Comparative analysis of organic pollutants fingerprints in brine-discharge wastewater from spent LiFePO<sub>4</sub> and NCM batteries via non-targeted GC-MS screening

ZHAO Yafei; SHI Fengqiong; ZHAO Yuehong; CAO Hongbin; SUN Dezhi

doi:10.13205/j.hjgc.202610004

Volume 44 Issue 10

Oct. 2026

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ZHAO Yafei, SHI Fengqiong, ZHAO Yuehong, CAO Hongbin, SUN Dezhi. Comparative analysis of organic pollutants fingerprints in brine-discharge wastewater from spent LiFePO4 and NCM batteries via non-targeted GC-MS screening[J]. ENVIRONMENTAL ENGINEERING , 2026, 44(10): 30-42. doi: 10.13205/j.hjgc.202610004

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ZHAO Yafei, SHI Fengqiong, ZHAO Yuehong, CAO Hongbin, SUN Dezhi. Comparative analysis of organic pollutants fingerprints in brine-discharge wastewater from spent LiFePO₄ and NCM batteries via non-targeted GC-MS screening[J]. ENVIRONMENTAL ENGINEERING , 2026, 44(10): 30-42. doi: 10.13205/j.hjgc.202610004

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Comparative analysis of organic pollutants fingerprints in brine-discharge wastewater from spent LiFePO₄ and NCM batteries via non-targeted GC-MS screening

doi: 10.13205/j.hjgc.202610004

1. Beijing Key Laboratory for Source Control Technology of Water Pollution, Beijing Forestry University, Beijing 100083, China;
2. Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Received Date: 2026-08-17
Available Online: 2026-11-10

Abstract

Abstract

With the rapid growth in the scale of spent lithium-ion batteries （LIBs）， their safe and efficient recycling has become an urgent need. Prior to mechanical crushing， spent LIBs are typically discharged by brine immersion to dissipate residual charge and prevent short circuits and thermal runaway； however， the resulting brine-discharge wastewater remains poorly characterized， and differences in pollution profiles across cathode chemistries are unclear. Here， solid-phase extraction coupled with gas chromatography-mass spectrometry （SPE-GC-MS） non-targeted screening was used to compare semi-volatile organic compounds in brine-discharge wastewater from spent lithium iron phosphate （LFP-33140） and nickel-cobalt-manganese （NCM-18650） batteries. After NIST library matching （match factor ≥ 80%） and retention-index verification （within ±20）， 86 compounds were identified （56 in LFP， 44 in NCM， 14 shared）， revealing distinct pollution profiles. LFP wastewater was characterized by polyethers and carboxylic acid derivatives， short-chain trialkyl phosphates， and chlorinated carbonates， whereas NCM wastewater was dominated by dimethyl alkylphosphonate homologues （P—C bonded）， hindered-phenol antioxidants and their oxidation products， and long-chain fatty acids. These differences reflect the cathode chemistry， electrolyte formulation， and binder/auxiliary materials of each battery type. Alkylphosphonate homologues and hindered phenols are potential indicators for distinguishing the two wastewater types， providing baseline data for classified treatment and targeted pollutant control of LIB recycling wastewater.
- spent lithium-ion batteries,
- cathode chemistry,
- discharge wastewater,
- organic pollutant fingerprint,
- non-targeted screening

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References(41)

