters, 2025, 10(6): 2913-2923.
ZHANG G Z, LI J W, CHI S S, et al. Molecular design of competitive solvation electrolytes for practical high-energy and long-cycling lithium-metal batteries[J]. Advanced Functional Materials, 2024, 34(13): 2312413. DOI:10.1002/adfm.202312413.
WANG R, LI J W, HAN B, et al. Unique double-layer solid electrolyte interphase formed with fluorinated ether-based electrolytes for high-voltage lithium metal batteries[J]. Journal of Energy Chemistry, 2024, 88: 532-542. DOI:10.1016/j.jechem. 2023.10.002.
WANG G Y, MA Q, ZHANG T, et al. A strong/weak solvents co-solvation electrolyte for fast-charging lithium metal batteries[J]. Nano Energy, 2025, 140: 111064. DOI:10.1016/j.nanoen.2025. 111064.
JI H J, XIANG J W, LI Y, et al. Liquid-liquid interfacial tension stabilized Li-metal batteries[J]. Nature, 2025, 643(8074): 1255-1262. DOI:10.1038/s41586-025-09293-4.
HUANG H, HU Y T, HOU Y J, et al. Delocalized electrolyte design enables 600 Wh/kg lithium metal pouch cells[J]. Nature, 2025, 644(8077): 660-667. DOI:10.1038/s41586-025-09382-4.
WANG X Y, JI C Y, CHEN H Q, et al. Size-induced high entropy effect for optimized electrolyte design of lithium-ion batteries[J]. Advanced Materials, 2025, 37(45): e14068. DOI:10.1002/adma. 202514068.
ZENG Y, LIU F Z, ZHANG Q, et al. A thermoresponsive electrolyte additive for high-energy, long-cycling, and safe lithium batteries[J]. Joule, 2025, 9(9): 102100. DOI:10.1016/j.joule. 2025.102100.
WU L Q, LI Z, LI H M, et al. Regulating amine substitution in fluorosulfonyl-based flame-retardant electrolytes for energy-dense lithium metal batteries[J]. Journal of the American Chemical Society, 2025, 147(19): 16506-16521. DOI:10.1021/jacs.5c03606.
ZHANG G Z, LI J W, WANG Q R, et al. A nonflammable electrolyte for high-voltage lithium metal batteries[J]. ACS Energy Letters, 2023, 8(7): 2868-2877. DOI:10.1021/acsenergylett.3c00706.
LIU Y Q, LI J, DENG X L, et al. Regulating electrolyte solvation structures via diluent-solvent interactions for safe high-voltage lithium metal batteries[J ] . Small, 202 4, 20(31): 2311812. DOI:10.1002/smll.202311812.
0
浏览量
13
下载量
0
CSCD
关联资源
相关文章
相关作者
相关机构
京公网安备11010802024621