层状结构的过渡金属氢氧化物(TMHs)以其丰富的法拉第氧化还原反应、多重离子价态、可调组分和高理论容量等优势,使其在超级电容器领域中受到广泛青睐。利用乙酸锌[Zn(CH3COO)2·2H2O]水溶液诱导镍钴金属醇盐微球(NiCo-GSs)一步水解得到三元过渡金属离氢氧化物(NiCoZn-OH)纳米片电极材料,探究了乙酸锌用量对目标电极材料形貌、结构以及电化学性能的影响。结果表明:在NiCo-GSs水解过程中,Zn2+离子进入氢氧化物主层结构,而CH3COO-离子则嵌入层间,扩大了层间距。Zn(CH3COO)2·2H2O用量为10mg时,所制NiCoZn-OH-10显示出典型的二维片层结构特点,其比表面积和孔体积分别高达175.9m2/g和0.67cm3/g。在三电极体系中,NiCoZn-OH纳米片在1A/g的电流密度下表现出760C/g的比容量,且在30A/g的电流密度下,依旧显示出优异的84.8%容量保持率;在10A/g电流密度的条件下循环充放电3000次后,NiCoZn-OH-10的比容量还可以达到初始值的89.95%,表明其具有优异的循环稳定性。
Transition metal hydroxides with layered structures have attracted wide attention in the field of supercapacitor owing to their merits,such as rich Faraday redox reactions,multiple ionic valance states,adjustable compositions and high theoretical capacity.In this work,the ternary transition metal hydroxide (NiCoZn-OH) nanosheets were prepared via one step hydrolysis of nickel cobalt alkoxide spheres (NiCo-GSs) in zinc acetate [Zn(CH3COO)2·2H2O] aqueous solution,and the effect of zinc acetate content on the micromorphology,structures and electrochemical properties of the target electrode materials were also explored.The results showed that during the hydrolysis of NiCo-GSs,Zn2+ ions entered the host layers of final hydroxides,while the CH3COO- ions were inserted into the interlayers,enlarging the layer distance.When the amount of Zn(CH3COO)2·2H2O was 10mg,the as-obtained NiCoZn-OH-10 samples exhibited the structural characteristics of two-dimensional materials,with a specific surface area and pore volume reaching 175.9m2/g and 0.67cm3/g,respectively.In the three-electrode system,the specific capacity of NiCoZn-OH-10 electrode was 760C/g at 1A/g,and it also displayed a favorable rate performance of 84.8% as the current density was increased to 30A/g.Impressively,the capacity retention could still reach 89.95% of its initial value after continuous charging/discharging 3000 cycles under 10A/g,indicating its excellent cycling stability.
[1] He W K,Li J J,Zhang Y Y,et al.High-performance supercapacitors using hierarchical and sulfur-doped trimetallic NiCo/NiMn layered double hydroxides[J].Small Methods,2023:2301167-2301177.
[2] Yang W,Zhang C X,Du S X,et al.Potentiostatic reconstruction of Nickel-Cobalt hydroxysulfate with self-optimized structure for enhancing energy storage[J].Advanced Energy Materials,2022,12(41):2202286.
[3] Wang G W,Meng Y,Chi C L,et al.Acetate ion-intercalated NiCo-LDH with quasi-theoretical capacitance for high energy/power density aqueous supercapacitors[J].Inorganic Chemistry Frontiers,2024,11(3):863-873.
[4] 郭容男,李太文,王栋,等.超级电容器用MOFs衍生纳米电极材料的研究进展[J].人工晶体学报,2023,52(11):1922-1930.
[5] 杨旋,于学文,许圣豪,等.氮磷硫共掺杂生物质基多孔炭的制备及其电化学性能[J].农业工程学报,2023,39(24):224-234.
[6] 张亚飞.碳纳米材料在超级电容器中的应用[J].材料导报,2023,37(z2):29-35.
[7] 王晓亮,于振秋,常雷明,等.电沉积法制备氢氧化物/氧化物超级电容器电极的研究进展[J].化工进展,2023,42(10):5272-5285.
[8] 朱晓军,朱再立,齐宁,等.三维结构钴镍基双金属硫化物对超级电容器的影响[J].有色金属工程,2023,13(9):57-63.
[9] Lu X Y,Xue H R,Gong H,et al.2D layered double hydroxide nanosheets and their derivatives toward efficient oxygen evolution reaction[J].Nano-Micro Letters,2020,12(1):1-32.