References

[1]	YANG X,ZHANG H,LIU Q,et al. The Li-ion battery industry and its challenges[J]. Nature Reviews Chemistry,2025,9（8）:497-508.
[2]	王海波,钱飞宏,林虹,等. 2025 年上半年中国电池行业运行情况[J]. 电池,2025,55:660-667. WANG H B,QIAN F H,LIN H,et al. Operation of China's battery industry in the first half of 2025[J]. Battery Bimonthly,2025,55:660-667.
[3]	BAUM Z J,BIRD R E,YU X,et al. Lithium-ion battery recycling:overview of techniques and trends[J]. ACS Energy Letters,2022,7（2）:712-719.
[4]	TEMBO P M,DYER C,SUBRAMANIAN V. Lithium-ion battery recycling:a review of the material supply and policy infrastructure[J]. NPG Asia Materials,2024,16（1）:43.
[5]	CHEN B B,ZHONG S J,PENG L W. Research progress in pretreatment technologies for spent lithium-ion battery recycling[J]. Rare Metals and Cemented Carbides,2026,54:146-155. 陈斌斌,钟思佳,彭梁武. 废旧锂离子电池回收预处理技术研究进展[J]. 稀有金属与硬质合金,2026,54:146-155.
[6]	HENSCHEL J,WIEMERS-MEYER S,DIEHL M,et al. Preparative hydrophilic interaction liquid chromatography of acidic organofluorophosphates formed in lithium ion battery electrolytes[J]. Journal of Chromatography A,2019,1603:438-441.
[7]	KRAFT V,GRÜTZKE M,WEBER W,et al. Two-dimensional ion chromatography for the separation of ionic organophosphates generated in thermally decomposed lithium hexafluorophosphate-based lithium ion battery electrolytes[J]. Journal of Chromatography A,2015,1409:201-209.
[8]	LAN Y,TAN L,WU N,et al. Current status and outlook of recycling spent lithium-ion batteries[J]. Journal of Energy Storage,2025,110:115374.
[9]	GUO L,ZHI F P,WEI Z H,et al. Current status of recovery technologies for valuable metals from spent lithium-ion battery ternary cathode materials[J]. Energy Storage Science and Technology,2026,15:152-165. 郭磊,智福鹏,魏致慧,等. 废旧锂电池三元正极材料中有价金属的回收技术现状[J]. 储能科学与技术,2026,15:152-165.
[10]	LEI S,SUN W,YANG Y. Solvent extraction for recycling of spent lithium-ion batteries[J]. Journal of Hazardous Materials,2022,424:127654.
[11]	HUANG H L,LIU C W,YAO S J,et al. Review of heat treatment process for spent lithium-ion batteries:from the perspective of pollutant migration and transformation[J]. The Chinese Journal of Process Engineering,2022,22:285-303. 黄翰林,刘春伟,姚少杰,等. 废锂离子电池的热处理:过程污染物迁移和转化[J]. 过程工程学报,2022,22:285-303.
[12]	PAN Y L,LU J W,ZHENG L X,et al. Progress in hydrometallurgical recovery process for spent lithium-ion batteries[J]. Zhejiang Chemical Industry,2024,55:31-36. 潘曜灵,陆剑伟,郑灵霞,等. 废旧锂离子电池湿法冶金回收工艺进展[J]. 浙江化工,2024,55:31-36.
[13]	QI Z,CAO Y,LI D,et al. Nontarget analysis of legacy and emerging PFAS in a lithium-ion power battery recycling park and their possible toxicity measured using high-throughput phenotype screening[J]. Environmental Science & Technology,2024,58（32）:14530-14540.
[14]	RENSMO A,SAVVIDOU E K,COUSINS I T,et al. Lithium-ion battery recycling:a source of per-and polyfluoroalkyl substances（PFAS）to the environment？[J]. Environmental Science:Processes & Impacts,2023,25（6）:1015-1030.
[15]	LI J,WANG G,XU Z. Generation and detection of metal ions and volatile organic compounds（VOCs）emissions from the pretreatment processes for recycling spent lithium-ion batteries[J]. Waste Management,2016,52:221-227.
[16]	LIU X B,ZHANG X H,XIONG M,et al. Analysis on the characteristic organic pollutants from discharge wastewater of spent lithium batteries[J]. Chemical Industry and Engineering Progress,2022,41:5619-5629. 刘肖贝,张西华,熊梅,等. 退役锂电池放电废水特征有机污染物解析[J]. 化工进展,2022,41:5619-5629.
[17]	WINDISCH-KERN S,GEROLD E,NIGL T,et al. Recycling chains for lithium-ion batteries:a critical examination of current challenges,opportunities and process dependencies[J]. Waste Management,2022,138:125-139.
[18]	HAREGEWOIN A M,WOTANGO A S,HWANG B J. Electrolyte additives for lithium ion battery electrodes:progress and perspectives[J]. Energy & Environmental Science,2016,9（6）:1955-1988.
[19]	WANG Y K,LI Z M,HU Y P,et al. Emerging electrolytes with fluorinated solvents for rechargeable lithium-based batteries[J]. Chemical Society Reviews,2023,52（8）:2710-2744.
[20]	KNOCH M,VON H B,WINTER M,et al. Organofluorophosphates as oxidative degradation products in high-voltage lithium ion batteries with NMC or LNMO cathodes[J]. Journal of the Electrochemical Society,2022,169（11）:110534.
