光辅助锂-二氧化碳电池催化剂的设计策略与反应机理研究进展

doi:10.11949/0438-1157.20240091

摘要/Abstract

摘要：

光辅助Li-CO₂电池具有理论能量密度高、环境友好等特点，是下一代高比能电池系统的重要发展方向。然而，正极处CO₂还原/析出反应存在动力学缓慢等问题，限制了Li-CO₂电池发展。光辅助技术利用正极负载的光催化剂吸收光能，产生电子和空穴以驱动化学反应，有利于提升电池性能。本文阐述了光辅助Li-CO₂电池的光化学原理及充放电反应机制，详细列举了正极光催化剂的设计策略及具体实例。通过深入探讨Li-CO₂电池的光催化反应机理，进一步理解了光催化剂结构对电池性能的影响机制。此外，还讨论了光辅助Li-CO₂电池的基本认识、当前面临的挑战以及对光催化剂发展前景的展望，为新能源材料领域的技术研究提供了重要的参考，有助于推动Li-CO₂电池的实用化进程。

关键词: Li-CO₂电池, 正极光催化剂, 反应机理, 设计策略

Abstract:

Photo-assisted Li-CO₂batteries have the characteristics of high theoretical energy density and environmental friendliness, which are important development direction for the next generation of high specific energy battery systems. However, the slow kinetics of CO₂ reduction/evolution reaction at the positive electrode limit the development of Li-CO₂batteries. Photo-assisted technology utilizes the photocatalyst loaded on the positive electrode to absorb light energy, generate electrons and holes to drive chemical reactions, which is beneficial for improving battery performance. This Review summarizes the photochemical principles and charge-discharge reaction mechanism of photo-assisted Li-CO₂batteries, lists design strategies and specific examples of cathode photocatalysts. The impact of photocatalyst structure on battery performance is further understood through in-depth exploration of the photocatalytic reaction mechanism of Li-CO₂batteries. In addition, the basic understanding of photo-assisted Li-CO₂ batteries, current challenges, and prospects for the development of photocatalysts were discussed, providing an important reference for technical research in the field of new energy materials and helps to promote the practical process of Li-CO₂ batteries.

Key words: Li-CO₂batteries, cathode photocatalyst, reaction mechanism, design strategy

中图分类号:

O 646

赵亭亭, 鄢立祥, 唐福利, 肖敏之, 谭烨, 宋刘斌, 肖忠良, 李灵均. 光辅助锂-二氧化碳电池催化剂的设计策略与反应机理研究进展[J]. 化工学报, DOI: 10.11949/0438-1157.20240091.

Tingting ZHAO, Lixiang YAN, Fuli TANG, Minzhi XIAO, Ye TAN, Liubin SONG, Zhongliang XIAO, Lingjun LI. Research progress on design strategies and reaction mechanisms of catalysts for photo-assisted Li-CO₂ batteries[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240091.

图/表 11

图1 Li-CO2电池光催化剂设计策略及机理发展时间线

Fig.1 Timeline of design strategies and mechanism development of photocatalysts for Li-CO2 batteries

图2 光辅助Li-CO2电池光催化反应过程示意[24]

Fig.2 Schematic diagram of the photocatal reaction process of photo assisted Li-CO2 batteries[24]

图3 光辅助Li-CO2电池中形成Li2CO3放电产物的可能路径图[40]

Fig.3 Possible pathway diagram for the formation of Li2CO3 discharge products in photo assisted Li-CO2 batteries[40]

图4 (a)光诱导放电过程的工作机制；(b)In2S3@CNT/SS的能带图；(c)ICS、In2S3NS/SS和CNT对紫外光的光电流响应[40]

Fig.4 (a)The working mechanism for the light-induced discharging process;(b)Band diagram of the In2S3@CNT/SS;(c)Photocurre nt response to UV light of ICS, In2S3NS/SS, and CNT[40]

