臺灣博碩士論文加值系統

本研究利用檸檬酸表面活性成功合成Li3V2(PO4)3與Na3V2(PO4)3，外表由碳層包覆，並且將5%與10%比例之磁性原子(Mn、Fe、Co、Ni)摻雜至樣品中。10%樣品在XRD實驗中發現有雜質，5%則皆為純相，當中皆無碳的峰值，代表碳為無序，由摻雜後晶格變化與吸收光譜實驗證實摻雜元素確實取代樣品中V之位置並且得知其價數。實驗主要以摻雜5%比例磁性原子之樣品與對照組比較彼此間的物性與電池性能關係。臨場變溫拉曼光譜實驗觀察外層無序的碳，分析D-band、G-band變化與強度比，得知碳層有序程度與V鍵結價數有關。
分別研究樣品在低電壓(銅極片)鋰/鈉離子嵌入能力與高電壓(鋁極片)鋰/鈉離子析出能力。測量變場50 cycle、c-rate實驗以觀察電容量穩定度與快速充放電的衰退度，所有樣品在快速至慢速充放電中皆有良好的回復性。在電池組抗分析趨勢中觀察Rct與V鍵結價數相關，且樣品表面因V鍵結價數影響碳層的電子，與碳層有序度導致表面的電荷轉移能力產生變化。離子擴散速度則與樣品晶格體積互相有些微之影響。在能量功率密度圖中發現，無論是LVP或是NVP，Fe離子是不錯的摻雜選擇。

In this study, Li3V2(PO4)3 and Na3V2(PO4)3 were successfully synthesized using the surface activated method of citric acid. The surface is covered by a carbon layer and doped with 5% and 10% magnetic atoms (Mn, Fe, Co, Ni). XRD experiments showed that impurities were found in 10%-doped samples but not in the 5% ones. No carbon signal was found in XFD experiments, which means the carbon formed disordered. The variation of lattice constants and the X-ray absorption spectra experiments confirmed that the doped elements have partially substituted the vanadium in the samples. This study mainly compares the relationship between the physical properties of the sample doped with 5% magnetic atoms and the pure ones in the battery performance. Varied magnetic fields and temperatures Raman spectra experiments displayed the disordered carbon at the outer layer. The changes of D-band, G-band, and their intensities ratio referred to the order of the carbon layer and correlated with the bond valence of vanadium.
Study the intercalation/deintercalation behaviors of lithium/sodium ions under low voltage (for copper case) and high voltage (for aluminum case). The varied magnetic field, 50 cycles, and C-rate experiments checked conductor stability and charge-discharge decay. In the C-rate experiment, all samples have good response and recovery during difference/charging rate. The electrochemical impedance spectroscopy experiment shows that Rct is related to V bond valence. The electrons of the carbon layer are affected by the V bond valence on the surface of the sample, and crystallization of the carbon layer lead to changes in Rct. The ion diffusion rate and the sample lattice volume slightly influence each other. The energy to power density plot indicates that Fe ions are good doping options for LVP and NVP cases.

目錄
摘要…………………………………………………………………..….I
Abstract………………………………………………………………......II目錄…………………………………………………………………...III圖目錄…………………………………………………………………..VI表目錄……………………………………………………..………….XIV