[10] 陈宇佳,杨保俊,王鑫,等.三元类水滑石超薄纳米片的制备及其除氯性能[J].化工环保,2022,42(3):344-349.
[11] 李静霄,叶发萍,解玉龙,等.钴铝双金属氢氧化物的制备及电化学性能研究[J].化学研究与应用,2023,35(3):662668.
[12] Yuan J Z,Li Y X,Lu G G,et al.Controlled synthesis of flower-like hierarchical NiCo-layered double hydroxide integrated with metal-organic framework-derived Co@C for supercapacitors[J].ACS Applied Materials & Interfaces,2023,15(30):36143-36153.
[13] Mule A R,Ramulu B,Arbaz S J,et al.Ag-integrated mixed metallic Co-Fe-Ni-Mn hydroxide composite as advanced electrode for high-performance hybrid supercapacitors[J].Journal of Energy Chemistry,2024,88:579-591.
[14] Ding Y J,Yan Z X,Wang G S,et al.Regulating the oxygen vacancy and electronic structure of NiCo layered double hydroxides by molybdenum doping for high-power hybrid supercapacitors[J].Small,2023,22(8):2306382.
[15] Wu B,Zhang G F,Ji J W,et al.ZIF-67-derived antivirus cobalt hydroxide LDH nanosheets produced through high-concentration cobalt ion-assisted hydration[J].Advanced Functional Materials,2024,34(14):2312941.
[16] Hao J Y,Yan L J,Zou X F,et al.Series of halogen engineered Ni(OH)2 nanosheet for pseudocapacitive energy storage with high energy density[J].Small,2023,19(35):2300467.
[17] Atika,Dutta R K.Role of different aliphatic diols on the structural and morphological aspects of Ni(OH)2 synthesized by thermal decomposition via refluxing method and their effect on charge storage properties[J].Journal of Alloys and Compounds,2023,934:167959.
[18] Hu Q,Wang H,Xiang F F,et al.Critical roles of molybdate anions in enhancing capacitive and oxygen evolution behaviors of LDH@PANI nanohybrids[J].Chinese Journal of Catalysis,2021,42(6):980-993.
[19] Iyi N,Sasaki T.Decarbonation of MgAl-LDHs (layered double hydroxides) using acetate-buffer/NaCl mixed solution[J].Journal of Colloid and Interface Science,2008,322(1):237-245.
[20] Chai L L,Bala Musa A,Pan J Q,et al.In-situ growth of NiAl layered double hydroxides on Ni-based metal-organic framework derived hierarchical carbon as high performance material for Zn-ion batteries[J].Journal of Power Sources,2022,544:231887.
[21] Lin Z T,Li L,Xi C H,et al.Fabrication of the hollow dodecahedral NiCoZn layered double hydroxide for high-performance flexible asymmetric supercapacitor[J].Journal of Colloid and Interface Science,2024,657:91.
[22] 蒋甜甜,许雪棠,王凡.卤离子调控的镍钴基电极材料生长及电容影响研究[J].无机盐工业,2022,54(8):66.
[23] Zhang G F,Qin P,Nasser R,et al.Synthesis of Co(CO3)0.5(OH)/Ni2(CO3)(OH)2 nanobelts and their application in flexible all-solid-state asymmetric supercapacitor[J].Chemical Engineering Journal,2020,387:124029.
[24] Miao Y D,Wang T D,Hua J L,et al.Design of a scalable dendritic copper@Ni2+,Zn2+ cation-substituted cobalt carbonate hydroxide electrode for efficient energy storage[J].ACS Applied Materials & Interfaces,2021,13(33):39205-39214.
[25] 尹青,杨姝涵,宋挚豪,等.米粒型氯插层NiFe层状双金属氢氧化物作为新概念氯离子电池正极材料[J].材料导报,2023,37(21):9-16.
[26] 杨文,丁倩瑶,翟冬梅,等.中空笼状多孔结构镍钴层状氢氧化物的制备及其电化学性能[J].物理学报,2022,71(1):293-302.
[27] 阳昌英,宋方祥,陈前林.双金属镍钴氢氧化物的制备及其电化学性能研究[J].功能材料,2023,54(10):10014-10020.
[28] Guan X H,Fan X Y,Zhu E Z,et al.Controlled establishment of advanced local high-entropy NiCoMnFe-based layered double hydroxide for zinc batteries and low-temperature supercapacitors[J].Journal of Colloid and Interface Science,2024,658:952-965.
基金资助
太原工业学院引进人才科研资助项目(2022LJ046和2023KJ009);山西省基础研究计划项目(202303021212279)
PDF
