Nano Energy
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2023
·
IF 17.6
Wei Zhong,Siwu Li,Mengchuang Liu,Qiang Wu,Ziqi Zeng,Shijie Cheng,Jia Xie
The self-sacrificing Li 2 C 2 O 4 is a promising lithium replenisher benefiting from its high specific capacity, residue-free and low-cost properties. However, the intrinsic low electrochemical activity leads to a decomposition potential up to 4.7 V, posing a challenge for the compatibility of electrolyte and cathode materials . Herein, a three-dimensional (3D) hierarchical spherical Mo 2 C/N-doped graphene co-catalysts is synthesized by self-polymerization and high-temperature annealing. It is shown that the synergistic catalytic effect of Mo 2 C and N-doped activated graphene enhances the reactivity of Li 2 C 2 O 4 and the hierarchical three-dimensional conducting network accelerates the electron-ion transport. When the nano-Li 2 C 2 O 4 is homogeneously encapsulated in the spherical catalytic center using a freeze-drying technique, the electrochemical reaction of Li 2 C 2 O 4 is greatly promoted, resulting a significant drop of decomposition potential from 4.7 V to 4.16 V. As a result, the specific capacity of Gr||LFP and SiC||LFP full cells with composite lithium replenisher can be increased by 15% and 22%, respectively. Moreover, the solid electrolyte interface (SEI) is appropriately strengthened with pre-lithiation and thus guarantees superior cycling performance.
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
高影响因子
Science China-Materials
·
2022
·Vol. 66
·期 3
·903-912
·
IF 8.64
Zhong Wei,Zhang Ce,Li Siwu,Zhang Wei,Zeng Ziqi,Cheng Shijie,Xie Jia
Irreversible lithium loss in the initial cycles appreciably reduces the energy density of lithium-ion batteries. Prelithiation is an effective way to compensate for such lithium loss, but current methods suffer from either the instability or low capacity of prelithiation reagents. Lithium oxalate (Li 2 C 2 O 4 ) has shown great potential as a lithium-compensation material because of its high theoretical capacity (equivalent to lithium metal), low cost, and air stability. However, the practical applications of Li 2 C 2 O 4 are limited by its low electrochemical activity and high critical decomposition voltage. In this study, we performed the prelithiation of a low-voltage cathode by using Mo 2 C catalysis and nano-Li 2 C 2 O 4 . Results show that the Mo 2 C catalyst changes the electron cloud distribution around Li 2 C 2 O 4 and greatly reduces the activation energy, thereby significantly accelerating the lithium release from Li 2 C 2 O 4 . The nano-Li 2 C 2 O 4 prepared by freeze-drying shows accelerated ionic and electronic conduction as well as close contact with Mo 2 C. Benefiting from the synergistic effect, the decomposition potential of Li 2 C 2 O 4 is decreased by 0.5 V with an efficiency close to 100%. The LiCoO 2 ∥SiO full cell empowered with the nano-Li 2 C 2 O 4 /Mo 2 C prelithiation composite demonstrates 46.9% higher capacity than the control and thus has great potential for practical applications.