图5 (a)中间LiCO2分子在TNA上的优化结构和吸附能；(b)中间LiCO2分子在TNA@AgNPs上的优化结构和吸附能；(c)电池表面和溶液介导反应途径的吉布斯自由能图[38]

Fig.5 (a)Optimized structures and adsorption energy of intermediate LiCO2 molecules on the TNAs;(b)Optimized structures and adsorption energy of intermediate LiCO2 molecules on the TNAs@AgNPs;(c)Gibbs free energy diagrams of battery surface and solution-mediated reaction pathways[38]

图6 (a)基于TiO2 NAs/CT和RuO2–TiO2 NAs/CT阴极的Li–CO2电池中Li2CO3不同生长机制的示意图；(b)Li2CO3在TiO2和RuO2表面上的优化结构和相应的结合能；(c)吸附在TiO2和RuO2表面上的CO2或Li2CO3的电荷密度差Δρ[37]

Fig.6 (a) Schematic illustration of different growth mechanisms of Li2CO3 in the Li–CO2 batteries based on TiO2 NAs/CT and RuO2–TiO2 NAs/CT cathodes; (b) The optimized structures and the corresponding binding energy of Li2CO3 on TiO2 and RuO2 surfaces;(b) The differential charge density Δρ of CO2 or Li2CO3 adsorbed on TiO2 and RuO2 surfaces[37]

图7 (a)使用TiO2/CC阴极的Li-CO2电池在照明和不照明情况下的充电曲线；(b)在0.5 mCO2饱和LiTFSI/DME溶液中，扫描速率为5 mV s-1，光照和不光照下TiO2/CC在CO2ER区域的LSV曲线；(c)相应的Tafel曲线；(d)采用TiO2/CC阴极的Li-CO2电池在光照和不光照下的恒流间歇滴定技术曲线；(e)照明下Li-CO2电池充电电压降低的能量图示意图[34]

Fig.7 (a) Charge curves of Li-CO2 batteries with TiO2/CC cathode with and without illumination; (b) LSV curves measured in the CO2ER region of TiO2/CC with and without illumination in 0.5 m CO2-saturated LiTFSI/DME solution at a scan rate of 5 mV s-1; (c) Corresponding Tafel curves; (d) Galvanostatic intermittent titration technique curves obtained from Li-CO2 battery with TiO2/CC cathode with and without illumination; (e) Schematic of energy diagrams for the reduced charge voltage of Li-CO2 battery under illumination[34]

表1 光辅助Li-CO2电池的结构和性能

Table 1 Structure and performance of photo assisted Li-CO2 batteries

光催化剂	首次效率（%）	电流密度（mA cm^-2）	放电比容量（mAh cm^-2）	充电/放电电压平台（V）	循环次数（圈）	参考文献
TiO₂/CC	97.2	0.01	0.01	2.82/2.88	30	[34]
RuO₂/TiO₂	95.5	250（mA g^-1）	1000（mAh g^-1）	2.78/2.91	238	[37]
TiO₂@Ag	87.1	0.01	0.1	2.49/2.86	100	[38]
Cu₂O/CNT	85	100 （mA g^-1）	100（mAh g^-1）	2.5/4.5	50	[39]
In₂S₃@CNT/SS	98.1	0.01	0.01	3.14/3.2	25	[40]
CNT@C₃N₄	98.8	0.02	0.02	3.24/3.28	100	[32]
SiC/RGO	84.4	20（mA g^-1）	0.01	2.77/3.28	20	[41]
CoPc–Mn–O	98.5	0.02	/	3.20/3.25	30	[33]
Au@TiO₂	92.4	0.01	0.01	2.95/3.49	200	[42]
混合相TiO₂	/	0.025	/	2.2/3.0	52	[43]

