成功大學博碩士論文系統

簡易檢索 / 詳目顯示

回結果列表

研究生：	馬亮瑜 Ma, Liang-Yu
論文名稱：	鋰電池電極材料資源化之探討 Recovery of electrode material from lithium ion batteries
指導教授：	王建力 Wang, Chien-Lee
學位類別：	碩士 Master
系所名稱：	工學院 - 資源工程學系 Department of Resources Engineering
論文出版年：	2020
畢業學年度：	108
語文別：	中文
論文頁數：	81
中文關鍵詞：	鋰離子電池、濕法冶金、還原焙燒
外文關鍵詞：	Lithium ion batteries, hydrometallurgy, reduction roasting
相關次數：	點閱：63 下載：0
分享至:	分享至facebook 分享至twitter

查詢本校圖書館目錄查詢臺灣博碩士論文知識加值系統勘誤回報

世界各國爭相發展再生能源，儲集設備及相關電力設施應然而生。鋰離子電池有著大量的需求量，相對衍生了廢棄及後續處置等問題。本研究藉由濕法冶金方法希望針對鋰、鈷、錳、鎳等有價金屬，設置一套妥善資源化對策。
本實驗採用NCM及NCA兩種材料，兩者差異為鈷、鎳金屬含量差異。分為四階段，第一階段將鋰電池之正極材料進行前處理及特性分析，以利後續之處理。第二階段進行酸浸漬參數調整，尋找較佳浸漬參數，本實驗分別使用硫酸及鹽酸等無機酸於兩種材料。考量實驗效率下，以硫酸為最佳浸漬劑，其中NCA粉末以5N硫酸、100 ml/g液固比、60℃下加入2.5 vol.% H2O2、持溫2.5小時為最佳。第三階段利用真空焙燒爐，選用碳黑為還原劑進行還原焙燒，以取代上一階段之雙氧水角色，最佳處理參數為6:1之正極粉末與還原劑之配比、反應溫度600℃下持溫3小時，可將目標金屬還原為價數較低之離子，有利於後續之回收處理。最後藉由水洗達到鋰金屬之減量及回收，純度達99%，利於後續錳金屬化學沉澱之回收，剩餘浸漬液之鈷鎳金屬經過回收可做為高介電常數材料，對於半導體業有很大供應商機。

Countries all over the world are scrambling to develop renewable energy, storage equipment and related power facilities are necessary. Lithium ion batteries have a large demand, relatively caused waste and subsequent disposal and other issues. In this study, by hydrometallurgy, it is hoped that an appropriate countermeasure should be set for the valuable metals such as lithium, cobalt, manganese and nickel.
In this experiment, it is divided into four stages. The first stage of the lithium-ion batteries, cathode material was subjected to pre-treatment and characteristic analysis to facilitate subsequent treatment. The second stage, acid leaching parameter adjustment, looking for the better parameters. Considering leaching efficiency, sulfuric acid is the best leaching agent, NCA powder’s parameter is 5N sulfuric acid, 100 ml/g liquid-to-solid ratio, 2.5 vol.% H2O2 added at 60℃, and holding temperature for 2.5 hours. The third stage, we took advantage of vacuum roasting furnace. The role of carbon black as reducing agent for reduction roasting is to replace the previous stage of the role of hydrogen peroxide, the best treatment parameters is 6:1 positive powder and reducing agent ratio, heating at 600℃ for 3 hours, the target metal can be reduced to a lower price of ions, beneficial to the subsequent recovery treatment. Finally, by water leaching, to achieve the reduction of lithium metal and recovery, purity up to 99%, beneficial to the subsequent recovery of manganese metal from chemical precipitation. In remaining leachate, cobalt and nickel metal after recovery could be used as a high dielectric constant material, has a large supplier machine for the semiconductor industry.

