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ELECTROCHIMICA ACTA · 2019 · IF 5.383

Nd2O3 encapsulation-assisted surface passivation of Ni-rich LiNi0.8Co0.1Mn0.1O2 active material and its electrochemical performance

Jie Zhu,Guolin Cao,Yunjiao Li,Shilei Wang,Shiyi Deng,Jia Guo,Yongxiang Chen,Tongxing Lei,Jinping Zhang,Shenghong Chang

The transition metals in ternary oxide cathode materials for lithium-ion batteries inevitably exchange with protons in LiPF 6 -containing electrolytes to be dissolved, leading to loss of the active material and rapid capacity fading. Here, a chemically inert Nd 2 O 3 interlayer is employed to avoid the direct contact of the active material (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) and electrolyte. As a result, Nd 2 O 3 -coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) shows improved cycle performances with a capacity retention of 88.0% after 100 cycles over 3.0–4.4 V, 9.3% higher than the retention of the bare NCM811. Even at an elevated temperature, Nd 2 O 3 -coated NCM811 exhibits better cycle performance as well. The superior electrochemical performances for Nd 2 O 3 -coated NCM811 are ascribed to that Nd 2 O 3 encapsulation-assisted surface passivation alleviates the undesirable interface side reactions and transition metal dissolution (TMD). These features suggest the promising potential of chemically inert Nd 2 O 3 as a long-acting surface modifier in passivating electrolyte/electrode interface.

CAS / MDL: 1344-28-1
研究领域: 材料科学 · 电化学 · 电池技术
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ACS Applied Materials & Interfaces · 2023 · IF 9.5

High-Voltage and Stable Manganese Hexacyanoferrate/Zinc Batteries Using Gel Electrolytes

Lei Luo,Yu Liu,Zhaoxi Shen,Zhaorui Wen,Shi Chen,Guo Hong

Because of the high safety and environmental friendliness, aqueous zinc-ion batteries have gained a lot of attention in recent years. Prussian blue and its analogues are regarded as a promising cathode material of zinc-ion batteries. Manganese hexacyanoferrate is appropriate among them due to its high operating voltage, large capacity, and cheap price. However, the poor cycling stability of manganese hexacyanoferrate, mainly caused by transition metal dissolution, side reaction, and phase transition, greatly restricts its practical application. In this work, gelatin is used to limit the content of free water in the electrolyte, thus reducing the dissolution effect of transition metal manganese. The introduction of gelatin improves the durability of the Zn anode as well. The optimized MnHCF/gel-0.3/Zn battery displays a high reversible capacity (120 mAh·g–1 at 0.1 A·g–1), an excellent rate performance (42.7 mAh·g–1 at 2 A·g–1), and a good capacity retention (65% at 0.5 A·g–1 after 1000 cycles).

研究领域: 材料科学 · 电化学
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Journal of Energy Storage · 2025 · IF 9.8

Suppression elevated-temperature transition metal dissolution in LiNi0.5Mn1.5O4 cathode via a HF-resistant bis[3-(trimethoxysilyl)propyl]amine coating

Liqin Xiong,Zheng Cheng,Guorong Hu,Yanbing Cao,Zhongdong Peng,Bin Zhang,Ke Du

High-voltage spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) emerges as an ideal cathode for high energy density lithium-ion batteries due to its 4.7 V operating voltage and low-cost manganese-rich composition. However, the severe interfacial degradation caused by transition metal dissolution and pervasive electrolyte decomposition compromises practical viability in commercial lithium-ion batteries, critically under elevated-temperature operation. To address this problem, we constructed a covalently anchored bis[3-(trimethoxysilyl)propyl]amine (BTPA) coating layer on the LNMO surface through atomic-scale grafting. The BTPA-coated LNMO confers exceptional cyclic stability and rate capability, representing a transformative advancement in cathode performance. At 50 °C, BTPA-coated LNMO cathode maintains 96.10 % capacity retention after 100 cycles at 1C, significantly outperforming pristine LNMO (58.92 % retention), while demonstrating exceptional rate capability with 109.42 mAh·g −1 delivered at 10C compared to 92.71 mAh·g −1 for the pristine LNMO. The synergistic suppression of Mn 3+ formation and parasitic reactions underpins unprecedented high-temperature cyclability, establishing a paradigm for extreme-condition energy storage.