图8 (a)通过基于等离子体和激子的方法描绘等离子体半导体纳米材料的太阳光谱光热效应的示意图；(b)Au@TiO2和TiO2表面温度升高的开/关响应；(c)和(d)光照条件下TiO2和Au@TiO2球体表面温度升高的分布；(e)Au@TiO2和TiO2球的I-T曲线；(f)光照条件下TiO2 （左）和Au@TiO2（右）球表面的电近场分布；(g)TiO2和Au@TiO2球在光照和无光照情况下的CDR过程的LSV曲线[42]

Fig.8 (a) Schematic depiction of the solar-spectrum photothermal effect of plasmonic semiconductor nanomaterials via plasmon-and exciton-based approaches;(b)On/off response of the surface temperature increase of Au@TiO2 and TiO2;(c) and (d)Distribution of the surface temperature increase on TiO2 and Au@TiO2 spheres under the illumination conditions; (e)I-T curves of Au@TiO2 and TiO2 spheres;(f)Distribution of the electric near field under the illumination conditions on TiO2(left) and Au@TiO2 (right) spheres surface;(g)LSV curves for the CDR process of TiO2 and Au@TiO2 spheres with and without illumination[42]

图9 (a)SiC薄片和RGO的协同效应示意图；(b) RGO、SiC/RGO和纯SiC的紫外可见漫反射光谱；(c)Tauc图；(d)Mott-Schottky图；(e)室温PL光谱；(f)SiC/RGO和SiC阴极在光照下的LSV曲线[41]

Fig.9 (a)Schematic diagram of the synergistic effect of SiC flakes and RGO;(b)UV-vis diffuse reflectance spectra of RGO, SiC/RGO and pure SiC; (c)The Tauc plot;(d) Mott-Schottky plots;(e)room-temperature PL spectra of SiC and SiC/RGO samples;(f)LSV curves of SiC/RGO and SiC cathodes under illumination[41]

图10 (a)双场辅助Li-CO2电池的工作机制；(b)首次循环的充/放电电压曲线；(c)循环性能；(d)采用TNA和TNA@AgNPs阴极的Li-CO2电池在光暗条件下的倍率能力；(e)TNA@AgNPs正极在1.0 mAh cm-2和2.0 mAh cm-2下的充/放电曲线；(f)和(g)双场辅助Li-CO2电池与一些基于电催化和光电催化机制的代表性Li-CO2电池的循环稳定性和倍率性能比较[38]

Fig.10 (a)Working mechanism of the dual-field assisted Li-CO2 battery;(b)Discharge/charge voltage profiles at the first cycle;(c)cycling performance;(d) rate capability of Li-CO2 batteries with TNAs and TNAs@AgNPs cathodes in light or dark;(e)Discharge/charge curves of the TNAs@AgNPs cathode in light at 1.0 mAh cm-2 and 2.0 mA cm-2;(f) and (g)Comparison of cycling stability and rate capability of the dual-field assisted Li-CO2 battery with some representative Li-CO2 batteries based on the electrocatalysis and photo electrocatalysis mechanisms[38]