研究领域:
储能
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材料科学
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电化学
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纳米技术
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DOI
高影响因子
JOURNAL OF POWER SOURCES
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2026
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IF 8.4
Yule Zeng,Shanshan Zhang,Chenglin Liu,Sen Lin
Particle-size engineering, conductive-network construction and catalysis were integrated. • Recrystallization and ball milling reduced Li 2 C 2 O 4 D50 from 142.8 to 0.55 μm. • A NiO/g-C 3 N 4 composite catalyst promoted Li 2 C 2 O 4 activation. • The decomposition potential decreased from 4.805 to 4.254 V. • The bilayer electrode delivered 267.49 mAh·g −1 additional capacity. Lithium oxalate is regarded as a promising cathode prelithiation additive for compensating irreversible active lithium loss during the initial cycle of lithium-ion batteries, owing to its high theoretical specific capacity, good air stability, and low cost. However, its intrinsically low electrochemical activity and high decomposition potential severely limit its practical application. Herein, a synergistic regulation strategy combining particle-size refinement, conductive-network construction, and NiO/g-C 3 N 4 catalyst modification was developed to promote the electrochemical activation of Li 2 C 2 O 4 . The reduced particle size shortens Li + transport pathways, while Ketjen black constructs an efficient conductive network and the NiO/g-C 3 N 4 composite catalyst promotes the electrochemical activation of Li 2 C 2 O 4 . As a result, the decomposition potential of Li 2 C 2 O 4 was reduced from 4.805 to 4.254 V, while a high discharge capacity of 510.2 mAh·g −1 was maintained. When applied in LiFePO 4 half-cells using a bilayer electrode configuration, the optimized prelithiation layer delivered an additional specific capacity of 267.49 mAh·g −1 without compromising cycling stability. This work provides a feasible strategy for improving the electrochemical utilization of Li 2 C 2 O 4 and demonstrates its potential as an efficient cathode prelithiation additive for lithium-ion batteries.
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DOI
高影响因子
Advanced Powder Materials
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2024
·
IF 28.6
Hongqiang Zhang,Tiansheng Bai,Jun Cheng,Fengjun Ji,Zhen Zeng,Yuanyuan Li,Chenwu Zhang,Jiaxian Wang,Weihao Xia,Naixuan Ci,Yixuan Guo,Dandan Gao,Wei Zhai,Jingyu Lu,Lijie Ci,Deping Li
The development of high-energy-density Li-ion batteries is hindered by the irreversible capacity loss during the initial charge-discharge process. Therefore, pre-lithiation technology has emerged in the past few decades as a powerful method to supplement the undesired lithium loss, thereby maximizing the energy utilization of LIBs and extending their cycle life. Lithium oxalate (Li 2 C 2 O 4 ), with a high lithium content and excellent air stability, has been considered one of the most promising materials for lithium compensation. However, the sluggish electrochemical decomposition kinetics of the material severely hinders its further commercial application. Here, we introduce a recrystallization strategy combined with atomic Ni catalysts to modulate the mass transport and decomposition reaction kinetics. The decomposition potential of Li 2 C 2 O 4 is significantly decreased from ∼4.90V to ∼4.30V with a high compatibility with the current battery systems. In compared to the bare NCM//Li cell, the Ni/N-rGO and Li 2 C 2 O 4 composite (Ni-LCO) modified cell releases an extra capacity of ∼11.7 %. Moreover, this ratio can be magnified in the NCM//SiO x full cell, resulting in a 30.4 % higher reversible capacity. Overall, this work brings the catalytic paradigm into the pre-lithiation technology, which opens another window for the development of high-energy-density battery systems.
研究领域:
材料科学
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能源存储与转换
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DOI
高影响因子
ChemSusChem
·
2026
·Vol. 19
·期 16
·e70968
·
IF 5.9
Hengyi Zhang,Piyu Gong,Yi Du,Linxiu Dai,Changhua An
Lithium oxalate (Li 2 C 2 O 4 ) is a promising cathode prelithiation reagent but suffers from a high activation voltage (>4.6 V). Herein, we establish a component–electronic structure–activity correlation by constructing a series of transition metal-loaded N,S co-doped carbon catalysts (M/NSC, M = Fe, Co, Ni, Ru, Rh, Ir). Distinct catalytic behaviors originate from metal-dependent electronic structures and their interactions with N/S co-doped carbon. Interestingly, the Fe-group metals exhibit stronger electronic coupling and higher redox flexibility than 4d/5d noble metals, resulting in more effective activation of Li 2 C 2 O 4 . The Co/NSC achieves the lowest decomposition voltage (4.17 V), attributed to uniform Co dispersion, optimized Co–N/S coordination, and defect-induced charge-transfer enhancement. The Co/NSC–Li 2 C 2 O 4 composite ensures nearly complete decomposition and delivers superior prelithiation performance. When applied to commercial LFP and NCM9055 cathodes, the Gr|| LiFePO 4 system shows a 22% capacity increase, meanwhile the Gr/SiC||NCM9055 cell achieves an initial coulombic efficiency (ICE) enhancement from 77% to 85.6%. This work highlights electronic–structure engineering as an effective strategy for enabling practical lithium compensation in high-energy lithium-ion batteries. Graphical Unlocking the structure–activity relationship of Li 2 C 2 O 4 prelithiation: uniformly dispersed Co nanoparticles on N,S co-doped carbon creates abundant active sites, Co–N/Co–S coordination modulates electronic structure, and defect-rich carbon ensures fast charge transfer. These structural advantages reduce decomposition voltage to 4.17 V and exhibit a capacity enhancement of 22%.
