ChemSusChem
·
2023
·Vol. 16
·期 7
·e202202252
·
IF 8.4
Wei-Chen Zheng,Zheng Huang,Chen-Guang Shi,Yaping Deng,Zi-Hao Wen,Zhen Li,Hui Chen,Zhongwei Chen,Ling Huang,Shi-Gang Sun
Graphical Ready, willing, and stable : Interphase stability issues affect the commercialization of Ni-rich cathode materials. In this study, interphase engineering improves the interphase stability of LiNi 0.83 Co 0.11 Mn 0.06 O 2 in lithium-ion batteries. A robust cathode-electrolyte interphase is constructed by a nucleophilic reaction in the commercial electrolyte and the cathode achieves long-term cycling stability in a Li||NCM83 cell. Ni-rich cathode materials are considered promising candidates for next-generation lithium-ion batteries because of their high energy density and low cost. However, interphase failure at the surface of Ni-rich cathodes negatively impacts cycling performance, making it challenging to meet the requirements of long-term applications. In this study, a strategy is developed to improve interphase properties through introduction of a nucleophilic reaction-based additive, using an appropriate amount of the inducer lithium isopropoxide (LIP) in the commercial electrolyte to achieve long-term cycling stability of Li||LiNi 0.83 Co 0.11 Mn 0.06 O 2 (NCM83) cells. This strategy enables Li||NCM83 cells to maintain a capacity of 148.7 mAh g −1 with a retention of 83.3 % even after 500 cycles. This outstanding cycling stability is attributed to a robust cathode-electrolyte interphase (CEI) constructed on NCM83 surface LIP-induce ring-opening polymerization of ethylene carbonate (EC). As a result, the organic-inorganic components of the CEI effectively constrain gas evolution and the corresponding phase transformation behavior. Furthermore, the CEI also suppresses microcrack formation and eventually sustains the Ni valence and coordination environment at high voltage.
研究领域:
材料科学
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电化学
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能源存储
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产品关联
DOI
PubMed
高影响因子
Nature Communications
·
2020
·Vol. 11
·期 1
·1-11
·
IF 12.121
Liu Wei,Li Jinxing,Li Wenting,Xu Hanying,Zhang Chao,Qiu Xinping
The low Coulombic efficiency during cycling hinders the application of Cobalt-free lithium-rich materials in lithium-ion batteries. Here we demonstrated that the dissolution of iron, rather than traditionally acknowledged manganese, is mainly responsible for the low Coulombic efficiency of the iron-substituted cobalt-free lithium-rich material. Besides, we presented an approach to inhibit the dissolution of transition metal ions by using concentrated electrolytes. We found that the cathode electrolyte interphase (CEI) layer formed in the concentrated electrolyte is a uniform and robust LiF-rich CEI, which is a sharp contrast with the uneven and fragile organic-rich CEI formed in the dilute electrolyte. The LiF-rich CEI not only effectively inhibits the dissolution of TMs but also stabilizes the cathode structure. The Coulombic efficiency, cycling stability, rate performance, and safety of the Fe-substituted cobalt-free lithium-rich cathode material in the concentrated electrolyte have been improved tremendously.