参考文献 72

1	Armand M, Tarascon J M. Building better batteries[J]. Nature, 2008, 451: 652-657.
2	Chen B, Chao D L, Liu E Z, et al. Transition metal dichalcogenides for alkali metal ion batteries: engineering strategies at the atomic level[J]. Energy & Environmental Science, 2020, 13(4): 1096-1131.
3	Don M. Building a better battery[J]. MRS Bulletin, 2020, 45(3): 246-247.
4	Li M, Lu J, Chen Z W, et al. 30 years of lithium-ion batteries[J]. Advanced Materials, 2018: e1800561.
5	Chen K, Yang D Y, Huang G, et al. Lithium-air batteries: air-electrochemistry and anode stabilization[J]. Accounts of Chemical Research, 2021, 54(3): 632-641.
6	Ohno S, Zeier W G. Toward practical solid-state lithium–sulfur batteries: challenges and perspectives[J]. Accounts of Materials Research, 2021, 2(10): 869-880.
7	Zhang L, Wang S, Wang Q, et al. Dendritic solid polymer electrolytes: a new paradigm for high-performance lithium-based batteries[J]. Advanced Materials, 2023, 35(35): e2303355.
8	Ma L, Yu T W, Tzoganakis E, et al. Fundamental understanding and material challenges in rechargeable nonaqueous Li–O₂ batteries: recent progress and perspective[J]. Advanced Energy Materials, 2018, 8(22): 1800348.
9	Xiao X, Zhang Z J, Yan A J, et al. Upgrading carbon utilization and green energy storage through oxygen-assisted lithium-carbon dioxide batteries[J]. Energy Storage Materials, 2024, 65: 103129.
10	Chen L, Zhou J W, Wang Y H, et al. Flexible, stretchable, water-/ fire-proof fiber-shaped Li-CO₂ batteries with high energy density[J]. Advanced Energy Materials, 2023, 13(1): 2202933.
11	Zhao W T, Yang Y, Deng Q H, et al. Toward an understanding of bimetallic MXene solid‐solution in binder-free electrocatalyst cathode for advanced Li-CO₂ batteries[J]. Advanced Functional Materials, 2022, 33(5): 1.
12	Sun X Y, Mu X W, Zheng W, et al. Binuclear Cu complex catalysis enabling Li–CO₂ battery with a high discharge voltage above 3.0 V[J]. Nature Communications, 2023, 14: 536.
13	Li X L, Zhang J X, Qi G C, et al. Vertically aligned N-doped carbon nanotubes arrays as efficient binder-free catalysts for flexible Li-CO₂ batteries[J]. Energy Storage Materials, 2021, 35: 148-156.
14	Zhou L J, Wang H, Zhang K, et al. Fast decomposition of Li₂CO₃/C actuated by single-atom catalysts for Li-CO₂ batteries[J]. Science China Materials, 2021, 64(9): 2139-2147.
15	Liu B, Sun Y L, Liu L Y, et al. Recent advances in understanding Li–CO₂ electrochemistry[J]. Energy & Environmental Science, 2019, 12(3): 887-922.
16	Lin J F, Ding J N, Wang H Z, et al. Boosting Energy Efficiency and Stability of Li-CO₂ Batteries via Synergy between Ru Atom Clusters and Single-Atom Ru-N₄ sites in the Electrocatalyst Cathode[J]. Advanced Materials, 2022, 34(17): e2200559.
17	Xiao Y, Hu S L, Miao Y, et al. Recent progress in hot spot regulated strategies for catalysts applied in Li-CO₂ batteries[J]. Small, 2024, 20(1): e2305009.
18	Lu B Y, Min Z W, Xiao X, et al. Recycled tandem catalysts promising ultralow overpotential Li-CO₂ batteries[J]. Advanced Materials, 2024, 36(1): e2309264.
19	Chourasia A K, Shavez M, Naik K M, et al. Candle soot nanoparticles versus multiwalled carbon nanotubes as a high-performance cathode catalyst for Li–CO_2Mars batteries for Mars exploration[J]. ACS Applied Energy Materials, 2023, 6(1): 378-386.
