高溫高壓之電解水產氫效率分析

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蔡宗澤(Tsung-tse Tsai) 查詢紙本館藏

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能源工程研究所

論文名稱

高溫高壓之電解水產氫效率分析
(Analysis of water electrolysis energy efficiency under high presssure and high temperature)

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摘要(中)

本論文主旨是為探討高溫高壓之下，電解水產氫的效率，主要以電流對電壓圖作為表現依據，其中，又將電流電壓表現，細分為四種不同的反應機制，個別加以詳細探討，四種不同反應機制如下:
1.可逆電位(reversible voltage) 2.活性極化(activation polarization) 3.歐姆極化(ohmic polarization) 4.濃度極化(concentration polarization)。
每個不同反應機制的結果為: 1.可逆電位:隨著溫度壓力愈高，其電位愈低。2.活性極化: 隨著溫度愈高，其過電位愈低，而活性過電位受到壓力的影響可以忽略。3.歐姆極化:分為電極電阻過電位以及氣泡電阻過電位來考慮，其中隨著溫度上升，電極電阻過電位增加，不受壓力影響，而隨著溫度上升，氣泡電阻過電位增加，隨著壓力上升，過電位下降，但在電流密度小於1A/cm2的情況下，氣泡電阻過電位十分小可以忽略4.濃度極化: 隨著溫度愈高，其過電位愈低，其受到壓力的影響可忽略。但在電流密度小於1A/cm2的情況下，濃度過電位十分小可忽略。
而最後的整體電能消耗部分，500bar/370oC比起1bar(約1atm)/80oC節省了約17%的電能，若我們再考慮把1bar的氣體壓縮到500bar的壓縮能量花費，則500bar/370oC節省了約22%的電能。

摘要(英)

This work aims at analysing the energy efficiency of a high pressure, high temperature water electrolysis by current-voltage diagram.
Four different kinds of reaction mechanisms,namely,1. reversible voltage, 2. activation polarization, 3. ohmic polarization,and 4. concentration polarization,are investigated in details.。
The results of each different reaction mechanisms are: 1. Reversible voltage: The higher the temperature and pressure are, the lower its potential is. 2.Activation polarization: The higher the temperature is, the lower its potential is. However,the influence of pressure can be neglected. 3. Ohmic polarization: it can be divided into electrode resistance and bubble resistance . Between them, the electrode resistance overpotential
rises with temperature, but is not effected by pressure. The bubble resistance overpotential increases as temperature rises,and drops as the pressure rises.However, as the current density is smaller than 1A/cm2, the bubble resistance overpotential is very small and can be neglected.4. Concentration polarization: As temperature gets higher, the concentration overpotential decreases, and the influence of pressure can be neglected.
The whole electric energy consumption at 500bar/370oC, compared with that at 1bar/80oC, is saved about 17%. If the consumption of compressing the gas from 1bar to 500bar is considered, then the water electrolysis at 500bar/370oC saves about 22% of the electric energy.

關鍵字(中)

★ 電解水
★ 高溫高壓水電解
★ 活性過電壓
★ 產氫

關鍵字(英)

