无机盐工业
主管:中海油天津化工研究设计院有限公司
主办:中海油天津化工研究设计院有限公司
   中海油炼油化工科学研究院(北京)有限公司
   中国化工学会无机酸碱盐专业委员会
ISSN 1006-4990 CN 12-1069/TQ
研究与开发

纳米片多面体锰基锂离子筛的制备及锂离子吸脱附特性

  • 韩红静 ,
  • 吴勇民 ,
  • 曹永生 ,
  • 韩婷婷 ,
  • 汤卫平
展开
  • 1.青海大学新能源光伏产业研究中心,青海 西宁 810016
    2.上海空间电源研究所
韩红静(1986— ),女,博士,讲师,主要研究方向为盐湖提锂锂离子筛吸附剂制备及工艺研究;E-mail:winniehjhan@163.com

收稿日期: 2021-10-25

  网络出版日期: 2022-08-11

基金资助

青海自然科学基金(2019-ZJ-937Q);上海航天科技创新基金项目(SAST2017-139)

Preparation of nano?flake polyhedral manganese based lithium ion sieve and its adsorption and desorption characteristic for Li+

  • Hongjing HAN ,
  • Yongmin WU ,
  • Yongsheng CAO ,
  • Tingting HAN ,
  • Weiping TANG
Expand
  • 1.New Energy(Photovoltaic) Industry Research Center,Qinghai University,Xining 810016,China
    2.State Key Laboratory of Space Power-sources Technology

Received date: 2021-10-25

  Online published: 2022-08-11

摘要

针对锰基锂离子筛容量发挥不充分、使用寿命短的问题,以电解二氧化锰、氯化锂及无水氯化铝为原料,采用水热法合成了铝原子掺杂锰基离子筛前驱体,经酸洗脱附锂离子后得到锰基锂离子筛H1.6(Mn1-x Al x1.6O4。扫描电镜结果表明,铝原子掺杂后,样品呈均匀光滑的纳米片多面体形貌,进一步的吸脱附等温线分析显示,样品的比表面积显著提高。锂离子吸脱附特性研究结果表明,Li1.6(Mn0.7Al0.31.6O4具有最佳的吸附提锂性能,锂离子溶液初始质量浓度为80 mg/L时,吸附容量为32.32 mg/L,5次循环提锂后,锂离子吸附容量可保持为初始吸附容量的95%。这些结果表明,结晶性好、比表面积大的纳米多面体锰基锂离子筛,吸附容量大、结构稳定性好,可为当前盐湖卤水中锂资源的开发和工艺优化提供技术参考。

本文引用格式

韩红静 , 吴勇民 , 曹永生 , 韩婷婷 , 汤卫平 . 纳米片多面体锰基锂离子筛的制备及锂离子吸脱附特性[J]. 无机盐工业, 2022 , 54(8) : 59 -65 . DOI: 10.19964/j.issn.1006-4990.2021-0646

Abstract

Aiming at the problems of insufficient capacity and short service life for manganese?based lithium ion sieve,electrolytic manganese dioxide,lithium chloride and anhydrous aluminum chloride were used as raw materials to prepare Al-doped manganese?based lithium ion sieve precursor through hydrothermal method.The manganese?based lithium ion sieve H1.6(Mn1-x Al x1.6O4 was obtained after acid extraction of Li+.SEM results indicated that a uniform and smooth nanosheet polyhedron morphology was obtained for the Al doped specimen.BET analysis further showed that the specific surface area was increased significantly.The results of the Li+ adsorption and desorption performance showed that Li1.6(Mn0.7Al0.31.6O4 owned the best property.The equilibrium adsorption capacity was 32.32 mg/L when the initial concentration for Li+ solution was 80 mg/L,and after 5 cycles,the Li+ adsorption capacity could be maintained at 95% of the initial adsorption capacity.These results showed that with good crystallinity and large specific surface area,the nano?flake polyhedral manganese based lithium ion sieve possessed large adsorption capacity and good structure stability,which could provide a technical reference in the exploitation and process improvement of extracting lithium resources form salt?lake brine.