目錄
摘要	I
致謝	X
目錄	XI
表目錄	XIV
圖目錄	XV
第一章 緒論	1
1.1 前言	1
1.2 研究動機與目的	3
第二章 理論基礎與文獻回顧	4
2.1 鋰三元離子電池概況	4
2.1.1 鋰三元離子電池	4
2.1.2 鋰金屬資源性質	5
2.1.3 鈷金屬資源性質	6
2.1.4 鎳金屬資源性質	7
2.1.5 錳金屬資源性質	8
2.2 鋰電池結構介紹	9
2.2.1 電池運作原理	9
2.2.2 電池單元介紹	10
2.2.3 鋰電池對環境之安全疑慮、危害	14
2.3 前處理技術	15
2.3.1 破碎法	16
2.3.2 分選法	16
2.3.3 鍛燒法	16
2.3.4 焙燒法	17
2.4 冶金與資源化技術	17
2.4.1 電解冶金	17
2.4.2 火法冶金	18
2.4.3 濕法冶金	18
2.5實驗反應機制	26
2.5.1 浸漬反應熱力學	26
2.5.2 浸漬反應動力學	29
2.5.3 化學沉澱分離	31
第三章 實驗材料及流程	32
3.1 實驗流程	32
3.2實驗材料及設備	33
3.2.1 實驗材料	33
3.2.2 實驗設備	34
3.3 實驗方法及步驟	41
3.3.1 前處理及原料分析	41
3.3.2 浸漬	42
3.3.3真空焙燒	43
3.3.4水浸漬及鋰金屬回收	43
3.3.5分離及錳金屬回收	44
第四章 結果與討論	45
4.1 鋰電池正極材料之特性分析	45
4.1.1 粒徑分析	48
4.1.2 微結構分析	49
4.1.3熱差分析	49
4.1.4 總量分析	50
4.2 鋰電池正極材料之浸漬	50
4.2.1 NCA粉末硫酸浸漬	51
4.2.2 NCA粉末鹽酸浸漬	55
4.2.3 NCA粉末醋酸浸漬	60
4.3 鋰電池正極材料焙燒處理	65
4.3.1 反應物配比選定	65
4.3.2 焙燒溫度選定     68
4.4 鋰電池正極材料回收	69
4.4.1 水洗處理	69
4.4.2 浸漬處理	71
4.4.3 化學沉澱	72
第五章 結論與建議	74
5.1 結論	74
5.2 建議	75
參考文獻	77

表目錄
表 2 1 正極材料之各材料組成	12
表 2 2 各種浸漬方法	20
表 3 1 實驗所需之化學藥品及材料	33
表 4 1 NCA粉末之總量分析	50
表 4 2 NCM粉末焙燒(水洗後)之總量分析	50

圖目錄
Fig 2- 1 鋰電池相關組成	5
Fig 2- 2 鋰電池相關構造	9
Fig 2- 3 鋰鈷鎳錳金屬之Eh - pH圖	28
Fig 2- 4 縮核模型	30
Fig 3- 1 實驗流程圖	32
Fig 3- 2  X光繞射分析儀	35
Fig 3- 3 原子吸收光譜儀	36
Fig 3- 4 雷射粒徑分析儀	36
Fig 3- 5 酸鹼度計	37
Fig 3- 6 連續刀切式破碎機	38
Fig 3- 7 振動篩分機	38
Fig 3- 8 電磁攪拌恆溫水槽	39
Fig 3- 9 真空焙燒爐	40
Fig 3- 10 傅立葉轉換紅外線光譜儀	40
Fig 4- 1 鋰電池正極材料	46
Fig 4- 2 正極粉末	46
Fig 4- 3 NCM粉末正極材料粒徑分布	47
Fig 4- 4 NCA粉末正極材料粒徑分布	47
Fig 4- 5 水洗處理後NCM粉末正極材料粒徑分布	48
Fig 4- 6 水洗處理後NCA粉末正極材料粒徑分布	48
Fig 4- 7 SEM圖示	49
Fig 4- 8 熱差分析	49
Fig 4- 9 硫酸濃度對浸漬率之影響	51
Fig 4- 10 硫酸與粉末之液固比對浸漬率之影響	52
Fig 4- 11 硫酸反應時間對浸漬率之影響	53
Fig 4- 12 還原劑添加量對硫酸浸漬率之影響	54
Fig 4- 13 硫酸反應溫度對浸漬率之影響	55
Fig 4- 14 鹽酸濃度對浸漬率之影響	56
Fig 4- 15 鹽酸與粉末之液固比對浸漬率之影響	57
Fig 4- 16 鹽酸反應時間對浸漬率之影響	58
Fig 4- 17 還原劑添加量對鹽酸浸漬率之影響	59
Fig 4- 18 鹽酸反應溫度對浸漬率之影響	60
Fig 4- 19 醋酸濃度對浸漬率之影響	61
Fig 4- 20 醋酸與粉末之液固比對浸漬率之影響	62
Fig 4- 21 醋酸反應時間對浸漬率之影響	63
Fig 4- 22 還原劑添加量對醋酸浸漬率之影響	64
Fig 4- 23 醋酸反應溫度對浸漬率之影響	65
Fig 4- 24 焙燒反應物配比之影響	66
Fig 4- 25 NCM粉末配比焙燒之影響	67
Fig 4- 26 NCA粉末配比焙燒之影響	67
Fig 4- 27 NCM粉末焙燒溫度之影響	68
Fig 4- 28 NCA粉末焙燒溫度之影響	69
Fig 4- 29 水洗處理後回收碳酸鋰	70
Fig 4- 30 碳酸鋰產物	70
Fig 4- 31 硫酸濃度對水洗後篩上物浸漬率之影響	71
Fig 4- 32 硫酸濃度對水洗後篩上物浸漬率之影響	72
Fig 4- 33 pH值於Na2S沉澱之影響	73





