TWI629254B - Method for adding cations to a niobium titanate ceramic material to change the thermoelectric properties of the material - Google Patents
Method for adding cations to a niobium titanate ceramic material to change the thermoelectric properties of the material Download PDFInfo
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Abstract
本發明係有關於一種在鉍鈦氧陶瓷材料添加陽離子以改變材料熱電特性之方法。係依照下列化學計量比例將陽離子添加於鉍鈦氧陶瓷材料中，鉍鈦氧陶瓷材料之化學式為Bi4Ti3O12，該化學計量比例為(Bi4-xAx)Ti3O12或Bi4(Ti3-yMy)O12或(Bi4-xAx)(Ti3-yMy)O12，其中A及M均為陽離子，x為小於4的實數，y為小於3的實數。藉由添加適當比例的陽離子，可改變鉍鈦氧陶瓷材料的熱電特性，增加鉍鈦氧陶瓷材料的應用領域。 This invention relates to a method of adding a cation to a niobium titanate ceramic material to modify the thermoelectric properties of the material. The cation is added to the niobium titanate ceramic material according to the following stoichiometric ratio. The chemical formula of the niobium titanate ceramic material is Bi 4 Ti 3 O 12 , and the stoichiometric ratio is (Bi 4-x A x )Ti 3 O 12 or Bi 4 (Ti 3-y M y )O 12 or (Bi 4-x A x )(Ti 3-y M y )O 12 , wherein A and M are both cations, x is a real number less than 4, and y is less than The real number of 3. By adding an appropriate proportion of cations, the thermoelectric properties of the niobium titanate ceramic material can be changed, and the application field of the niobium titanate ceramic material can be increased.
Description
本發明係有關於一種在鉍鈦氧陶瓷材料添加陽離子以改變材料熱電特性之方法，所述鉍鈦氧陶瓷材料的化學式為Bi4Ti3O12，所述方法係將部分鉍離子(Bi3+)或鈦離子(Ti4+)以其它陽離子取代，藉此改變鉍鈦氧陶瓷材料的熱電特性。 The present invention relates to a method for adding a cation to a thermoelectric property of a cerium-titanium oxy-ceramic material, the chemical formula of the cerium-titanium oxy-ceramic material being Bi 4 Ti 3 O 12 , which is a partial cerium ion (Bi 3 ) + ) or titanium ions (Ti 4+ ) are substituted with other cations, thereby changing the thermoelectric properties of the cerium-titanium oxy-ceramic material.
熱電材料就是在無任何特定外力下，即可將熱能和電能兩種不同型態的能量做交互轉換的材料，能夠在足夠的溫差下產生電動勢，達到以熱生電的現象。傳統熱電材料之開發以合金為主，主要是因為有較好的熱電轉換效率。 The thermoelectric material is a material that can exchange energy of two different types of heat energy and electric energy without any specific external force, and can generate an electromotive force under a sufficient temperature difference to achieve the phenomenon of generating electricity by heat. The development of traditional thermoelectric materials is mainly based on alloys, mainly because of the better thermoelectric conversion efficiency.
參閱N.T.Tinh,T.Tsuji,“Thermoelectric Properties of Heavily Doped Polycrystalline SrTiO3,”Physics and Engineering of New Materials,Springer Proceedings in Physics Volume 127,pp.209-217,2009.或者M.Ohtaki,D.Ogura,K.Eguchi,H.Arai,“High-temperature thermoelectric properties of(Zn1-xAlx)O,”J.Appl.Phys.79,pp.1816-1818,1996.或者H.Ohta,K.Sugiura,K.Koumoto,“Recent progress in oxide thermoelectric materials：p-type Ca3Co4O9 and n-Type SrTiO3”Inorg.Chem.,47,pp.8429-8436,2008.等研究，近一二十年具類似鈣鈦礦結構的Ca3Co4O9、SrTiO3等氧化物陶瓷材料也被發現具有相當優異的熱電特性而吸引眾人研究。 See NTTinh, T. Tsuji, "Thermoelectric Properties of Heavily Doped Polycrystalline SrTiO 3 ," Physics and Engineering of New Materials, Springer Proceedings in Physics Volume 127, pp. 209-217, 2009. or M. Ohtaki, D. Ogura, K .Eguchi, H. Arai, "High-temperature thermoelectric properties of (Zn 1-x Al x )O," J. Appl. Phys. 79, pp. 1816-1818, 1996. or H. Ohta, K. Sugiura, K. Koumoto, "Recent progress in oxide thermoelectric materials: p-type Ca 3 Co 4 O 9 and n-Type SrTiO 3 "Inorg. Chem., 47, pp. 8429-8436, 2008. Oxide ceramic materials such as Ca 3 Co 4 O 9 and SrTiO 3 having a perovskite structure have also been found to have quite excellent thermoelectric properties and have attracted research.