★ hydrogen production
★ activation overvoltage
★ water electrolysis

論文目次

摘要 ............................................................................................................I
ABSTRACT..............................................................................................II
目錄.........................................................................................................III
表目錄.....................................................................................................VI
圖目錄...................................................................................................VII
符號說明.................................................................................................X
第一章緒論............................................................................................1
1-1前言............................................................................................1
1-2產氫............................................................................................3
1-3文獻回顧....................................................................................3
1-4研究目的與動機 ........................................................................6
第二章理論基礎.....................................................................................8
2-1電解水製氫之基本原理.............................................................8
2-2可逆電位..................................................................................10
2-3法拉第定律..............................................................................10
2-4吉布斯自由能 ..........................................................................11
2-5極化作用..................................................................................12
2-5-1濃度極化 .......................................................................13
2-5-2活性極化 .......................................................................14
2-5-3歐姆極化 .......................................................................15
2-5-3-1電極片造成的歐姆極化 ...................................15
2-5-3-2氣泡造成的歐姆極化 .......................................16
第三章理論模型與計算方法...............................................................18
3-1可逆電位..................................................................................19
3-1-1可逆電位的計算方法...................................................19
3-1-2可逆電位的計算結果與討論.......................................20
3-2活性過電位...............................................................................20
3-2-1活性過電位的計算方法........................................................21
3-2-2活性過電位的計算結果與討論............................................22
3-3歐姆極化:歐姆過電位之計算及結果與討論..........................23
3-3-1電極片上線段部分造成的歐姆過電位........................23
3-3-1-1電極片上線段部分造成的歐姆過電位之計算方法......................................................................................23
3-3-1-2電極片上線段部分造成的歐姆過電位之計算結果與討論..........................................................................24
3-3-2氣泡造成的歐姆過電位之計算方法及結果與討論....25
3-4濃度過電位之計算及結果與討論 ...........................................25
3-5不考慮最後須要壓縮氣體的能量之能量效率比較...............26
3-6考慮最後須要壓縮氣體的能量之能量效率比較...................28
第四章結論與未來研究建議...............................................................30
4-1結論..........................................................................................30
4-2未來研究建議..........................................................................31
參考文獻 ................................................................................................33
表 ............................................................................................................37
圖 ............................................................................................................41
附錄........................................................................................................54
附錄圖....................................................................................................59
表(3-1) 可逆電位隨溫度及壓力的變化................................................37
表(3-2) 可逆電位隨溫度及壓力的變化，利用線性內插法得到........37
表(3-3) 常溫常壓下0.5m(莫爾重量濃度) NaOH溶液的各種性質.....38
表(3-4) 離子特性受到溫度的影響........................................................38
表(3-5) 常溫下離子遷移數跟壓力的關係，其中t+表示陽離子遷移數..............................................................................................................39
表(3-6) 常溫下擴散係數跟壓力的關係，其中D指的是擴散係數，Dp/Do指的是該壓力之下跟常壓下的擴散係數比值............................39
表(3-7) 常溫時總當量電導度跟壓力的關係........................................40
圖(1-1) 1850年至2150年，世界能源過渡圖......................................41
圖(1-2) 氫/碳的原子數比.......................................................................41
圖(3-1) 電極片背面示意圖....................................................................42
圖(3-2) 電極片側面示意圖....................................................................42
圖(3-3) 水的三相圖................................................................................43
圖(3-4) 可逆電位跟溫度壓力的關係....................................................43
圖(3-5) 80oC及370oC之下，未考慮交換電流密度受溫度改變時，所計算出的活性過電位與電流的關係......................................................44
圖(3-6) 80oC及370oC之下，考慮交換電流密度受溫度改變時，所計算出的活性過電位與電流的關係..........................................................44
圖(3-7) 80oC之下，比較不修正及修正，交換電流密度為溫度的函數，的活性過電位對電流關係......................................................................45
圖(3-8) 370oC之下，比較不修正及修正，交換電流密度為溫度的函數，的活性過電位對電流關係......................................................................45
圖(3-9) 電極片的線段，的歐姆過電位和電流之關係(截面積為1mm2 ).......................................................................................................46
圖(3-10) 電極電極片的線段，的歐姆過電位和電流之關係(截面積為10mm2).....................................................................................................46
圖(3-11) Kuhn等人的實驗值，氣泡造成的歐姆過電位和電流的關係..............................................................................................................47
圖(3-12) 本文根據Roy等人的經驗公式繪出的圖，顯示氣泡造成的過電位對電流的關係..............................................................................47
圖(3-13) 常溫常壓下，濃度過電位和電流的關係..............................48
圖(3-14) 80oC 總供應電壓跟電流密度對各壓力的關係.....................48
圖(3-15) 170oC總供應電壓跟電流密度對各壓力的關係....................49
圖(3-16) 300oC 總供應電壓跟電流密度對各壓力的關係...................49
圖(3-17) 370oC/500bar總供應電壓跟電流密度的關係........................50
圖(3-18) 固定壓力為500bar 各溫度之下總供應電壓對電流的關係.50
圖(3-19) 固定壓力為100bar 各溫度之下總供應電壓對電流的關係.51
圖(3-20) 800C/1bar，線段截面積為1mm2之下，三個反應機制佔總供應電壓之權重..........................................................................................51
圖(3-21) 800C/500bar，線段截面積為10mm2之下，三個反應機制佔總供應電壓之權重......................................................................................52
圖(3-22) 800C/1bar，線段截面積為1mm2之下，三個反應機制佔總供應電壓之權重..........................................................................................52
圖(3-23) 3700C/500bar，線段截面積為1mm2之下，三個反應機制佔總供應電壓之權重......................................................................................53
圖(3-24) 3700C/500bar，線段截面積為10mm2之下，三個反應機制佔總供應電壓之權重..................................................................................53
附錄圖(1) Marshall等人的電解水實驗數據.........................................59
附錄圖(2) Yangjian 等人的電解水實驗數據........................................59
附錄圖(3) 用Nagai等人的理論企圖擬合出特性電阻........................60

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指導教授

洪勵吾(Lih-wu Hourng)

審核日期

2009-7-14

推文