                                    

[1] P. Meshram, B. Pandey, and T. Mankhand., "Hydrometallurgical processing of spent lithium ion batteries (LIBs) in the presence of a reducing agent with emphasis on kinetics of leaching, "Chemical Engineering Journal, vol. 281, pp. 418-427, 2015.
[2] A. Nayl, R. Elkhashab, S. M. Badawy, and M. El-Khateeb, "Acid leaching of mixed spent Li-ion batteries, "Arabian Journal of Chemistry, vol. 10, pp. S3632-S3639, 2017.
[3] H. Wen zhi et al.,"Recovery of Co and Li from spent lithium-ion batteries by combination method of acid leaching and chemical precipitation, "Transactions of Nonferrous Metals Society of China, vol. 22, no. 9, pp. 2274-2281, 2012.
[4] C. Pillot., "Battery Market Development for Consumer
, Automotive, and Industrial: Materials Requirements and Trends,
" presentation at China International Battery Fair, 2014.
[5] J. Ordoñez, E.J. Gago, A. Girard.," Processes and technologies for the recycling and recovery of spent lithium-ion batteries, "Renewable and Sustainable Energy Reviews,60 , pp. 195-205, 2016.
[6] B. L. Ellis, K. T. Lee, and L. F. Nazar, "Positive electrode materials for Li-ion and Li-batteries, "Chemistry of materials, vol. 22, no. 3, pp. 691-714, 2010.
[7] U.S. Geological Survey., "MINERAL COMMODITY SUMMARIES 2020, "2020.
[8] J. Clean. Prod., "Carbon footprint analysis of lithium ion secondary battery industry: two case studies from China, "163 , pp. 241-251,2016.
[9] Pellow .MA , Ambrose. H, Mulvaney. D, Betita. R , Shaw. S., "Research gaps in environmental life cycle assessments of lithium ion batteries for grid-scale stationary energy storage systems: End-of-life options and other issues, "End-of-life options and other issues, no. 3, 2020.
[10] 劉如熹., "鋰離子二次電池材料簡介, "化學, vol. 57, no. 2, pp. 149-150, 1999.
[11] V. Etacheri, R. Marom, R. Elazari, G. Salitra, and D. Aurbach., "Challenges in the development of advanced Li-ion batteries: a review, "Energy & Environmental Science, vol. 4, no. 9, pp. 3243-3262, 2011.
[12] O. E. Bankole, C. Gong, and L. Lei., "Battery recycling technologies: Recycling waste lithium ion batteries with the impact on the environment in-view, "Journal of Environment and Ecology, vol. 4, no. 1, pp. 14-28, 2013.
[13] Yazami, R., and Touzain, P., "A reversible graphite-lithium anode for batteries, " J. Power Sources 9, 1983.
[14] Leyuan Zhang, Liang Chen, Hao Luo, Xufeng Zhou, Zhaoping Liu., "Large‐Sized Few‐Layer Graphene Enables an Ultrafast and Long‐Life Aluminum‐Ion Battery, " Advanced energy materials.15,2017.
[15] Hao Chen, Fan Guo, Yingjun Liu, Tieqi Huang, Bingna Zheng, Nimrodh Ananth, Zhen Xu, Weiwei Gao, and Chao Ga, A., "Defect-Free Principle for Advanced Graphene Cathode of Aluminum-Ion Battery," Advanced materials.12,2017.
[16] Zheng, GX, Yin, JH, Chen, MH, Tian, SY, Li, BT, Gao, QM., "Puffed Rice Inspired Porous Carbon Co-MOFs Derived Composite Electrode for Lithium Ion Batteries, "JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY.7, 2020.
