Effect of Cu2+ concentration in cathode on power generation and copper removal of thermally regenerative ammonia-based battery

TANG Zhiqiang1,2 ZHANG Liang1,2 ZHU Xun1,2 LI Jun1,2 FU Qian1,2 LIAO Qiang1,2

(1.Key Laboratory of Low-grade Energy Utilization Technologies and Systems (Chongqing University), Ministry of Education, Chongqing, China 400030)
(2.Institute of Engineering Thermophysics, Chongqing University, Chongqing, China 400030)

【Abstract】The thermally regenerative ammonia-based battery (TRAB) exhibits unique advantages and good application prospects in the recycling of waste resources. By constructing TRAB to treat Cu2+-containing waste liquid and recovering electric energy and copper resources, the effects of different Cu2+ concentrations on the battery power generation performance and Cu2+ removal of waste liquid were studied. The results showed that, with the increasing Cu2+ concentration less than 0.2 mol/L, the maximal power, the total charge, the energy density, and copper removal rate increased during the discharging. A very-low final concentration and a high removal rate of Cu2+ indicated that TRAB was feasible for the treatment of the waste water containing Cu2+. The two-step treatment method using TRAB combined with the electrocoagulation method in the follow-up study is expected to further improve the treatment effect, and has good economic and application prospects.

【Keywords】 thermally regenerative ammonia-based battery; Cu2+ concentration; maximal power; Cu2+ removal rate; electrochemistry; wastewater; recovery;


【Funds】 National Natural Science Foundation of China (51606022) Natural Science Foundation of Chongqing, China (cstc2017jcyjAX0203) Scientific Research Foundation for Returned Overseas Chinese Scholars of Chongqing, China (cx2017020) Fundamental Research Funds for the Central Universities of Ministry of Education of China (10611 2016CDJXY 145504) Research Funds of Key Laboratory of Low-grade Energy Utilization Technologies and Systems (Chongqing University) (LLEUTS-2018005)

Download this article


    [1] Yan Z, Xiong Y, Wang K J, et al. Induction crystallization process for treatment of copper-containing wastewater [J]. CIESC Journal, 2009, 60 (10): 2603–2608 (in Chinese).

    [2] Chen X, Xu X Y, Zhao B, et al. Treatment of copper–nickel mixed wastewater by spray bed electrodeposition [J]. CIESC Journal, 2015, 66 (12): 5060–5066 (in Chinese).

    [3] Zhang H, Shi L J, Yang C, et al. Research progress in electroplating wastewater treatment technology [J]. Plating & Finishing, 2018, (2): 36–41 (in Chinese).

    [4] General Administration of Quality Supervision, Inspection and Quarantine of the People’s Republic of China, Standardization Administration of the People's Republic of China. Copper, nickel and cobalt industrial pollutant discharge standards: GB 25467-2010 [S]. Beijing: China Environmental Science Press, 2010 (in Chinese).

    [5] Adhoum N, Monser L, Bellakhal N, et al. Treatment of electroplating wastewater containing Cu2+, Zn2+ and Cr(Ⅵ) by electrocoagulation [J]. J. Hazard. Mater., 2004, 112: 207–213.

    [6] Chiu H, Tsang K, Lee R. Treatment of electroplating wastes [J]. Water Pollut. Control (GB), 1987, 86: 12.

    [7] Peng C, Chai L, Tang C, et al. Study on the mechanism of copper–ammonia complex decomposition in struvite formation process and enhanced ammonia and copper removal [J]. Journal of Environmental Sciences, 2017, 51(1): 222.

    [8] Verma A, Bishnoi N R, Gupta A. Optimization study for Pb(Ⅱ) and COD sequestration by consortium of sulphate-reducing bacteria [J]. Applied Water Science, 2017, 7 (5): 2309–2320.

    [9] Li H, Chen Y, Long J, et al. Simultaneous removal of thallium and chloride from a highly saline industrial wastewater using modified anion exchange resins [J]. Journal of Hazardous Materials, 2017, 333: 179–185.

    [10] Li X F, Shi S Y, Cao H B, et al. Comparative study of chromium(Ⅵ) removal from simulated industrial wastewater with ion exchange resins [J]. Russian Journal of Physical Chemistry A, 2018, 92 (6): 1229–1236.

    [11] Lee C G, Lee S, Park J A, et al. Removal of copper, nickel and chromium mixtures from metal plating wastewater by adsorption with modified carbon foam [J]. Chemosphere, 2017, 166: 203–211.

    [12] Park J A, Kang J K, Lee S C, et al. Electrospun poly(acrylic acid)/poly(vinyl alcohol) nanofibrous adsorbents for Cu(Ⅱ) removal from industrial plating wastewater [J]. RSC Advances, 2017, 7 (29): 18075–18084.