CAS / MDL: 2530-85-0
研究领域: 材料科学 · 电化学 · 能源存储 · 纳米材料 · 界面化学 · 锂离子电池
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2025 · IF 4.1

Artificial CEI construction via fluorosulfonates additive in high voltage lithium batteries to inhibit the transition metals dissolution

Zhicheng Dai,Shiyu Cao,Wenfeng Shi,Bokang Liu,Guanchao Yin,Fei Chen

Increasing the voltage of lithium batteries represents the most direct and effective strategy for enhancing battery capacity. However, excessively high charging voltages can result in the degradation of battery interfacial contacts and the dissolution of transition metals in the cathode, thereby limiting the cycling performance of the battery. This paper employs a fluorosulfonic acid salt electrolyte as a sacrificial agent to in situ construct a stable CEI (Cathode Electrolyte Interface) and SEI (Solid Electrolyte Interface). The resulting membrane is characterized by a uniform distribution of LiF and LiSO x , which exhibit high lithium-ion conductivity and mitigate dissolution of active materials under high voltage. This membrane effectively restricts further electrolyte consumption, allowing the remaining electrolyte to wet the interface and reduce interfacial impedance adequately. Moreover, the CEI can suppress the dissolution of transition metals from the cathode and prevent them from shuttling to the anode side. When implemented in lithium batteries, the use of the sacrificial agent enables the NCM523/Li battery (with an initial discharge capacity of 105 mAh/g) to achieve a high capacity retention of 85.7 % after 800 cycles at a 1 C rate and 30 °C.

研究领域: 电化学 · 材料科学 · 能源存储 · 电池技术 · 界面化学 · 锂离子电池
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JOURNAL OF POWER SOURCES · 2021 · IF 9.127

Cathode-anode reaction products interplay enabling high performance of LiNi0.8Co0.1Mn0.1O2/artificial graphite pouch batteries at elevated temperature

Huajun Zhao,Yunxian Qian,Guangfu Luo,Jian Chang,Chaoyang Wang,Jun Wang,Huaiyu Shao,Yonghong Deng

LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) cathode coupling with artificial graphite (AG) is a promising tendency for high-energy-density batteries . However, realization of long-term lifespan under current realistic conditions remains a “Gordian knot” for large-scale commercialization-oriented realm owing to the aggressive and highly reactive Ni 4+ sites on the delithiated cathodes and electrolyte exhaustion. Vinylene carbonate (VC) is commonly employed as the additive for graphite anode in carbonate electrolytes. However, VC has limited protection ability for NCM811/AG, especially for high-temperature cycling, showing conspicuous gas generation and large interfacial resistance . Herein, advanced carbonate-based electrolytes containing vinylene carbonate (VC) and phosphate compounds like triallyl phosphate (TPPC2) and tripropargyl phosphate (TPPC3) as electrolyte additives are reported to improve the performance of NCM811/AG pouch cells at elevated temperature. Theoretical calculations and comprehensive characterizations reveal that these two electrolytes well regulate the electrodes interface with more robust and homogenous films. Moreover, the TPPC2 and TPPC3 additives exhibit stronger tendency to eliminate the corrosive active oxygen ( 1 O 2 ) released from NCM811. These merits mitigate the electrolyte decomposition, decrease the gas generation, inhibit the dissolution of transition metals from cathode, and protect the structure stability of NCM811. Such outstanding electrochemical performance reveals promising prospects in the commercialized application of NCM811/AG batteries .