第一章　簡介……………………………………………………………1
　　1.1　電池材料……………………………………………………...1
　　1.2　文獻回顧……………………………………………………...3
1.3　實驗目的………………………………………………...…..21
第二章　實驗理論……………………………………………………..23
　　2.1　X光粉末繞射理論…………..……………..……………….23
　 2.2　拉曼原理…………………………………………………….26
2.3　X光吸收光譜..………………..…………………………….28
2.4　電池原理..……………………..…………………………….31
2.5　電池充放電測量..……………………..…………………….33
　　　　2.5.1　前三次充放電曲線測量…..……………..……….….33
2.5.2　循環充放電測量…..……………………..…….…….35
2.5.3　 C-rate測量…..…………………………..………….36
2.6　電化學阻抗譜..………………………..…………………….37
第三章　實驗方法與儀器……………………………………………..42
　　3.1　樣品製程…………………………………………………….42
　　　　3.1.1　樣品粉末製成…………………..……………………42
3.1.2　陽極極片製成………………………………..………44
3.1.3　電池製成……………………………………..………44
　　3.2　實驗儀器…………………………………………………….46
　　　　3.2.1　X-Ray粉末繞射儀………………………..................46
　　　　3.2.2　拉曼光譜儀…………………..………………………47
　　　　3.2.3　微小電流電池自動化充放電測試主機…..…………48
　　　　3.2.4　阻抗分析儀…………………..………………………49
　　　　3.2.5　 BL16A1吸收光譜實驗站…..………………………50
第四章　實驗數據分析……………………………………………..51
　　4.1　XRD分析…………...……………………………………….51
　　4.2　吸收光譜分析……....……………………………………….63
　　4.3　Raman光譜實驗…..……………………..………………….67
　　4.4　電池實驗分析………...…………………….……………….73
　　4.5　電池阻抗分析………....…………………………………….88
　　4.6　電池能量功率密度分析………....………………………….93　
第五章　結論…………………………………………………………..96
參考文獻………………………………………………………………..99 
圖目錄
圖(1.1)　 LVP結構圖。………….…………………………2
圖(1.2)　 NVP結構圖。……………………………………3
圖(1.3)　 Li3V1-xFexP之循環充放電圖。(a)x=0 (b)x=0.01 (c)x=0.02 (d)x=0.04 (e)x=0.06。 3
圖(1.4)　CV測量圖(a) Li3V2(PO4)3 (b)Li3Fe0.02V1.98(PO4)3。...4
圖(1.5)　 (a)NVP之SEM圖(b)Raman圖(c)TG圖。…………4
圖(1.6)　 (a)NVP/C XRD (b)sample1(c)sample2 TEM。 5
圖(1.7)　 充放電NVP變化之XRD圖。…………………….5
圖(1.8)　 LVP(a)充放電曲線(b)對應之XRD圖。 6
圖(1.9)　 LVP充放電曲線。 6
圖(1.10)　 NaxV2(PO4)3在不同電壓對應圖。 7
圖(1.11)　 NaxV2(PO4)3(a) CV curves (b) 前三次充放電曲線。 7
圖(1.12)　(a) NVP (b) NTP CV curves。 8
圖(1.13)　(a) NTP(Cu)/NVP (b) NTP(Al)/NVP CV curves。 8
圖(1.14)　(a) Na3V2-xMnx(PO4)3 1000次(b) x=0.2，30C 1000次循環充放電測量。…………………………………...9

圖(1.15)　 Na3V2-xTix(PO4)3 1000次(a) C-rate (b) 100次循環充放電測量。……………………………………………10
圖(1.16)　 NVP不同燒結溫度之 (a) XRD圖 (b) C-rate充放電測量圖。………………………………………..…10
圖(1.17)　 NVP不同燒結溫度之 (a) XRD圖 (b) C-rate充放電測量圖。 11
圖(1. 18)　 NVP不同Fe比例摻雜C-rate。 11
圖(1. 19)　 NVP不同Mo比例摻雜C-rate。 11
圖(1. 20)　 NVP不同Zr比例摻雜(a)C-rate (b)1000 cycle。 12
圖(1. 21)　 NVP/Ag 100次循環充放電測量。 12
圖(1. 22)　 NVP摻雜碳層比較 C-rate。 12
圖(1. 23)　 NVP不同N比例摻雜至碳層(a)XRD圖 (b、c、d)SEM圖。 13
圖(1. 24)　 NVP不同N比例摻雜至碳層1000次循環充放電測量。 13
圖(1. 25)　 XRD、SEM和示意圖(a)(d)(g)NVP/AC(b)(e)(h) NVP/CNT (c)(f)(i) NVP/graphite。 14
圖(1. 26)　 NVP/AC、NVP/CNT和NVP/graphite (a)不同充放電速度 (b)200次循環充放電測量。 14
圖(1. 27)　 NVP不同溫度下XRD (a)放電前(b)放電後。 15
圖(1. 28)　 LVP拉曼實驗擬合圖。 15
圖(1. 29)　 LVP之拉曼光譜實驗與理論預測圖。 16
圖(1. 30)　 Li3V2(PO4)3-xBrx 100次循環充放電測量。 18
圖(1. 31)　 Li3V2(PO4)3-xBrx 與LVP(a)10次(b)20次充放電後EIS測量。 19
圖(1. 32)　 NVP(a)變磁場XRD圖(b)Raman實驗變溫變場擬合圖。 20
圖(1. 33)　研究規劃示意圖。 21
圖(2. 1)　 布拉格定律示意圖。 23
圖(2. 2)　 光干涉示意圖。 24
圖(2. 3)　 NVP碳層拉曼擬合圖。 27
圖(2. 4)　 能階定義示意圖。 28
圖(2. 5)　 V K-edge XANES圖。………………………... 29
圖(2. 6)　 CR2032電池組件。 ……………………..……31
圖(2. 7)　 電池內部運作示意圖。 …………………..……32
圖(2. 8)　 NVP前三次充放電曲線圖。 33
圖(2. 9)　 NVP循環充放電圖。……….…………………... 35
圖(2. 10)　NVP C-rate實驗圖。……..……………………... 36
圖(2. 11)　 LVP_Mn EIS實驗圖。…….…………………... 39
圖(2. 12)　 鈕扣電池EIS有效電路圖。……..…………... 41
圖(3. 1)　 藥品水溶液烘乾後產物。 43
圖(3. 2)　 LVP_Co樣品粉末。 43
圖(3. 3)　 CR3023電池組件。 45
圖(3. 4)　 X-ray粉末繞射儀之外觀。 46
圖(3. 5)　 拉曼光譜儀之外觀。 47
圖(3. 6)　微小電流電池自動化充放電測試主機外觀。 48
圖(3. 7)　 阻抗分析儀外觀。 49
圖(3. 8)　 BL16A1吸收光譜外觀。 50