20	Zhou J W, Cheng J L, Wang B, et al. Flexible metal–gas batteries: a potential option for next-generation power accessories for wearable electronics[J]. Energy & Environmental Science, 2020, 13(7): 1933-1970.
21	Gowda S R, Brunet A, Wallraff G M, et al. Implications of CO₂ contamination in rechargeable nonaqueous Li-O2 batteries[J]. The Journal of Physical Chemistry Letters, 2013, 4(2): 276-279.
22	Zhao Z W, Huang J, Peng Z Q. Achilles' heel of lithium-air batteries: lithium carbonate[J]. Angewandte Chemie International Edition, 2018, 57(15): 3874-3886.
23	Yang S X, He P, Zhou H S. Exploring the electrochemical reaction mechanism of carbonate oxidation in Li–air/CO₂ battery through tracing missing oxygen[J]. Energy & Environmental Science, 2016, 9(5): 1650-1654.
24	Li J X, Zhang K, Wang B J, et al. Light-assisted metal-air batteries: progress, challenges, and perspectives[J]. Angewandte Chemie International Edition, 2022, 61(51): e202213026.
25	Savunthari K V, Chen C H, Chen Y R, et al. Effective Ru/CNT cathode for rechargeable solid-state Li-CO₂ batteries[J]. ACS Applied Materials & Interfaces, 2021, 13(37): 44266-44273.
26	Guo C, Zhang F L, Han X, et al. Intrinsic descriptor guided noble metal cathode design for Li-CO₂ battery[J]. Advanced Materials, 2023, 35(33): e2302325.
27	Wang Y F, Ji G J, Song L N, et al. A highly reversible lithium–carbon dioxide battery based on soluble oxalate[J]. ACS Energy Letters, 2023, 8(2): 1026-1034.
28	Fan L, Shen H M, Ji D X, et al. Biaxially compressive strain in Ni/Ru core/shell nanoplates boosts Li-CO₂ batteries[J]. Advanced Materials, 2022, 34(30): e2204134.
29	Zhou J W, Wang T S, Chen L, et al. Boosting the reaction kinetics in aprotic lithium-carbon dioxide batteries with unconventional phase metal nanomaterials[J]. Proceedings of the National Academy of Sciences of the United States of America, 2022, 119(40): e2204666119.
30	Chen L, Zhou J W, Zhang J X, et al. Copper indium sulfide enables Li-CO₂ batteries with boosted reaction kinetics and cycling stability[J]. ENERGY & ENVIRONMENTAL MATERIALS, 2023, 6(5): 12415.
31	Zhang Z, Yang C, Wu S S, et al. Exploiting synergistic effect by integrating ruthenium–copper nanoparticles highly co-dispersed on graphene as efficient air cathodes for Li–CO₂ batteries[J]. Advanced Energy Materials, 2019, 9(8): 1802805.
32	Li J X, Zhang K, Zhao Y, et al. High-efficiency and stable Li-CO₂ battery enabled by carbon nanotube/carbon nitride heterostructured photocathode[J]. Angewandte Chemie International Edition, 2022, 61(4): e202114612.
33	Wang J H, Li S, Chen Y F, et al. Phthalocyanine based metal–organic framework ultrathin nanosheet for efficient photocathode toward light-assisted Li–CO₂ battery[J]. Advanced Functional Materials, 2022, 32(49): 2210259.
34	Wang X X, Guan D H, Li F, et al. A renewable light-promoted flexible LiCO₂ battery with ultrahigh energy efficiency of 97.9%[J]. Small, 2021, 17(26): e2100642.
35	Zhu T, Wang S, Yu Z Q, et al. High-performance Li-CO₂ battery based on carbon-free porous Ru@QNFs cathode[J]. Small, 2023, 19(33): e2301498.
36	Ma Y, Wang X L, Jia Y S, et al. Titanium dioxide-based nanomaterials for photocatalytic fuel generations[J]. Chemical Reviews, 2014, 114(19): 9987-10043.
37	Wang C Z, Shang Y, Lu Y C, et al. Photoinduced homogeneous RuO₂ nanoparticles on TiO₂ nanowire arrays: a high-performance cathode toward flexible Li–CO₂ batteries[J]. Journal of Power Sources, 2020, 475: 228703.