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DOI
高影响因子
ACS Applied Materials & Interfaces
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2021
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IF 9.229
Ningning Feng,Bingliang Wang,Zhuo Yu,Yuming Gu,Lili Xu,Jing Ma,Yonggang Wang,Yongyao Xia
Li–CO2 batteries have attracted worldwide attention because of their dual characteristics of high energy density and effective CO2 capture. However, the basic electrochemistry mechanism involved has been unclear, which is mainly confused by the complicated decomposition of organic electrolytes. Herein, water-in-salt (WIS, LiTFSI/H2O 21.0 mol/1 kg) has been explored as a suitable electrolyte for the first time to investigate the reaction mechanism of Li–CO2 batteries with different cathodes (carbon nanotube (CNT) and Mo2C/CNT, respectively). An Mo2C-based Li–CO2 battery with WIS delivers a higher energy efficiency of 83% and a superior cyclability, compared to those of the CNT-based counterpart cell. Through various ex/in situ qualitative/quantitative characterizations, the Mo2C-based Li–CO2 battery with WIS can operate on the reversible conversion of CO2-to-Li2C2O4 ((e–/CO2)ideal = 1) at lower discharge/charge overpotentials, while the CNT-based counterpart cell is based on the formation/decomposition of Li2CO3 ((e–/CO2)ideal ≈ 1.33) at high overpotentials. Such a difference in CO2 reduction products stems from the stronger interaction between Mo2C(101) and Li2C2O4 than that of the CNT and Li2C2O4 based on the density functional theory calculations, resulting in the selective stabilization of the intermediate product Li2C2O4 on the Mo2C surface.
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
·
2024
·Vol. 15
·期 1
·1-11
·
IF 14.7
Li Wei,Zhang Menghang,Sun Xinyi,Sheng Chuanchao,Mu Xiaowei,Wang Lei,He Ping,Zhou Haoshen
Li-CO 2 batteries offer a promising avenue for converting greenhouse gases into electricity. However, the inherent challenge of direct electrocatalytic reduction of inert CO 2 often results in the formation of Li 2 CO 3 , causing a dip in output voltage and energy efficiency. Our innovative approach involves solid redox mediators, affixed to the cathode via a Cu(II) coordination compound of benzene-1,3,5-tricarboxylic acid. This technique effectively circumvents the shuttle effect and sluggish kinetics associated with soluble redox mediators. Results show that the electrochemically reduced Cu(I) solid redox mediator efficiently captures CO 2 , facilitating Li 2 C 2 O 4 formation through a dimerization reaction involving a dimeric oxalate intermediate. The Li-CO 2 battery employing the Cu(II) solid redox mediator boasts a higher discharge voltage of 2.8 V, a lower charge potential of 3.7 V, and superior cycling performance over 400 cycles. Simultaneously, the successful development of a Li-CO 2 pouch battery propels metal-CO 2 batteries closer to practical application.
研究领域:
电化学
·
材料科学
·
能源存储
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）