[17] A. González, E. Goikolea, J.A. Barrena, R. Mysyk., "Review on supercapacitors: Technologies and materials, " Renewable and Sustainable Energy Reviews. 58 ,2016.
[18] Liwen Ji Meng Gu Yuyan Shao Xiaolin Li Mark H. Engelhard Bruce W. Arey Wei Wang Zimin Nie Jie Xiao Chongmin Wang Ji‐Guang Zhang Jun Liu., "Controlling SEI Formation on SnSb‐Porous Carbon Nanofibers for Improved Na Ion Storage, "advanced materials.26,2014.
[19] Patrice Simon, Yury Gogotsi., "Materials for electrochemical capacitors, "Nature Materials.7,2008.
[20]Mizushima,K.,Jones,P.C.,Wiseman,P.J.,andGoodenough,J.B., "Lithium cobalt oxide(LixCoO2) (0<x≤1): a new cathode material for batteries of high energy density, "Mater. Res. Bull. 15,1980.
[21] 林月微., "高性能電池正極材料介紹," 工業材料, vol. 157, p. 153, 2000.
[22] 鄭如翔和黃炳照., "鋰離子電池正極材料之發展," 化工, vol. 58, no. 5, pp. 10-39, 2011.
[23] Wang, Q. S., Ping P., and Sun, J.H., "Catastrophe analysis of cylindrical lithium ion battery, "Nonlinear Dynam. 61, 2010.
[24] Wang, Q. S., Ping P., Zhao, X, Chu, G., Zhao, X., Sun, J.H., et al., "Thermal runaway caused ﬁre and explosion of lithium ion battery, "J. Power Sources 208, 2012.
[25] Shariﬁ-Asl, S., Lu, J., Amine, K., and Shahbazian-Yassar, R., "Oxygen release degradation in Li-Ion battery cathode materials: mechanisms and mitigating approaches, "Adv. Energy Mater. 9, 2019.
[26] Pesaran, A. A., Kim, G.-H., and Smith, K Designing ., "Safe Lithium-Ion Battery Packs Using Thermal Abuse Models, "2008.
[27 ] Li, Z., Xiong, Y., Sun, S., Zhang, L., Li, S., Liu, X., et al., "Trilayer nonwoven membrane with shutdown property and high robustness as a high-safety lithium ion battery separator, "J. Memb. Sci. 565,2018.
[28 ] Teyeb Ould Ely, Dana Kamzabek, Dhritiman Chakraborty., "Batteries Safety: Recent Progress and Current Challenge, " Energy Research,2019.
[29 ] Kalhoﬀ, J., Eshetu, G. G., Bresser, D., and Passerini, S., "Safer electrolytes for lithium-ion batteries: state of the art and perspectives, "Chem Sus Chem 8,2015.
[30 ] Alias, N., and Mohamad, A. A., "Advances of aqueous rechargeable lithium-ion battery: a review,".J. Power Sources 274, 2015.
[31 ] Kim, H., Hong, J., Park, K.-Y., Kim, H., Kim, S.-W., and Kang, K. , "Aqueous rechargeable Li and Na ion batteries, "Chem. Rev. 114, 2014.
[32 ] Kong, L., Li, C., Jiang, J., and Pecht, M. G. , "Li-ion battery ﬁre hazards and safety strategies, " Energies 11, 2018.
[33] Roth, E. P., Doughty, D. H., and Pile, D. L., "Eﬀects of separator breakdown on abuse response of 18650 Li-ion cells, "J. Power Sources 174, 2007.
[34] Xianlai Zeng, Jinhui Li, Narendra Singh, "Recycling of Spent Lithium-Ion Battery, "A Critical Review Critical Reviews in Environmental Science and Technology44,2014.
[35] 李洪桂, "濕法冶金學," 中南大學出版社, 2005, pp. 30-35