研究领域:
材料科学
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电化学
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能源存储
✓ 已验证
DOI
高影响因子
ACS Applied Energy Materials
·
2024
·
IF 5.4
Peng Zhang,Jian-Hua Cao,Wei-Hua Liang,Yue Li,Ya-Kun Wang,Da-Yong Wu
Solid electrolytes are generated through in situ polymerization within batteries, which is one of the most promising methods for achieving solid-state lithium metal batteries with good interfacial contact, high safety, and high performance. Poly-1,3-dioxolane (PDOL), although a good in situ solidified electrolyte for lithium stability, has poor applicability in high-voltage battery systems. In order to improve the interfacial compatibility between PDOL and both the cathode and anode of high-voltage batteries. we herein design a sacrificial additive, diethyl (2,2,2-trifluoroethyl) phosphite (DETFPi), with a lower lowest unoccupied molecular orbital (LUMO) and higher highest occupied molecular orbital (HOMO) energy, through methods of calculation. After being loaded into the battery, DETFPi-DOL is in situ polymerized to form DETFPi-PDOL electrolyte. The Li||DETFPi-PDOL||Li symmetric battery operates stably for 2000 h at 0.5 mA cm–2, with an overpotential of only 16 mV. XPS analysis shows that an SEI layer with high LiF content is formed on the surface of the lithium anode after cycling, which promotes the uniform deposition of lithium ions and inhibits the growth of lithium dendrites. After 300 cycles, the NCM811||DETFPi-PDOL||Li battery exhibits a remaining capacity of 154.8 mAh g–1 (81%) within the 3.0–4.35 V range, meanwhile demonstrating excellent rate performance. Moreover, a uniform CEI layer containing pentavalent phosphorus and low LiF content is formed on the surface of the cathode after battery cycling. Finally, due to the improvement of the cathode interface, the increase of interfacial impedance of the battery after 300 cycles is reduced to half that of the PDOL battery.
研究领域:
材料科学
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电化学
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电池技术
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产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Hong Tan,Pan Wang,Guocai Yuan,Huan Yang,Jiang Ye,Kai Lu,Gang Chen,Biyou Peng,Qinyong Zhang
The advancement of aqueous zinc-ion batteries (AZIBs) is impeded by challenges encompassing cathodic and anodic aspects, such as limited capacity and dendrite formation, constraining their broader utilization. Herein, pyrrole, an economically viable and readily accessible compound, is proposed as a versatile electrolyte additive to address these challenges. Experiments and DFT calculations reveal that pyrrole and its derivatives preferentially adsorb onto zinc foil, facilitating the formation of a pyrrole-based solid electrolyte interphase (SEI), which effectively guides uniform Zn 2+ deposition through strong attraction force and suppresses hydrogen evolution reactions and parasitic reactions. On the cathode side, the additive promotes the formation of a durable cathode electrolyte interphase (CEI) enriched with poly-pyrrole (Ppy) analogues. Such layer significantly contributes to extra capacity of both polyaniline (PANI) and MnO 2 cathodes by leveraging the electrochemical reactivity of Ppy towards Zn 2+ and improves their cyclic stability. Consequently, a dendrite-free Zn anode is realized with an extended cyclic lifespan surpassing 6000 h in Zn//Zn cell, coupled with an average Coulombic efficiency of 99.7 % in Cu//Zn cell. Moreover, the PANI//Zn and MnO 2 //Zn full cells demonstrate enhanced capacities along with improved cycling stability. This work provides a new additive strategy towards concurrent stabilization of cathode and Zn anode in AZIBs.
研究领域:
材料科学
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电化学
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能源存储
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2025
·
IF 19
Kangshuai Zhu,Jing Yang,Yuxuan Li,Tongle Xu,Qinmin Pan
Solid polymer electrolytes (SPEs) have attracted significant attention in next-generation solid-state batteries (SSBs). However, SPEs-based SSBs suffer from performance fading and safety concerns at high temperatures caused by the thermal instability and degradation of their electrode/electrolyte interfaces. Herein, a poly(vinylene carbonate-co-methyl acrylate)-based solid polymer electrolyte (PVC-MA-SPE) with a highly self-adaptive structure is designed. The resulting PVC-MA-SPE exhibits an ionic conductivity of 4.93 × 10 −4 S cm −1 at 120 °C and high adhesion to electrodes. At zero pressure, solid-state Li|PVC-MA-SPE|LFP batteries maintain 152.6 mAh g −1 discharge capacity and 95.4% capacity retention after 150 cycles at 1C and 120 °C. The mechanism for the improved performance is attributed to the strong intermolecular interaction of the poly(vinylene carbonate-co-methyl acrylate) (PVC-MA) network with volatile molecules. Importantly, the PVC-MA network not only enables the SPE to tightly contact with electrodes, but also contributes to forming thermally stable SEI/CEI enriched in flexible polymeric components and LiF. These properties result in enhanced interfacial stability at high temperature. This work presents a novel approach to enhance the intrinsic safety of solid-state batteries at high temperatures.
