過渡金屬硼酸鹽具有成本低、環(huán)保友好、電壓極化低和氧化還原電位合適等優(yōu)點(diǎn),是一種極具應(yīng)用前景的新興材料。硼原子與氧原子的鍵合可以形成具有高電負(fù)性位點(diǎn)的陰離子(如BO33-、BO45-和BO69-),這些陰離子可以與過渡金屬陽離子鍵合,使得過渡金屬硼酸鹽具有不同的結(jié)構(gòu)。盡管一些過渡金屬硼酸鹽表現(xiàn)出比相應(yīng)的過渡金屬氧化物更優(yōu)越的初始庫侖效率(ICE),但它們?cè)诨谔妓狨ル娊庖旱拟c離子電池中具有較差的倍率性能和循環(huán)壽命,阻礙了其實(shí)際應(yīng)用。
基于此,四川大學(xué)高分子科學(xué)與工程學(xué)院王延青特聘研究員課題組,在材料領(lǐng)域知名期刊Advanced Science上發(fā)表題為“Combustion activation induced solid-state synthesis for N, B co-doped carbon/zinc borate anode with a boosting of sodium storage performance”的研究論文。
Figure 1. Na+ storage mechanism and rate performance of CBZG anode.
本文要點(diǎn)
要點(diǎn)一:基于插層誘導(dǎo)燃燒活化法合成了N、 B共摻雜碳/硼酸鋅(CBZG)
Figure 2. a) Illustration of the synthesis process for CBZG. TG curves of b) the mixture of Zn(NO3)2·6H2O and glycine, c) H3BO3, and d) the mixture of Zn(NO3)2·6H2O, glycine and H3BO3.
要點(diǎn)二: CBZG的形貌結(jié)構(gòu)
Figure 3. Structure and morphology of the obtained materials. a) XRD patterns of BZ, CBZ, and CBZG. b) SEM image of CBZG. c) Element mapping images of CBZG. d) TEM image of CBZG. e, f) High-resolution TEM images of CBZG.
要點(diǎn)三: CBZG在醚/酯基電解液中的鈉離子電池性能
Figure 4. Na+ storage performance of CBZG as the half-cell anode in ether- or ester-based electrolyte. a, b) CV curves at 0.2 mV s-1. c) Discharge/charge profiles at 0.05 A g-1. d) Rate capability. e) Comparison between CBZG anode and previously reported SIB anodes in capacity. Cycling performance at f) 2 A g-1 and g) 10 A g-1.
要點(diǎn)四: CBZG在醚/酯基電解液中的儲(chǔ)鈉機(jī)理
Zn6O(OH)(BO3)3+Na++e-?3ZnO+Zn3B2O6+NaBO2+0.5H2①
Zn3B2O6+6Na++6e-?3Zn+3Na2O+B2O3②
反應(yīng)①在醚基電解液中不可逆,而在酯基電解液中可逆。
Figure 5. Na+ storage process analysis of CBZG as the half-cell anode in ether- or ester-based electrolyte. Discharge/charge profiles at 0.05 A g-1 and ex situ XRD patterns under various stages in a) ether-based electrolyte and b) ester-based electrolyte.
要點(diǎn)五: CBZG在醚/酯基電解液中的動(dòng)力學(xué)過程
Figure 6. Kinetics analysis of Na+ storage of CBZG anode in ether- or ester-based electrolyte. a, b) CV curves at different scan rates. c) b-value calculation. d, e) Capacitive contributions at 1.0 mV s-1. f) Capacitive contributions at different scan rates. g) GITT potential profiles with a pulse current of 0.05 A g-1 for 0.5 h, followed by a 1.0 h relaxation process. h) Na+ diffusion coefficients calculated from the GITT potential profiles for the discharge process. i) Nyquist plots.
文章鏈接:Combustion activation induced solid-state synthesis for N, B co-doped carbon/zinc borate anode with a boosting of sodium storage performance
DOI:10.1002/advs.202207751
http://doi.org/10.1002/advs.202207751
通訊作者簡(jiǎn)介
王延青博士,男,四川大學(xué)特聘研究員,四川省“海外高層次人才引進(jìn)計(jì)劃”特聘專家,國家制革技術(shù)研究推廣中心特聘專家,四川省專家服務(wù)團(tuán)專家,日本政府高端引進(jìn)外國人(日本高度人才1號(hào))。入選四川大學(xué)“雙百人才工程”計(jì)劃(2019-2023),日本學(xué)術(shù)振興會(huì)(JSPS)外國人特別研究員(2015-2017)。2019年加入四川大學(xué)高分子科學(xué)與工程學(xué)院高材系獨(dú)立開展研究工作,成立先進(jìn)碳與能源材料應(yīng)用研究室。主要從事超長碳納米管的單分散原理、碳基材料的設(shè)計(jì)制備及其在能源、環(huán)境相關(guān)領(lǐng)域的應(yīng)用研究,主要包括:超長碳納米管在非/弱極性有機(jī)體系的分散研究、新型高倍率快充鋰電池導(dǎo)電劑、低溫鋰電池負(fù)極、鈉電池硬碳負(fù)極、電磁屏蔽/吸波材料、超級(jí)電容器、碳基導(dǎo)熱/散熱材料、柔性顯示材料、先進(jìn)高分子功能材料等,在Advanced Science(2篇),Carbon(8篇),Chemical Engineering Journal,Small,J Mater Chem A,Energy Storage Materials等高水平學(xué)術(shù)期刊上發(fā)表論文40余篇。研究成果獲得了山東省科技進(jìn)步一等獎(jiǎng)、國家優(yōu)秀自費(fèi)留學(xué)生獎(jiǎng)學(xué)金、中國專利優(yōu)秀獎(jiǎng)、山東省專利獎(jiǎng)、四川省特聘專家、JSPS外國青年學(xué)者研究獎(jiǎng)勵(lì)、北海道大學(xué)私費(fèi)外國人留學(xué)生特待制度、四川大學(xué)優(yōu)秀科技人才獎(jiǎng)、鹽都特聘專家等。
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