以浮除法分離水相中之石墨和磷酸鋰鐵｜國立臺灣科技大學博碩士論文系統

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研究生：	張安潔 An-Chieh Chang
論文名稱：	以浮除法分離水相中之石墨和磷酸鋰鐵 Flotation Separation of Graphite and Lithium Iron Phosphate in Aqueous Solution
指導教授：	劉志成 Jhy-Chern Liu
口試委員:	顧洋 Young Ku 郭俞麟 Yu-Lin Kuo
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2023
畢業學年度：	111
語文別：	英文
論文頁數：	74
中文關鍵詞：	石墨、磷酸鋰鐵、浮選、分離、界面活性劑
外文關鍵詞：	Flotation, Graphite, Lithium iron phosphate, Separation
相關次數：	點閱：317 下載：1
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隨著科技發展，鋰電池應用逐漸興盛。磷酸鋰鐵 (LFP) 為鋰電池陰極的材料，相較傳統鋰電池，具備價格平價、使用壽命長和高能量密度等優點，逐漸成為主流電池。在廢磷酸鋰鐵電池粉末中，檢測得知碳含量的比例很高，約26%左右，主要來自於電池中的陽極石墨。高碳含量不利於濕法冶金程序，會影響金屬處理量及增加能源消耗。本研究主要目的在於探討浮選作為預處理程序，移除電池中的石墨的可行性。研究中先使用純石墨及純磷酸鋰鐵，分別探討浮選中使用不同表面活性劑、表面活性劑劑量、pH值對單一材料影響，並檢測界達電位及粒徑變化。接續依據與廢棄物相同比例的石墨及磷酸鋰鐵做混合材料實驗，最終嘗試以實際廢磷酸鋰鐵電池浮選分離。
本研究使用四種不同的表面活性劑：十六烷基三甲基溴化銨 (CTAB)、十二烷基硫酸鈉 (SDS)、油酸鈉 (NaOL) 和 Triton X-100 (TX-100)。研究結果顯示在劑量4 mg/L，CTAB相較其他表面活性劑，可以有效將石墨與磷酸鋰鐵從水中分離，在pH 9.5時回收效率分別為85.24% 和 76.09%。CTAB 能將兩材料從水中分離有效分離是由於負表面與帶正電荷的表面活性劑之間的靜電吸引力。從界達電位分析可看到兩材料使用CTAB後電位顯著提升，且使粒徑大小變得更大。混合實驗及廢磷酸鋰鐵電池實驗由CTAB進行，結果顯示在混合兩材料和廢磷酸鋰鐵電池實驗中，CTAB能都將兩材料同時從水中移除。可是並無法選擇性分離兩者，主要限制應是其等電位點接近。有待後續研究克服。

With the rapid advancement of technology, the utilization of lithium batteries is gaining immense popularity. Among the various materials employed in the cathode of lithium batteries, lithium iron phosphate (LFP) has emerged as a dominant choice. In the spent LFP battery powder, a significant fraction of carbon content, approximately 26%, was found, mainly from the graphite anode in the battery. The high carbon content is unfavorable to the hydrometallurgical process, which affects the metal processing efficiency and increases energy consumption.
The main objective of this study is to investigate the feasibility of using flotation as a pretreatment process to remove the carbon from the waste. In this study, pure graphite and pure LFP were used to investigate the effects of surfactant type, surfactant doses, and pH, while the zeta potential and particle size variation were examined as well. The graphite and LFP mixture in the same proportions as the spent LFP batteries was then used for the experiments, and finally the actual spent LFP batteries were tested.
Four different types of surfactants were used in this study: cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), sodium oleate (NaOL), and Triton X-100 (TX-100). The results showed that CTAB was effective in separating graphite and LFP, respectively, from water at a dose of 4 mg/L, with recovery efficiencies of 85.24% and 76.09% at pH 9.5. It was attributed to the electrostatic attraction between the negatively charged surfaces and the positively charged surfactant. The mixed-sample experiment using CTAB showed that CTAB was able to remove both materials from water simultaneously in both the mixed and spent LFP experiments. However, it was not possible to have a selective separation of graphite and LFP.

摘要..........................................................................i
ABSTRACT.....................................................................ii
ACKNOWLEDGEMENT.............................................................iii
TABLE OF CONTENTS............................................................iv
LIST OF FIGURES.............................................................vii
LIST OF TABLES...............................................................ix
CHAPTER 1 INTRODUCTION......................................................1-1
1 Background..............................................................1-1
2 Objectives of study.....................................................1-2
CHAPTER 2 LITERATURE REVIEW.................................................2-1
1 Lithium iron phosphate battery..........................................2-1
1.1 Battery demand and structure..........................................2-1
1.2 Recycling lithium iron phosphate batteries using flotation technology.2-4
1.3 Recycling graphite using flotation technology.........................2-7
2 Flotation...............................................................2-8
2.1 Flotation parameter...................................................2-9
2.1.1 Surfactant type.....................................................2-9
2.1.2 Concentration of flotation reagent.................................2-10
2.1.3 pH.................................................................2-11
2.1.4 Gas flow rate and bubble size......................................2-12
CHAPTER 3 MATERIALS AND METHODS.............................................3-1
1 Materials...............................................................3-1
2 Equipment and Instruments...............................................3-2
3 Experimental framework and procedures...................................3-4
4 Experimental methods....................................................3-5
4.1 Zeta potential and particle size measurement..........................3-5
4.2 Flotation experiment..................................................3-6
4.3 Elemental Analyzer EA000200...........................................3-8
CHAPTER 4 RESULTS AND DISCUSSION............................................4-1
1 Characterization........................................................4-1
1.1 XRD result of spent LFP...............................................4-1
1.2 Elemental Analyzer result.............................................4-2
1.2.1 Spent LFP...........................................................4-2
1.2.2 Pure graphite and pure LFP..........................................4-3
1.3 Zeta potential of pure graphite and LFP...............................4-4
2 Single material.........................................................4-5
2.1 Effect of different surfactant types..................................4-5
2.1.1 Pure graphite recovery..............................................4-7
2.1.2 Pure graphite particle size........................................4-10
2.1.3 Pure LFP recovery..................................................4-11
2.1.4 Pure LFP particle size.............................................4-13
2.2 Effect of surfactant concentration...................................4-14
2.2.1 Pure LFP and pure graphite recovery................................4-14
2.2.2 Pure LFP and pure graphite particle size...........................4-16
3 Mixed material.........................................................4-17
3.1 Mixed sample recovery with CTAB......................................4-17
4 Spent LFP..............................................................4-20
CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS................. .................5-1
1 Conclusions.............................................................5-1
2 Recommendations.........................................................5-3
REFERENCES..................................................................R-1
APPENDIX....................................................................A-1
                                

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