研究领域:
材料科学
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储能
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电化学
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高分子化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Bao Zhang,Yongkang Liu,Yunfeng Gu,Ziliang Feng,Enfeng Zhang,Peng Luo,Quanyi Zhang,Peng Dong,Yingjie Zhang,Yannan Zhang
Spinel lithium manganate (LiMn 2 O 4 ) is considered a highly promising cobalt-free cathode material for lithium-ion batteries (LIBs) owing to its three-dimensional Li-ion diffusion channels and the abundance of manganese. However, its practical applications are limited due to the substantial capacity deterioration induced by the Jahn-Teller effect and interfacial instability with the organic electrolyte. In this work, we propose a polyanion-based surface engineering strategy that enables simultaneous doping and the formation of a protective coating on the LiMn 2 O 4 cathode. Boric acid surface modification can selectively stabilize the MnO₆ octahedron, while effectively suppressing manganese dissolution and interfacial side reactions. Additionally, the partial surface boron component reacts with PF 6 − in the electrolyte to form thermodynamically stable BF 4 − , which reduces the generation of HF in the electrolyte and stabilizes the cathode electrolyte interphase (CEI). Therefore, the modified BO3-LMO exhibits remarkable cycling stability, with a capacity retention rate of 80.6 % after 900 cycles at 1C, which is significantly superior to that of the unmodified LMO (61.1 %). Additionally, the BO3-LMO demonstrates excellent rate capability and thermal stability, retaining high performance even at elevated temperatures (55 °C) and under high-rate operation (5C). Through a combination of advanced characterization techniques—such as XRD refinement, XPS, HR-TEM and density functional theory calculations, we uncover the origins of the improved electrochemical stability after surface modification. The BO3-LMO demonstrates a higher density of states at the Fermi level, stronger Mn O electron bonding, and a lower lithium-ion diffusion energy barrier. This integrated strategy not only solves the interfacial instability and structural degradation challenges but also establishes a scalable strategy for designing high-performance, cobalt-free spinel manganese-based lithium-ion batteries (LIBs).
研究领域:
材料科学
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电化学
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储能技术
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表面工程
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纳米技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nature Communications
·
2022
·Vol. 13
·期 1
·1-11
·
IF 17.694
Zhang Danfeng,Liu Ming,Ma Jiabin,Yang Ke,Chen Zhen,Li Kaikai,Zhang Chen,Wei Yinping,Zhou Min,Wang Peng,He Yuanbiao,Lv Wei,Yang Quan-Hong,Kang Feiyu,He Yan-Bing
High-voltage lithium metal batteries suffer from poor cycling stability caused by the detrimental effect on the cathode of the water moisture present in the non-aqueous liquid electrolyte solution, especially at high operating temperatures (e.g., ≥60 °C). To circumvent this issue, here we report lithium hexamethyldisilazide (LiHMDS) as an electrolyte additive. We demonstrate that the addition of a 0.6 wt% of LiHMDS in a typical fluorine-containing carbonate-based non-aqueous electrolyte solution enables a stable Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) coin cell operation up to 1000 or 500 cycles applying a high cut-off cell voltage of 4.5 V in the 25 °C−60 °C temperature range. The LiHMDS acts as a scavenger for hydrofluoric acid and water and facilitates the formation of an (electro)chemical robust cathode|electrolyte interphase (CEI). The LiHMDS-derived CEI prevents the Ni dissolution of NCM811, mitigates the irreversible phase transformation from layered structure to rock-salt phase and suppresses the side reactions with the electrolyte solution.