其中，熱電材料的性能指標是以熱電優值ZT(Figure of Merit)來判斷其實用性，ZT=S2σ T/κ。其中S係Seebeck係數，σ係導電率，κ係熱導率，T係絕對溫度。而前述各研究主要是針對提高Seebeck係數以增加其熱電優值ZT。 Among them, the performance index of thermoelectric materials is judged by the thermoelectric figure ZT (Figure of Merit), ZT = S 2 σ T / κ. Among them, S is the Seebeck coefficient, σ system conductivity, κ system thermal conductivity, and T system absolute temperature. The foregoing studies are mainly aimed at increasing the Seebeck coefficient to increase its thermoelectric figure of merit ZT.
本發明是採取降低κ值來改變熱電優值ZT，而鉍鈦氧陶瓷材料(Bi4Ti3O12)具有較前述氧化物陶瓷材料低的κ值，且本發明之發明人發現鉍鈦氧陶瓷材料(Bi4Ti3O12)亦為一種優異的熱電陶瓷材料，故本發明使用鉍鈦氧陶瓷材料(Bi4Ti3O12)進行試驗。本發明將鉍鈦氧陶瓷材料中的鉍離子(Bi3+)或鈦離子(Ti4+)以其它陽離子取代，藉此改變鉍鈦氧陶瓷材料的熱電特性，使其成為具有半導性之新熱電陶瓷材料。 The present invention adopts a decrease in the κ value to change the thermoelectric figure of merit ZT, and the bismuth titanate ceramic material (Bi 4 Ti 3 O 12 ) has a lower κ value than the foregoing oxide ceramic material, and the inventors of the present invention have found that strontium titanate The ceramic material (Bi 4 Ti 3 O 12 ) is also an excellent thermoelectric ceramic material, so the present invention was tested using a niobium titania ceramic material (Bi 4 Ti 3 O 12 ). The present invention replaces cerium ions (Bi 3+ ) or titanium ions (Ti 4+ ) in the cerium-titanium oxy-ceramic material with other cations, thereby changing the thermoelectric properties of the cerium-titanium oxy-ceramic material to make it semi-conductive. New thermoelectric ceramic materials.
因此，本發明係一種在鉍鈦氧陶瓷材料添加陽離子以改變材料熱電特性之方法。該方法包括：依照下列化學計量比例將陽離子添加於一鉍鈦氧陶瓷材料中，該鉍鈦氧陶瓷材料之化學式為Bi4Ti3O12，該化學計量比例為(Bi4-xAx)Ti3O12、Bi4(Ti3-yMy)O12或(Bi4-xAx)(Ti3-yMy)O12，其中A及M均為陽離子，x為小於4的實數，y為小於3的實數。 Accordingly, the present invention is a method of adding a cation to a niobium titanate ceramic material to change the thermoelectric properties of the material. The method comprises: adding a cation to a tantalum titanium oxy-ceramic material according to the following stoichiometric ratio, the chemical formula of the niobium titanate ceramic material is Bi 4 Ti 3 O 12 , and the stoichiometric ratio is (Bi 4-x A x ) Ti 3 O 12 , Bi 4 (Ti 3-y M y )O 12 or (Bi 4-x A x )(Ti 3-y M y )O 12 , wherein A and M are both cations, and x is less than 4 Real number, y is a real number less than 3.
進一步，該化學計量比例為Bi4(Ti3-yMy)O12，且M為鈮離子，y為0.1。 Further, the stoichiometric ratio is Bi 4 (Ti 3-y M y )O 12 , and M is a cerium ion, and y is 0.1.
進一步，該化學計量比例為(Bi4-xAx)Ti3O12，且A為鍶離子，x為0.1或0.2。 Further, the stoichiometric ratio is (Bi 4-x A x )Ti 3 O 12 , and A is a cerium ion, and x is 0.1 or 0.2.
進一步，所述添加陽離子之鉍鈦氧陶瓷材料以反應燒結法製成。更進一步，燒結溫度介於900℃至1000℃之間。 Further, the cation-added niobium titanate ceramic material is produced by a reaction sintering method. Further, the sintering temperature is between 900 ° C and 1000 ° C.
