N, P共掺杂香蒲基炭气凝胶的制备、表征及其电化学性能

doi:10.3969/j.issn.0253-2417.2022.04.001

摘要/Abstract

摘要：

以香蒲花序为原料，NH₄H₂PO₄为掺杂剂，经酸性NaClO₂预处理、超声波细胞破碎处理、冷冻干燥、高温炭化制备N、P共掺杂香蒲基炭气凝胶(NPCA)。采用SEM、N₂吸附/脱附、XRD、XPS对NPCA的形貌、孔隙结构、晶相结构、表面化学组成进行表征，系统研究了掺杂量和炭化温度对NPCA电化学性能的影响。研究结果表明：NPCA是由无定形炭组成的三维网状立体结构；NPCA表面氮元素以吡啶氮(N-6)、吡咯氮(N-5)、石墨化氮(N-Q)和氧化氮(N-X)的形式存在，磷元素以P—O和P—C的形式存在。NH₄H₂PO₄的掺杂量和炭化温度影响NPCA的孔隙结构及表面化学结构。NPAC的较佳制备条件为：香蒲纤维素与NH₄H₂PO₄的质量比为1∶2，炭化温度800 ℃。此条件下制备的NPAC-2-800具有丰富的孔隙结构和表面官能团，比表面积为599.88 m²/g，总孔容积为0.27 cm³/g，微孔容积为0.20 cm³/g，平均孔径为3.69 nm，并且NPCA的N、P质量分数分别为5.69%和5.12%。电化学性能测试结果表明：在6 mol/L KOH溶液、三电极体系中，在1 A/g的电流密度下NPCA-2-800的比电容为249 F/g，比未掺杂NH₄H₂PO₄样品的比电容(106.7 F/g)增加了133.4%，并且具有较好的倍率性能。

关键词: 香蒲, 炭气凝胶, 电化学性能

Abstract:

N and P co-doped carbon aerogels(NPCA) were prepared from cattail inflorescence with NH₄H₂PO₄ as dopant by pretreatment with acidic sodium chlorite, ultrasonic cell fragmentation, freeze-drying and carbonization at high temperature. The surface morphology, pore structure, crystalline structure and surface chemical composition of NPCA were characterized by SEM, N₂ adsorption/desorption, XRD and XPS. The effects of doping amounts and carbonization temperatures on the electrochemical properties of NPCA were systematically studied. The results of research showed that NPCA was a three-dimensional network structure that composed of amorphous carbon. The nitrogen element on the surface of NPCA existed in the form of pyridine nitrogen(N-6), pyrrole nitrogen(N-5), graphitization nitrogen(N-Q) and oxidation state of nitrogen(N-X), and the phosphorus element existed in the form of P—O and P—C. The pore structure and surface chemical structure of NPCA were greatly affected by doping amount of NH₄H₂PO₄ and carbonization temperature. The optimum preparation conditions of NPAC were that the mass ratio of cattail-based cellulose to ammonium dihydrogen phosphate was 1∶2 and the carbonization temperature was 800 ℃. The NPAC-2-800 prepared under this condition has rich pore structure and surface functional groups. Furthermore, the specific surface area was 599.88 m²/g, the total pore volume was 0.27 cm³/g, the micropore volume was 0.20 cm³/g, and the average pore size was 3.69 nm, the N and P contents of NPCA were 5.69% and 5.12%, respectively. The electrochemical properties of the NPCA were measured by three electrode system in 6 mol/L KOH solution. The specific capacitance of NPCA-2-800 was 249 F/g at a current density of 1 A/g, which was 133.4% higher than that of the undoped sample(106.7 F/g), and had good rate performance.

Key words: cattail, carbon aerogel, electrochemical performance

中图分类号:

TQ35

黄举, 孙佳明, 张坤, 吴振威, 李伟, 刘守新. N, P共掺杂香蒲基炭气凝胶的制备、表征及其电化学性能[J]. 林产化学与工业, 2022, 42(4): 1-8.

Ju HUANG, Jiaming SUN, Kun ZHANG, Zhenwei WU, Wei LI, Shouxin LIU. Preparation, Characterization and Electrochemical Performance of N, P Co-doped Cattail-derived Carbon Aerogels[J]. Chemistry and Industry of Forest Products, 2022, 42(4): 1-8.

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样品 samples	m(NH₄H₂PO₄)/m(纤维素) m(NH₄H₂PO₄)/m(cellulose)	炭化温度/ ℃ carbonization temp.	S_BET/(m²·g^-1)	V_tot/(cm³·g^-1)	V_mic/(cm³·g^-1)	D_ave/nm
CA	0	800	466.45	0.22	0.17	3.57
NPCA-2-800	2	800	599.88	0.27	0.20	3.69
NPCA-4-800	4	800	619.26	0.29	0.23	3.73
NPCA-6-800	6	800	635.99	0.32	0.24	4.07
NPCA-2-600	2	600	385.89	0.20	0.12	3.06
NPCA-2-700	2	700	463.42	0.24	0.16	3.82
NPCA-2-900	2	900	515.57	0.25	0.17	4.22

样品 samples	各元素的原子百分比/% elementary composition				不同形式氮的原子百分比¹⁾/% content of nitrogen species				不同形式磷的原子百分比/% content of phosphorus species
样品 samples	C	O	N	P	N-6	N-5	N-Q	N-X	P—C	P—O
NPCA-2-600	65.64	18.99	6.57	8.80	15.81	24.57	31.01	28.61	21.85	78.15
NPCA-2-700	68.64	18.12	6.42	6.82	18.56	19.46	36.24	25.74	35.04	64.96
NPCA-2-800	71.69	17.50	5.69	5.12	21.83	14.20	41.42	22.55	40.97	59.03
NPCA-2-900	76.31	14.85	5.17	3.66	22.49	10.58	47.79	19.14	65.52	34.48

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