研究领域:
电化学
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材料科学
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电池技术
✓ 已验证
DOI
PubMed
高影响因子
ELECTROCHIMICA ACTA
·
2025
·
IF 5.6
Tao Huang,Yongwei Chen,Xiangzhen Zheng,Ying Pan,Maoxiang Wu
Layered lithium-rich oxides(LRO) materials have garnered significant attention due to their high reversible capacity and broad operating voltage range. However, the practical application of LRO materials is still restricted by the serious interfacial instability and surface structure reconstruction during long-term cyclic test. In this study, we use 2-(Trimethoxysilyl)ethyl methacrylate (TSM) as a multifunctional electrolyte additive to enhance the electrochemical performance of the Li/LRO cell. The capacity retention of the Li/LRO cell improves significantly from 67.2 % to 85.8 % after 100 cycles at 0.5C (1C = 300 mAh g -1 ) between 2.0 and 4.8 V with the addition of 2 % TSM. Under harsh conditions (with the addition of 1000 ppm H 2 O to the electrolytes), Li/LRO cell with TSM additives maintains the capacity retention of 82.5 % after 100 cycles, which is significantly higher than the cell without additives (38.0 %). Both theoretical calculations and experiments results demonstrate that TSM exhibits higher oxidation activity than the solvents, forming a uniform cathode electrolyte interphase (CEI) on the LRO surface. The TSM-derived CEI layer effectively mitigates the interfacial parasitic reactions and prevents structural degradation of LRO. Furthermore, theoretical calculations and nuclear magnetic resonance (NMR) results confirm that TSM effectively eliminates water (H 2 O) and hydrofluoric acid (HF), mitigating their adverse effects.
研究领域:
材料科学
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电化学
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能量存储
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纳米技术
·
表面化学
✓ 已验证
DOI
高影响因子
Nature Communications
·
2023
·Vol. 14
·期 1
·1-14
·
IF 16.6
Zhang Junbo,Zhang Haikuo,Weng Suting,Li Ruhong,Lu Di,Deng Tao,Zhang Shuoqing,Lv Ling,Qi Jiacheng,Xiao Xuezhang,Fan Liwu,Geng Shujiang,Wang Fuhui,Chen Lixin,Noked Malachi,Wang Xuefeng,Fan Xiulin
Elevating the charging cut-off voltage is one of the efficient approaches to boost the energy density of Li-ion batteries (LIBs). However, this method is limited by the occurrence of severe parasitic reactions at the electrolyte/electrode interfaces. Herein, to address this issue, we design a non-flammable fluorinated sulfonate electrolyte by multifunctional solvent molecule design, which enables the formation of an inorganic-rich cathode electrolyte interphase (CEI) on high-voltage cathodes and a hybrid organic/inorganic solid electrolyte interphase (SEI) on the graphite anode. The electrolyte, consisting of 1.9 M LiFSI in a 1:2 v / v mixture of 2,2,2-trifluoroethyl trifluoromethanesulfonate and 2,2,2-trifluoroethyl methanesulfonate, endows 4.55 V-charged graphite||LiCoO 2 and 4.6 V-charged graphite||NCM811 batteries with capacity retentions of 89% over 5329 cycles and 85% over 2002 cycles, respectively, thus resulting in energy density increases of 33% and 16% compared to those charged to 4.3 V. This work demonstrates a practical strategy for upgrading the commercial LIBs.
研究领域:
材料科学
·
电化学
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电池技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Small
·
2023
·
IF 13.3
Ling Lv,Haikuo Zhang,Jinze Wang,Di Lu,Shuoqing Zhang,Ruhong Li,Tao Deng,Lixin Chen,Xiulin Fan
The utilization of layered oxides as cathode materials has significantly contributed to the advancement of the lithium-ion batteries (LIBs) with high energy density and reliability. However, the structural and interfacial instability triggered by side reactions when charged to high voltage has plagued their practical applications. Here, this work reports a novel multifunctional additive, id est , 7-Anilino-3-diethylamino-6-methyl fluoran (ADMF), which exhibits unique characteristics such as preferential adsorption, oxygen scavenging, and electropolymerization protection for high-voltage cathodes. The ADMF demonstrates the capability to ameliorate the growth of cathode-electrolyte interphase (CEI), effectively diminishing the dissolution of transition metal (TM) ions, reducing the interface impedance, and facilitating the Li + transport. As a result, ADMF additive with side reaction-blocking ability significantly enhances the cycling stability of MCMB||NCM811 full-cells at 4.4 V and MCMB||LCO full-cells at 4.55 V, as evidenced by the 80% retention over 600 cycles and 87% retention after 750 cycles, respectively. These findings highlight the potential of the additive design strategy to modulate the CEI chemistry, representing a new paradigm with profound implications for the development of next-generation high-voltage LIBs.