38	Zhang K, Li J X, Zhai W J, et al. Boosting cycling stability and rate capability of Li-CO₂ batteries via synergistic photoelectric effect and plasmonic interaction[J]. Angewandte Chemie International Edition, 2022, 61(17): e202201718.
39	Jena A, Hsieh H C, Thoka S, et al. Curtailing the overpotential of Li–CO₂ batteries with shape-controlled Cu₂O as cathode: effect of illuminating the cathode[J]. ChemSusChem, 2020, 13(10): 2719-2725.
40	Guan D H, Wang X X, Li M L, et al. Light/electricity energy conversion and storage for a hierarchical porous In₂S₃@CNT/SS cathode towards a flexible Li-CO₂ battery[J]. Angewandte Chemie International Edition, 2020, 59(44): 19518-19524.
41	Li Z, Li M L, Wang X X, et al. In situ fabricated photo-electro-catalytic hybrid cathode for light-assisted lithium–CO₂ batteries[J]. Journal of Materials Chemistry A, 2020, 8(29): 14799-14806.
42	Guan D H, Wang X X, Li F, et al. All-solid-state photo-assisted Li-CO₂ battery working at an ultra-wide operation temperature[J]. ACS Nano, 2022, 16(8): 12364-12376.
43	Long L Z, Ding Y Y, Liang N N, et al. A carbon-free and free-standing cathode from mixed-phase TiO₂ for photo-assisted Li-CO₂ battery[J]. Small, 2023, 19(27): e2300519.
44	Jiang J J, Gao J Y, Li T R, et al. Visible-light-driven photo-Fenton reaction with α-Fe₂O₃/BiOI at near neutral pH: boosted photogenerated charge separation, optimum operating parameters and mechanism insight[J]. Journal of Colloid and Interface Science, 2019, 554: 531-543.
45	Piercy R, Hampson N A. The electrochemistry of indium[J]. Journal of Applied Electrochemistry, 1975, 5(1): 1-15.
46	Zhao Z W, Wang E K, Wang J W, et al. Kinetics of the CO₂ reduction reaction in aprotic Li–CO₂ batteries: a model study[J]. Journal of Materials Chemistry A, 2021, 9(6): 3290-3296.
47	Yang C, Guo K K, Yuan D W, et al. Unraveling reaction mechanisms of Mo₂C as cathode catalyst in a Li-CO₂ battery[J]. Journal of the American Chemical Society, 2020, 142(15): 6983-6990.
48	Xu S M, Das S K, Archer L A. The Li–CO₂ battery: a novel method for CO₂ capture and utilization[J]. RSC Advances, 2013, 3(18): 6656-6660.
49	Wang S, Song H C, Zhu T, et al. An ultralow-charge-overpotential and long-cycle-life solid-state Li-CO₂ battery enabled by plasmon-enhanced solar photothermal catalysis[J]. Nano Energy, 2022, 100: 107521.
50	Pipes R, Bhargav A, Manthiram A. Nanostructured anatase titania as a cathode catalyst for Li–CO₂ batteries[J]. ACS Applied Materials & Interfaces, 2018, 10(43): 37119-37124.
51	Xu Y Y, Gong H, Ren H, et al. Highly efficient Cu-porphyrin-based metal-organic framework nanosheet as cathode for high-rate Li-CO₂ battery[J]. Small, 2022, 18(45): e2203917.
52	Gong H, Wang T, Xue H R, et al. Photo-enhanced lithium oxygen batteries with defective titanium oxide as both photo-anode and air electrode[J]. Energy Storage Materials, 2018, 13: 49-56.
53	Baek K, Jeon W C, Woo S, et al. Synergistic effect of quinary molten salts and ruthenium catalyst for high-power-density lithium-carbon dioxide cell[J]. Nature Communications, 2020, 11: 456.
54	Ahmadiparidari A, Warburton R E, Majidi L, et al. A long-cycle-life lithium–CO₂ battery with carbon neutrality[J]. Advanced Materials, 2019, 31(40): 1902518.
55	Guo Q, Zhou C Y, Ma Z B, et al. Fundamentals of TiO₂ photocatalysis: concepts, mechanisms, and challenges[J]. Advanced Materials, 2019, 31(50): e1901997.