研究领域: 电化学 · 材料科学 · 能源存储 · 锂离子电池 · 界面化学 · 电极材料 · 电解质工程
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Carbon Energy · 2025 · IF 24.2

Amorphous Protective Layers to Reshape Inorganic-Rich Interphases for High-Voltage Sodium-Ion Batteries

Chang Guo,Xin-Yu Fan,Mengting Liu,Shao-Wen Xu,Guang-Xu Wei,Zhen-Bang Chen,Zhao-Kun Guan,Yao Xiao,Hanshen Xin,Peng-Fei Wang

Although sodium-ion batteries (SIBs) are competitive for large-scale electrical energy storage, the high-voltage instability of the cathode–electrolyte interphase (CEI) formed on the cathode surface results in the dissolution of the transition metal (TM) and the sluggish interfacial electrochemical reaction kinetics, which deteriorates both the energy density and the cycle life of the SIBs. Herein, we propose a surface modification strategy to reconstruct the interphase of P2-type Na 0.7 Li 0.03 Mg 0.03 Ni 0.27 Mn 0.6 Ti 0.07 O 2 (LM′NMT) cathode with amorphous SiO 2 (denote as SiO 2 @LM′NMT) by a wet chemical method. This approach facilitates the reconfiguration of a more stable, inorganic-rich CEI due to enhanced adsorption catalysis of an amorphous coating with ample defects, resulting in improved Na + transport kinetics and inhibition of subsequent side reactions, TM dissolution, and structural degradation. As a result, the modified SiO 2 @LM′NMT-5 cathode exhibits an impressive capacity of 131.6 mAh g −1 at 0.1 C and maintains exceptional cycling stability, with 91.7% capacity retention after 150 cycles at 1 C within the voltage window of 2.2 to 4.4 V. This study grasps insights into optimizing the CEI to push forward practical application of SIBs under high voltages.

研究领域: 材料科学 · 电化学 · 能源存储 · 纳米材料 · 界面化学
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Nature Communications · 2020 ·Vol. 11 ·期 1 ·1-11 · IF 12.121

Inhibition of transition metals dissolution in cobalt-free cathode with ultrathin robust interphase in concentrated electrolyte

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 · 电化学 · 能源存储
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Nature Communications · 2019 ·Vol. 10 ·期 1 ·1-9 · IF 11.878

Overlooked electrolyte destabilization by manganese (II) in lithium-ion batteries

Wang Cun,Xing Lidan,Vatamanu Jenel,Chen Zhi,Lan Guangyuan,Li Weishan,Xu Kang

Transition-metal dissolution from cathode materials, manganese in particular, has been held responsible for severe capacity fading in lithium-ion batteries, with the deposition of the transition-metal cations on anode surface, in elemental form or as chelated-complexes, as the main contributor for such degradations. In this work we demonstrate with diverse experiments and calculations that, besides interfacial manganese species on anode, manganese(II) in bulk electrolyte also significantly destabilizes electrolyte components with its unique solvation-sheath structure, where the decompositions of carbonate molecules and hexafluorophosphate anion are catalyzed via their interactions with manganese(II). The manganese(II)-species eventually deposited on anode surface resists reduction to its elemental form because of its lower electrophilicity than carbonate molecule or anion, whose destabilization leads to sustained consumption. The reveal understanding of the once-overlooked role of manganese-dissolution in electrolytes provides fresh insight into the failure mechanism of manganese-based cathode chemistries, which serves as better guideline to electrolyte design for future batteries.

研究领域: 材料科学 · 电化学 · 电池技术
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JOURNAL OF POWER SOURCES · 2022 · IF 9.794

Targeted stabilization of solid electrolyte interphase and cathode electrolyte interphase in high-voltage lithium-metal batteries by an asymmetric sustained-release strategy

Fengwei Bai,Yan Li,Ziyu Chen,Yongchao Zhou,Chengzong Li,Tao Li

High-voltage lithium (Li)-metal batteries with cell-level energy density over 350 Wh kg −1 are promising energy storage systems . However, the aggressive interphase chemistries associated with highly reactive Li-metal anode and high-voltage cathodes impede their practical applications. Herein, we demonstrate the targeted stabilization of solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI) in high-voltage Li-metal batteries by asymmetrically sustained-releasing different additives. An asymmetric sustained-release film loaded with lithium bis-(oxalate)borate (LiBOB) and LiNO 3 on each side is investigated as a proof-of-concept. The sustained-releasing of LiBOB and LiNO 3 can maintain a localized concentration at the high-voltage cathode and Li-metal anode fronts respectively, thus forming a stable B-containing CEI and N-containing SEI. As such, issues like dendrites growth, parasitic side reactions and transition metals dissolution under high-voltage are addressed simultaneously. Based on this strategy, the 30 μm Li|LiNi 0.5 Co 0.2 Mn 0.3 O 2 (4.1 mAh cm −2 ) batteries deliver a capacity retention of 80% after 173 cycles under a cut-off voltage of 4.5 V.