研究领域:
材料科学
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电化学
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电池技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Materials Today Energy
·
2025
·
IF 8.6
Yilian Song,Haoran Li,Kang Dong,Youjun Xing,Minghui Zhang,Mingzhu Yang,Xiang Huang,Wei Liu,Yongcheng Jin
The pursuit of high-voltage nickel-based layered terminal oxide materials (NCM) has gained significant research momentum owing to their compelling combination of cost-effectiveness and high energy density. However, critical challenges persist in mitigating parasitic interfacial reactions, electrolyte oxidative decomposition, and structural degradation mechanisms under elevated operating voltages (>4.3 V vs. Li/Li + ). Here, we propose a synergistic dual-additive electrolyte strategy by adding tris(pentafluorophenyl)borane (TPFPB) and lithium difluoro(oxalato)borate (LiDFOB) to a conventional carbonate-based electrolyte, aiming to enhance the performance of high-voltage LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622). Theoretical and experimental analyses show that LiDFOB reduces harmful side products (e.g., HF, PF 5 ) by inhibiting LiPF 6 decomposition, while TPFPB's rigid structure promotes a uniform and dense cathode electrolyte interface (CEI) film on the cathode. The two additives work synergistically to enabling the Li/NCM622 half-cells to maintain a capacity retention of up to 76.8 % after 500 cycles at 1C under 4.5 V high voltage, while the cell prepared with an electrolyte without any additives only retained 7.6 % capacity after cycling. The synergistic strategy employing TPFPB and LiDFOB to enhance the high-voltage cycling stability provides a promising practical feasibility of high-voltage batteries for industrial application.
研究领域:
电化学
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能源材料
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锂离子电池
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表面与界面工程
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电解液化学
✓ 已验证
产品关联
DOI
高影响因子
Energy Storage Materials
·
2025
·
IF 20.2
Fang Fu,Jianfei Lin,Shiyuan Zhang,Ying Liu,Tianzong Ma,Ruonan Jing,Liqun Sun,Haiming Xie
The inadequate room-temperature ionic conductivity and unstable electrode-electrolyte interfaces have encumbered the widespread adoption of high-voltage solid-state Li metal batteries (SSLMBs). Here, we report a molecularly engineered polymer electrolyte synthesized by grafting poly(ethylene glycol) diacrylate (PEGDA) and 2,2,2-trifluoroethyl methacrylate (TFEMA) onto a tri(2-hydroxyethyl) isocyanurate triacrylate (THEICTA) framework, coupled with interface engineering strategies. The hierarchical coordination competition within the polymer matrix facilitates rapid Li⁺ transport, achieving an ionic conductivity of 0.95 mS cm⁻¹ at room temperature. Advanced characterization techniques including X-ray photoelectron spectroscopy (XPS), in situ X-ray diffraction (XRD), and high-resolution transmission electron microscopy (HRTEM) reveal the formation of a robust, nitrided and boronized cathode electrolyte interphase (CEI) on LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622), effectively suppressing oxidative decomposition and mitigating structural degradation at high voltages (≥4.5 V). As a result, the Li||NCM622 cell delivers a high initial discharge capacity of 188.6 mAh g⁻¹ with 70.4 % capacity retention after 700 cycles. Furthermore, a Li metal pouch cell featuring an energy density of 456 Wh kg⁻¹ demonstrates excellent cycling stability, maintaining a capacity retention rate of 87.8 % after 130 cycles. This study provides a scalable molecular design strategy for polymer electrolytes, advancing the development of high-voltage SSLMBs for next-generation energy storage.
研究领域:
材料科学
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电化学
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储能技术
·
聚合物化学
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电池技术
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）