参考文献

1 FLEXER V, BASPINEIRO C F, GALLI C I.Lithium recovery from brines:A vital raw material for green energies with a potential environmental impact in its mining and processing[J].Science of the Total Environment,2018,639:1188-1204.
2 王琪,赵有璟,刘洋,等.高镁锂比盐湖镁锂分离与锂提取技术研究进展[J].化工学报,2021,72(6):2905-2921,3433.
2 WANG Qi, ZHAO Youjing, LIU Yang,et al.Recent advances in magnesium/lithium separation and lithium extraction technologies from salt lake brine with high magnesium/lithium ratio[J].CIESC Journal,2021,72(6):2905-2921,3433.
3 LIU Gui, ZHAO Zhongwei, GHAHREMAN A.Novel approaches for lithium extraction from salt?lake brines:A review[J].Hydrometallurgy,2019,187:81-100.
4 吴静,任秀莲,魏琦峰.盐湖卤水中锂的分离提取研究进展[J].无机盐工业,2020,52(12):1-6.
4 WU Jing, REN Xiulian, WEI Qifeng.Research progress on separation and extraction of lithium from salt?lake brine[J].Inorganic Chemicals Industry,2020,52(12):1-6.
5 KUMAR A, FUKUDA H, HATTON T A,et al.Lithium recovery from oil and gas produced water:A need for a growing energy industry[J].ACS Energy Letters,2019,4(6):1471-1474.
6 GAO Aolei, HOU Xinjuan, SUN Zhenhua,et al.Lithium?desorption mechanism in LiMn2O4,Li1.33Mn1.67O4,and Li1.6Mn1.6O4 according to precisely controlled acid treatment and density functional theory calculations[J].Journal of Materials Chemistry A,2019,7(36):20878-20890.
7 CHITRAKAR R, KANOH H, MIYAI Y,et al.A new type of manganese oxide(MnO2·0.5H2O) derived from Li1.6Mn1.6O4 and its lithium ion?sieve properties[J].Chemistry of Materials,2000,12(10):3151-3157.
8 柏春,郭敏,张慧芳,等.离子筛型锂吸附剂吸附法从盐湖卤水/海水中提锂的研究进展[J].化工进展,2017,36(3):802-809
8 BAI Chun, GUO Min, ZHANG Huifang,et al.The research progress of extracting lithium from brine by lithium ion sieve[J].Chemical Industry and Engineering Progress,2017,36(3):802-809
9 GAO Aolei, SUN Zhenhua, LI Shaopeng,et al.The mechanism of manganese dissolution on Li1.6Mn1.6O4 ion sieves with HCl[J].Dalton Transactions,2018,47(11):3864-3871.
10 杨珊珊,阮慧敏,沈江南,等.尖晶石型锂锰氧化物离子筛的制备方法及构效性能分析[J].化工进展,2015,34(6):1690-1698,1736.
10 YANG Shanshan, RUAN Huimin, SHEN Jiangnan,et al.Preparation methods and analyses of structural performance of spinel?type lithium manganese oxide ion sieves[J].Chemical Industry and Engineering Progress,2015,34(6):1690-1698,1736.
11 QIAN Fangren, ZHAO Bing, GUO Min,et al.Enhancing the Li+ adsorption and anti?dissolution properties of Li1.6Mn1.6O4 with Fe,Co doped[J].Hydrometallurgy,2020,193.Doi:10.1016/j.hydromet.2020.105291 .
12 MA Liwen, CHEN Baizhen, SHI Xichang,et al.Stability and Li+ extraction/adsorption properties of LiM x Mn2- x O4(M=Ni,Al,Ti;0≤x≤1) in aqueous solution[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2010,369(1/2/3):88-94
13 CHEN Minmin, WU Ruyun, JU Shengui,et al.Improved performance of Al-doped LiMn2O4 ion-sieves for Li+ adsorption[J].Microporous and Mesoporous Materials,2018,261:29-34.
14 许乃才,黎四霞,曹佳佳,等.锰氧化物锂离子筛的掺杂改性及吸附性能研究[J].无机盐工业,2020,52(4):37-41.
14 XU Naicai, LI Sixia, CAO Jiajia,et al.Research on doping modification and adsorption performance of manganese oxides lithium ion sieve[J].Inorganic Chemicals Industry,2020,52(4):37-41.
15 LI Xiaowei, CHEN Linlin, CHAO Yanhong,et al.Amorphous TiO2-derived large?capacity lithium ion sieve for lithium reco?
15 very[J].Chemical Engineering & Technology,2020,43(9):1784-1791.
16 LI Li, QU Wenjie, LIU Fang,et al.Surface modification of spinel λ-MnO2 and its lithium adsorption properties from spent lithium ion batteries[J].Applied Surface Science,2014,315:59-65.
17 SHAO-HORN Y, MIDDAUGH R L.Redox reactions of cobalt,aluminum and titanium substituted lithium manganese spinel compounds in lithium cells[J].Solid State Ionics,2001,139(1/2):13-25.
18 XUE Feng, WANG Boyang, CHEN Minmin,et al.Fe3O4-doped lithium ion?sieves for lithium adsorption and magnetic separ?
18 ation[J].Separation and Purification Technology,2019,228.Doi:10.1016/j.seppur.2019.115750 .
19 WANG Shimin, XIANG Mingwu, LU Yao,et al.Facile solid?state combustion synthesis of Al-Ni dual?doped LiMn2O4 cathode materials[J].Journal of Materials Science:Materials in Electronics,2020,31(8):6036-6044.
20 ZHU Guiru, WANG Pan, QI Pengfei,et al.Adsorption and desorption properties of Li+ on PVC-H1.6Mn1.6O4 lithium ion-sieve membrane[J].Chemical Engineering Journal,2014,235:340-348
21 HAN H J, QU W, ZHANG Y L,et al.Enhanced performance of Li+ adsorption for H1.6Mn1.6O4 ion?sieves modified by Co doping and micro array morphology[J].Ceramics International,2021,47(15):21777-21784.
22 ZHANG Guotai, ZHANG Jingze, ZHOU Yuan,et al.Synthesis of aluminum?doped ion?sieve manganese oxides powders with enhanced adsorption performance[J].Colloids and Surfaces A:Phy?
22 sicochemical and Engineering Aspects,2019,583.Doi:10.1016/j.colsurfa.2019.123950 .
文章导航

/