圖(4. 1.1)　 (a) Li3V2(PO4)3 (b) Na3V2(PO4)3之XRD圖。 51
圖(4. 1.2)　 Li3V2(PO4)3 摻雜Mn(a)5% (b)10%；Fe (c)5% (d)10%；Co(a)5% (b)10%；Ni(a)5% (b)10% 之XRD圖。 55
圖(4. 1.3)　 Na3V2(PO4)3 摻雜Mn(a)5% (b)10%；Fe (c)5% (d)10%；Co(a)5% (b)10%；Ni(a)5% (b)10% 之XRD圖。 56
圖(4. 1.4)　 (a) Li3V2(PO4)3 (b) Na3V2(PO4)3 之存放時間XRD圖。 57
圖(4. 1.5)　 LVP與不同元素摻雜(a) a 軸 (b) b軸 (c) c軸(d)體積隨磁場變化圖。 58
圖(4. 1.6)　 NVP與不同元素摻雜(a) a 軸 (b) c軸 (c)體積隨磁場變化圖。 60
圖(4. 2.1)　樣品V K-edge XAFS圖。 63
圖(4. 2.2)　對比樣品V K-edge XAFS圖。 64
圖(4. 2.3)　摻雜樣品對(a) Mn K-edge (b) Fe K-edge (c)Co K-edge XAFS圖。 64
圖(4. 2.4)　標準樣品對(a) Mn K-edge (b) Fe K-edge (c)Co K-edge XAFS圖。 65
圖(4. 3.1)　 NVP大範圍掃描Raman圖。 67
圖(4. 3.2)　 (a)LVP(b) LVP_Mn (c) LVP_Fe (d) LVP_Co (e) LVP_Ni 變溫變場Raman擬合圖。 68
圖(4. 3.3)　 (a)NVP(b) NVP_Mn (c) NVP_Fe (d) NVP_Co (e) NVP_Ni 變溫變場Raman擬合圖。 69
圖(4. 3.4)　變磁場碳層G-band(a)LVP系列(b)NVP系列比較圖。 71
圖(4. 4.1)　(a)LVP (b) LVP_Mn (c) LVP_Fe (d) LVP_Co (e) LVP_Ni 銅極片電池前三次充放電曲線圖。 74