研究领域: 储能系统 · 电池技术 · 材料科学 · 电化学
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Journal of the American Chemical Society · 2023 · IF 15

A Semisolvated Sole-Solvent Electrolyte for High-Voltage Lithium Metal Batteries

Zhihong Piao,Xinru Wu,Hong-Rui Ren,Gongxun Lu,Runhua Gao,Guangmin Zhou,Hui-Ming Cheng

Lithium metal batteries (LMBs) coupled with a high-voltage Ni-rich cathode are promising for meeting the increasing demand for high energy density. However, aggressive electrode chemistry imposes ultimate requirements on the electrolytes used. Among the various optimized electrolytes investigated, localized high-concentration electrolytes (LHCEs) have excellent reversibility against a lithium metal anode. However, because they consist of thermally and electrochemically unstable solvents, they have inferior stability at elevated temperatures and high cutoff voltages. Here we report a semisolvated sole-solvent electrolyte to construct a typical LHCE solvation structure but with significantly improved stability using one bifunctional solvent. The designed electrolyte exhibits exceptional stability against both electrodes with suppressed lithium dendrite growth, phase transition, microcracking, and transition metal dissolution. A Li||Ni0.8Co0.1Mn0.1O2 cell with this electrolyte operates stably over a wide temperature range from −20 to 60 °C and has a high capacity retention of 95.6% after the 100th cycle at 4.7 V, and ∼80% of the initial capacity is retained even after 180 cycles. This new electrolyte indicates a new path toward future electrolyte engineering and safe high-voltage LMBs.

研究领域: 材料科学 · 电化学 · 能源存储
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ADVANCED FUNCTIONAL MATERIALS · 2025 ·Vol. 35 ·期 38 ·2503713 · IF 19

Synergistic Solvent Design for Fluorine-Free Electrolytes in High-Performance Lithium-Ion Batteries

Caiyan Shen,Dichang Guan,Wenchao Liu,Yanbing Cao,Zhongdong Peng,Yu Ren,Litao Kang,Jinhao Meng,Zhichen Xue,Ke Du

The development of fluorine-free electrolytes offers a promising route for more environmentally sustainable lithium-ion batteries (LIBs). However, the low solubility of fluorine-free lithium salts in conventional carbonate solvents limits this progress. Additionally, while strongly coordinating solvents enhance salt dissolution, their use can lead to co-intercalation in graphite, complicating electrolyte design. Herein, lithium bis(oxalate)borate (LiBOB) is chosen as lithium salt, and a synergistic electrolyte design strategy is employed, combining a strongly coordinating solvent (tris(2-methylpropyl) phosphine oxide, TMP) and weakly coordinating solvent (dimethyl carbonate, DMC). This approach enables the use of fluorine-free lithium salts while ensuring compatibility with graphite by modulating the primary coordination shell. Furthermore, this solvation structure enables the formation of an inorganic-dominated cathode electrolyte interphase (CEI) on the LiMn 2 O 4 (LMO) and a solid electrolyte interphase (SEI) on the graphite, improving lithium-ion conductivity and overall electrochemical performance. Additionally, compared to lithium hexafluorophosphate (LiPF 6 ), fluorine-free lithium salt minimized the formation of HF by-products, suppressing transition metals (TMs) dissolution. As a result, 1 Ah LMO||graphite pouch cell with fluorine-free electrolyte retains 92.8% of its capacity after 200 cycles, demonstrating excellent cycling stability and delivering high-rate capacity of 0.8486 Ah at 2 C, compared to 84.8% retention and 0.652 Ah with the conventional electrolyte.

CAS / MDL: 24937-79-9
研究领域: 电化学 · 能源材料 · 电池技术 · 可持续化学 · 材料科学
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