[21]	TAWALBEH T,RANGARAJAN S,LIU H,et al. Fluorinated substances in lithium-ion batteries and solid state batteries:recycling challenges and environmental impacts[J]. Journal of Power Sources,2025,652:237635.
[22]	LIANG M Y,FAN D L,GU W,et al. Research development of non-targeted screening techniques for pollutants in environmental media[J]. Environmental Monitoring and Forewarning,2020（12）:14-20. 梁梦园,范德玲,古文,等. 环境介质中有机污染物非靶向筛查技术研究进展[J]. 环境监控与预警,2020（12）:14-20.
[23]	SCHYMANSKI L E,JUNGHO J,GULZER R,et al. Identifying small molecules via high resolution mass spectrometry:communicating confidence[J]. Environmental Science & Technology,2014,48（4）:2097-2108.
[24]	FELTEN Y,EIDEN M,KARUNANITHI C,et al. Classyfire:automated chemical classification with a comprehensive,computable taxonomy[J]. Journal of Cheminformatics,2016,8:61.
[25]	WIEMERS-MEYER S,WINTER M,NOWAK S. Mechanistic insights into lithium ion battery electrolyte degradation:a quantitative NMR study[J]. Physical Chemistry Chemical Physics,2016,18（38）:26595-26601.
[26]	DING P,TU H,WANG Z,et al. Chlorination design for carbonate-based electrolytes toward advanced lithium metal batteries[J]. ACS Sustainable Chemistry & Engineering,2025,13（37）:15738-15746.
[27]	WANG M L,XUE Y R,HU W Q,et al. Design and research of all-ether high-entropy electrolyte for low-temperature lithium iron phosphate batteries[J]. Energy Storage Science and Technology,2024,13:2131-2140. 王美龙,薛煜瑞,胡文茜,等. 低温磷酸铁锂电池用全醚高熵电解液的设计研究[J]. 储能科学与技术,2024,13:2131-2140.
[28]	DOSE W M,LI W,TEMPRANO I,et al. Onset potential for electrolyte oxidation and ni-rich cathode degradation in lithium-ion batteries[J]. ACS Energy Letters,2022,7（10）:3524-3530.
[29]	ORTIZ D,STEINMETZ V,DURAND D,et al. Radiolysis as a solution for accelerated ageing studies of electrolytes in lithium-ion batteries[J]. Nature Communications,2015,6（1）:6950.
[30]	PESCHEL C,van WICKEREN S,PREIBISCH Y,et al. Comprehensive characterization of shredded lithium-ion battery recycling material[J]. Chemistry,2022,28（22）:e202200485.
[31]	HENSCHEL J,SCHWARZ J L,GLORIUS F,et al. Further insights into structural diversity of phosphorus-based decomposition products in lithium ion battery electrolytes via liquid chromatographic techniques hyphenated to ion trap-time-of-flight mass spectrometry[J]. Analytical Chemistry,2019,91（6）:3980-3988.
[32]	HE M X,LI Y T,LIU Y T,et al. Nonflammable phosphate electrolytes for high-safety lithium-sulfur batteries[J]. Chinese Journal of Engineering,2024,46:765-774. 何孟雪,李一涛,刘亚涛,等. 磷酸酯基阻燃电解液用于高安全锂硫电池[J]. 工程科学学报,2024,46:765-774.
[33]	LU Y,YAN S S,MA X,et al. Low-temperature electrolytes and their application in lithium batteries[J]. Energy Storage Science and Technology,2024,13:2224-2242. 陆洋,闫帅帅,马骁,等. 低温锂电池电解液的研究与应用[J]. 储能科学与技术,2024,13:2224-2242.
[34]	PRAŽANOVÁ A,KOČÍ J,MÍKA M H,et al. Pre-recycling material analysis of NMC lithium-ion battery cells from electric vehicles[J]. Crystals,2023,13（2）:214.
[35]	FREUNBERGER S A,CHEN Y,DREWETT N E,et al. The lithium-oxygen battery with ether-based electrolytes[J]. Angewandte Chemie International Edition,2011,50（37）:8609-8613.
[36]	NIEN Y H,CHANG C N,CHUANG P L,et al. Fabrication and characterization of nylon 66/pan nanofibrous film used as separator of lithium-ion battery[J]. Polymers,2021,13（12）:1984.
[37]	LIU X,WANG W,QIU J,et al. Amphiphilic long-chain polyamide membranes for high-rate lithium-ion battery separators[J]. ACS Applied Energy Materials,2025,8（11）:7257-7264.
[38]	AGUILÓ-AGUAYO N,HUBMANN D,KHAN F U,et al. Water-based slurries for high-energy life PO₄ batteries using embroidered current collectors[J]. Scientific Reports,2020,10（1）:5565.
[39]	DI LECCE D,CARBONE L,GANCITANO V,et al. Rechargeable lithium battery using non-flammable electrolyte based on tetraethylene glycol dimethyl ether and olivine cathodes[J]. Journal of Power Sources,2016,334:146-153.
[40]	WEILING M,PFEIFFER F,LECHTENFELD C,et al. Comprehensive study on cell components in high-voltage pouch cells with lithium perchlorate:decomposition,transesterification,chlorination,deposition,and self-discharge[J]. Batteries & Supercaps,2025,8（4）:e202400568.
[41]	KIM J H,HYUN J H,KIM S,et al. Phosphorus-based flame-retardant electrolytes for lithium batteries[J]. Advanced Energy Materials,2025,15（23）:2500587.