圖(4. 4.2)　(a)NVP (b) NVP_Mn (c) NVP_Fe (d) NVP_Co (e) NVP_Ni 銅極片電池前三次充放電曲線圖。 75
圖(4. 4.3)　 (a)LVP (b) LVP_Mn (c) LVP_Fe (d) LVP_Co (e) LVP_Ni 鋁極片電池前三次充放電曲線圖。 76
圖(4. 4.4)　 (a)NVP (b) NVP_Mn (c) NVP_Fe (d) NVP_Co (e) NVP_Ni 鋁極片電池前三次充放電曲線圖。 77
圖(4. 4.5)　(a)LVP系列 (b) NVP系列銅極片電池50次充放電後變場電容量穩定度圖。 78
圖(4. 4.6)　(a)LVP系列 (b) NVP系列銅極片電池50次充放電後變場電容量圖。 79
圖(4. 4.7)　(a)LVP (b) LVP_Mn (c) LVP_Fe (d) LVP_Co (e) LVP_Ni (f)NVP (g)NVP_Mn (h)NVP_Fe (i)NVP_Co (j)NVP_Ni 銅極片電池50次充放電電容值圖。 80
圖(4. 4.8)　(a)LVP系列 (b) NVP系列鋁極片電池50次充放電後變場電容量穩定度圖。 81
圖(4. 4.9)　(a)LVP系列 (b) NVP系列鋁極片電池50次充放電後變場電容量圖。 82
圖(4. 4.10)　(a)LVP (b) LVP_Mn (c) LVP_Fe (d) LVP_Co (e) LVP_Ni (f)NVP (g)NVP_Mn (h)NVP_Fe (i)NVP_Co (j)NVP_Ni 鋁極片電池50次充放電電容值圖。 83
圖(4. 4.11)　(a)LVP系列 (b) NVP系列銅極片電池不同充放電速度電容量圖。 84
圖(4. 4.12)　(a)LVP (b) LVP_Mn (c) LVP_Fe (d) LVP_Co (e) LVP_Ni (f)NVP (g)NVP_Mn (h)NVP_Fe (i)NVP_Co (j)NVP_Ni 銅極片電池C-rate圖。 85
圖(4. 4.13)　(a)LVP系列 (b) NVP系列鋁極片電池不同充放電速度電容量圖。 86
圖(4. 4.14)　(a)LVP (b) LVP_Mn (c) LVP_Fe (d) LVP_Co (e) LVP_Ni (f)NVP (g)NVP_Mn (h)NVP_Fe (i)NVP_Co (j)NVP_Ni 鋁極片電池C-rate圖。 87
圖(4. 5.1)　銅極片電池(a)LVP系列 (b) NVP系列；鋁極片電池(c) LVP系列 (d) NVP系列EIS圖。 88
圖(4. 5.2)　鋁極片電池(a)LVP系列 (b)NVP系列Rct與V價數比較圖。 91
圖(4. 5.3)　 LVP系列晶格體積與銅/鋁極片電池之離子擴散速度比較圖。 91
圖(4. 5.4)　 NVP系列(a) 晶格體積與銅極片電池(b) c軸晶格常數與鋁極片電池離子擴散速度比較圖。 92




圖(4. 6.1)　 LVP系列(a)銅極片(b)鋁極片電池；NVP系列(c)銅極片(d)鋁極片電池(e)整體比較不同充放電速度(f)文獻電池能量密度與功率密度作圖。 ………………93
圖(4. 6.2)　 LVP系列(a)銅極片(b)鋁極片電池；NVP系列(c)銅極片(d)鋁極片電池不同變磁場能量密度與功率密度作圖。 95

 
表目錄
表(一)　 Nasicon結構中(PO4)3-在空間群R-3m之對稱相關性。 17
表(二)　各種Nasicon結構銅磷酸鹽之紅外頻率。 17
表(三)　藥品資訊表。 43
表(四)　Li3V2(PO4)3原子位子表。 52
表(五)　 Na3V2(PO4)3原子位子表。 52
表(六)　 Li3V1.9Fe0.1(PO4)3原子位子表。 54
表(七)　 Na3V1.9Fe0.1(PO4)3原子位子表。 54
表(八)　 LVP摻雜變場晶格常數與磁致伸縮表。 59
表(九)　 NVP摻雜變場晶格常數與磁致伸縮表。 61
表(十)　 V鍵結價數表。 62
表(十一) 對應離子價數之離子半徑表。 66
表(十二)　ID/IG強度比表。 71
表(十三)　變場阻抗、離子擴散速數表。 89

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