56	Hu J Y, Su C B, Li R J, et al. High-performance Li-CO₂ batteries enabled by synergistic interaction of iron dopant-modulated catalysts and nitrogen-modified substrates[J]. Journal of Alloys and Compounds, 2024, 976: 173146.
57	Liu J, Ma N K, Wu W, et al. Recent progress on photocatalytic heterostructures with full solar spectral responses[J]. Chemical Engineering Journal, 2020, 393: 124719.
58	Low J, Yu J G, Jaroniec M, et al. Heterojunction photocatalysts[J]. Advanced Materials, 2017, 29(20): 1601694.
59	Jin Y C, Liu Y, Song L, et al. Interfacial engineering in hollow NiS₂/FeS₂-NSGA heterostructures with efficient catalytic activity for advanced Li-CO₂ battery[J]. Chemical Engineering Journal, 2022, 430: 133029.
60	Sun Z M, Wang D, Lin L, et al. Ultrathin hexagonal boron nitride as a van der Waals' force initiator activated graphene for engineering efficient non-metal electrocatalysts of Li-CO₂ battery[J]. Nano Research, 2022, 15(2): 1171-1177.
61	Cheng Z B, Wu Z Y, Tang Y Y, et al. Cationic metal-organic framework derived ruthenium-copper nano-alloys in porous carbon to catalytically boost the cycle life of Li-CO₂ batteries[J]. Nanoscale, 2022, 14(40): 15073-15078.
62	Han J R, Wu H Y, Song R L, et al. Defect-rich porous carbon as a metal-free catalyst for high-performance Li-CO₂ batteries[J]. Electrochimica Acta, 2024, 477: 143779.
63	Qie L, Lin Y, Connell J W, et al. Highly rechargeable lithium-CO₂ batteries with a boron- and nitrogen-codoped holey-graphene cathode[J]. Angewandte Chemie International Edition, 2017, 56(24): 6970-6974.
64	王禹婷, 杨天怡, 章应辉. 卟啉框架材料在光催化领域的应用[J]. 应用化学, 2020, 37(6): 611-619.
	Wang Y T, Yang T Y, Zhang Y H. Application of porphyrin-based framework materials on photocatalysis[J]. Chinese Journal of Applied Chemistry, 2020, 37(6): 611-619.
65	焦帅, 杨磊, 武婷婷, 等. 混合盐模板法制备超级电容器用氮掺杂分级多孔碳纳米片[J]. 化工学报, 2021, 72(5): 2869-2877.
	Jiao S, Yang L, Wu T T, et al. Synthesis of nitrogen doped hierarchically porous carbon nanosheets for supercapacitor by mixed salt template[J]. CIESC Journal, 2021, 72(5): 2869-2877.
66	后振中, 彭龙贵, 李颖, 等. 分级多孔聚吡咯膜的界面自组装合成与电化学电容性[J]. 化工学报, 2018, 69(9): 4121-4128.
	Hou Z Z, Peng L G, Li Y, et al. Interfacial self-assembly synthesis and electrochemical capacitance of hierarchical porous polypyrrole films[J]. CIESC Journal, 2018, 69(9): 4121-4128.
67	Hu C, Tu S C, Tian N, et al. Photocatalysis enhanced by external fields[J]. Angewandte Chemie International Edition, 2021, 60(30): 16309-16328.
68	Sun Z H, Yin H, Liu K L, et al. Machine learning accelerated calculation and design of electrocatalysts for CO₂ reduction[J]. SmartMat, 2022, 3(1): 68-83.
69	Liu J W, Luo W Z, Wang L, et al. Toward excellence of electrocatalyst design by emerging descriptor-oriented machine learning[J]. Advanced Functional Materials, 2022, 32(17): 2110748.
70	Németh K, Srajer G. CO₂/oxalate cathodes as safe and efficient alternatives in high energy density metal–air type rechargeable batteries[J]. RSC Advances, 2014, 4(4): 1879-1885.
71	Qiao Y, Yi J, Wu S C, et al. Li-CO₂ electrochemistry: a new strategy for CO₂ fixation and energy storage[J]. Joule, 2017, 1(2): 359-370.
72	Su L W, Zhou Z, Qin X, et al. CoCO₃ submicrocube/graphene composites with high lithium storage capability[J]. Nano Energy, 2013, 2(2): 276-282.

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