    [13] Jesus J M S, Scarazzato T, Tenorio J A S, et al. Permselectivity study of ion-exchange membranes in the presence of Cu-HEDP complexes from a copper plating wastewater treatment [M] //Applications of Process Engineering Principles in Materials Processing, Energy and Environmental Technologies. Springer International Publishing, 2017.

    [14] Chang S H. A comparative study of batch and continuous bulk liquid membranes in the removal and recovery of Cu(Ⅱ) ions from wastewater [J]. Water Air & Soil Pollution, 2018, 229 (1): 22.

    [15] Sun H, Wang H, Wang H, et al. Enhanced removal of heavy metals from electroplating wastewater through electrocoagulation using carboxymethyl chitosan as corrosion inhibitor for steel anode [J]. Environmental Science: Water Research & Technology, 2018, 4 (8): 1105–1113.

    [16] Min K J, Choi S Y, Jang D, et al. Separation of metals from electroplating wastewater using electrodialysis [J]. Energy Sources Part A Recovery Utilization and Environmental Effects, 2019, (3): 1–10.

    [17] Fu F, Wang Q. Removal of heavy metal ions from wastewaters: a review [J]. Journal of Environmental Management, 2011, 92 (3): 407–418.

    [18] Xu P, Zeng G M, Huang D L, et al. Use of iron oxide nanomaterials in wastewater treatment: a review [J]. Science of the Total Environment, 2012, 424: 1–10.

    [19] Azmi A A, Jai J, Zamanhuri N A, et al. Precious metals recovery from electroplating wastewater: a review [C] //IOP Conference Series: Materials Science and Engineering. IOP Publishing, 2018, 358 (1): 012024.

    [20] Yang Y, Lee S W, Ghasemi H, et al. Charging-free electrochemical system for harvesting low-grade thermal energy [J]. Proceedings of the National Academy of Sciences of the United States of America, 2014, 111 (48): 17011–17016.

    [21] Rahimi M, Straub A P, Zhang F, et al. Emerging electrochemical and membrane-based systems to convert low-grade heat to electricity [J]. Energy & Environmental Science, 2018, 11 (2): 276–285.

    [22] Zhang F, Liu J, Yang W, et al. A thermally regenerative ammonia-based battery for efficient harvesting of low-grade thermal energy as electrical power [J]. Energy Environ. Sci., 2015, 8 (1): 343–349.

    [23] Zhang F, Labarge N, Yang W, et al. Enhancing low-grade thermal energy recovery in a thermally regenerative ammonia battery using elevated temperatures [J]. ChemSusChem, 2015, 8 (6): 1043–1048.

    [24] Rahimi M, D'Angelo A, Gorski C A, et al. Electrical power production from low-grade waste heat using a thermally regenerative ethylenediamine battery [J]. Journal of Power Sources, 2017, 351: 45–50.

    [25] Rahimi M, Kim T, Gorski C A, et al. A thermally regenerative ammonia battery with carbon-silver electrodes for converting low-grade waste heat to electricity [J]. Journal of Power Sources, 2018, 373: 95–102.

    [26] Rahimi M, Zhu L, Kowalski K L, et al. Improved electrical power production of thermally regenerative batteries using a poly(phenylene oxide) based anion exchange membrane [J]. Journal of Power Sources, 2017, 342: 956–963.

    [27] Zhu X, Rahimi M, Gorski C A, et al. A thermally-regenerative ammonia-based flow battery for electrical energy recovery from waste heat [J]. ChemSusChem, 2016, 9 (8): 873–879.

    [28] Li Y X, Zhang L, Zhu X, et al. Effect of mass transfer on the performance of thermally regenerative ammonia-based battery [J]. Journal of Engineering Thermophysics, 2019, (3): 668–671 (in Chinese).

    [29] Wang W, Shu G, Tian H, et al. A numerical model for a thermally-regenerative ammonia-based flow battery using for low grade waste heat recovery [J]. Journal of Power Sources, 2018, 388: 32–44.

    [30] Chen S S. Determination of copper ion concentration in water by improved spectrophotometry [J]. Global Market Information Herald: Theory, 2014, (8): 224 (in Chinese).

    [31] Yang R P, Li X X, Ding L, et al. Rapid determination of copper ion concentration in polluted water [J]. Chinese Journal of Health Laboratory Technology, 2007, 17 (12): 2217–2218 (in Chinese).

    [32] Mollah M Y, Schennach R, Parga J R, et al. Electrocoagulation (EC)—science and applications [J]. Journal of Hazardous Materials, 2001, 84 (1): 29–41.

This Article


CN: 11-1946/TQ

Vol 70, No. 12, Pages 4804-4810

December 2019


Article Outline


  • Introduction
  • 1 Experimental materials and methods
  • 2 Results and discussion
  • 3 Conclusions
  • Symbols
  • References