[36] Preston Devasia ,K.A. Natarajan, "Biotechnology in the Mining Industry, " Bacterial leaching,2004.
[37] Basudev, Swain., K. Saringe., Das, R.P., "Separation of Cadmium and Zinc by Supported Liquid Membrane Using TOPS‐99 as Mobile Carrier, "Separation Science and Technology,39(9),2005.
[38] F. Wang, R. Sun, J. Xu, Z. Chen, M. Kang, "Recovery of cobalt from spent lithium ion batteries using sulphuric acid leaching followed by solid-liquid separation and solvent extraction, "RSC Adv., 6 (88),2016.
[39] Shih, Yu-Jen; Chien, Shih-Kai; Jhang, Syu-Ruei., "JOURNAL OF THE TAIWAN INSTITUTE OF CHEMICAL ENGINEERS",100, 2019.
[40] Xiangping Chen, BaoXu Tao Zhou, Depei Liu, Hang Hu, Shaoyun Fan, "Separation and recovery of metal values from leaching liquor of mixed-type of spent lithium-ion batteries, " Separation and Purification Technology144,2015
[41] Li, Quan; Fung, Ka Yip; Nee, Ka Ming, "Separation of Ni, Co, and Mn from Spent LiNi0.5Mn0.3Co0.2O2 Cathode Materials by Ammonia Dissolution, " SUSTAINABLE CHEMISTRY & ENGINEERING.,7(15),2019.
[42] A.A. Naylab, Mostafa M. Hamedb, S.E. Rizkb, "Selective extraction and separation of metal values from leach liquor of mixed spent Li-ion batteries, "Journal of the Taiwan Institute of Chemical Engineers,55,2015.
[43] E Sayilgan , T Kukrer ,NO Yigit, G Civelekoglu, M Kitis, "Acidic leaching and precipitation of zinc and manganese from spent battery powders using various reductants, "Journal of Hazardous Materials,173,2010.
[44] Ma, Liwen, Xi, Xiaoli, Wang, Kaifeng., "Adsorption of Li by a lithium ion-sieve using a buffer system and application for the recovery of Li from a spent lithium-ion battery, " RESEARCH ON CHEMICAL INTERMEDIATES,44(11),2018.
[45] Chiu, Kai-Lun, Chen, Wei-Sheng., "Recovery and Separation of Valuable Metals from Cathode Materials of Spent Lithium-Ion Batteries (LIBs) by Ion Exchange, " SCIENCE OF ADVANCED MATERIALS, 9(12), 2017.
[46] N. Takeno, "Atlas of Eh-pH Diagrams, Intercomparison of Thermodynamic Databases.," National Institute of Advanced Industrial Science and Technology, no. 419, 2005.
[47] J. Ortiz-Landeros, C. Gómez-Yáñez, R. López-Juárez, I. Dávalos-Velasco, and H. Pfeiffer, "Synthesis of advanced ceramics by hydrothermal crystallization and modified related methods," Journal of Advanced Ceramics, vol. 1, no. 3, pp. 204-220, 2012.
[48] C. Dickinson and G. Heal, "Solid–liquid diffusion controlled rate equations," Thermochimica Acta, vol. 340, pp. 89-103, 1999.
[49] H.-l. SUN, H.-y. YU, B. WANG, Y. MIAO, G.-f. TU, and S.-w. BI, "Leaching dynamics of 12CaO· 7Al 2 O 3," The Chinese Journal of Nonferrous Metals, vol. 18, no. 10, pp. 1920-1925, 2008.
[50] V. Safari, G. Arzpeyma, F. Rashchi, and N. Mostoufi, "A shrinking particle—shrinking core model for leaching of a zinc ore containing silica," International journal of mineral processing, vol. 93, no. 1, pp. 79-83, 2009.

校內：2025-07-01公開
校外：2025-07-01公開

簡易檢索 / 詳目顯示

相關論文