根據上述技術特徵可達成以下功效： According to the above technical features, the following effects can be achieved:
1.利用不同價電子數的陽離子取代鉍鈦氧陶瓷材料中部分的鉍離子(Bi3+)或鈦離子(Ti4+)，以改變鉍鈦氧陶瓷材料的熱電特性，可使鉍鈦氧陶瓷材料應用領域更為廣泛。 1. Using a cation with a different valence electron number to replace some of the cerium ions (Bi 3+ ) or titanium ions (Ti 4+ ) in the cerium-titanium oxy-ceramic material to change the thermoelectric properties of the cerium-titanium oxy-ceramic material, so that the cerium-titanium oxide can be made. Ceramic materials are used in a wider range of applications.
2.根據產品的不同需求，可以依照前述化學計量比例調整用來取代鉍離子(Bi3+)或鈦離子(Ti4+)的陽離子添加量。 2. The amount of cation added to replace the cerium ion (Bi 3+ ) or the titanium ion (Ti 4+ ) may be adjusted according to the stoichiometric ratio described above according to the different requirements of the product.
[第一圖]係為本發明實施例中，以反應燒結法所製成之Bi4Ti3O12鉍鈦氧陶瓷材料(BTO)的SEM顯微圖。 [First Image] is an SEM micrograph of a Bi 4 Ti 3 O 12铋 titanium oxy-ceramic material (BTO) produced by a reaction sintering method in the examples of the present invention.
[第二圖]係為本發明實施例中，以反應燒結法所製成之Bi4Ti3O12鉍鈦氧陶瓷材料(BTO)之電阻率(logρ)隨溫度變化曲線圖。 [Second diagram] is a graph showing the resistivity (log ρ) of a Bi 4 Ti 3 O 12铋 titanium oxy-ceramic material (BTO) prepared by a reaction sintering method as a temperature change in the examples of the present invention.
[第三圖]係為本發明實施例中，以反應燒結法所製成之Bi4Ti3O12鉍鈦氧陶瓷材料(BTO)之Seebeck係數隨溫度變化曲線圖。 [Third image] is a graph showing the Seebeck coefficient as a function of temperature of a Bi 4 Ti 3 O 12铋 titanium oxy-ceramic material (BTO) prepared by a reaction sintering method in an embodiment of the present invention.
[第四圖]係為本發明實施例中，利用10%莫耳鈮離子(Nb5+)取代部分鈦離子(Ti4+)，以反應燒結法所製成之鉍鈦氧陶瓷材料(BTO-N)的SEM顯微圖。 [Fourth figure] is a titanium-titanium-oxygen ceramic material (BTO) prepared by a reaction sintering method by using a 10% molar ion (Nb 5+ ) instead of a part of titanium ion (Ti 4+ ) in the embodiment of the present invention. SEM micrograph of -N).
[第五圖]係為本發明實施例中，利用10%莫耳鈮離子(Nb5+)取代部分鈦離子(Ti4+)之鉍鈦氧陶瓷材料(BTO-N)之電阻率(logρ)隨溫度變化曲線圖。 [Fifth diagram] is the resistivity (logo) of a niobium titanate ceramic material (BTO-N) in which a part of titanium ions (Ti 4+ ) is replaced by 10% molybdenum ions (Nb 5+ ) in the embodiment of the present invention. ) A graph of changes with temperature.
[第六圖]係為本發明實施例中，利用10%莫耳鈮離子(Nb5+)取代部分鈦離子(Ti4+)之鉍鈦氧陶瓷材料(BTO-N)之Seebeck係數隨溫度變化曲線圖。 [Sixth image] is a Seebeck coefficient of a bismuth titanium oxide ceramic material (BTO-N) which replaces a part of titanium ions (Ti 4+ ) with 10% molar ions (Nb 5+ ) according to the temperature in the embodiment of the present invention. Change graph.
[第七圖]係為本發明實施例中，利用10%莫耳鍶離子(Sr2+)取代部分鉍離子(Bi3+)，以反應燒結法所製成之鉍鈦氧陶瓷材料(BTO-S1)之SEM顯微圖。 [Seventh] is a bismuth titanium oxide ceramic material (BTO) prepared by a reaction sintering method by using a 10% molar ion (Sr 2+ ) instead of a part of cerium ion (Bi 3+ ) in the embodiment of the present invention. SEM micrograph of -S1).
[第八圖]係為本發明實施例中，利用10%莫耳鍶離子(Sr2+)取代部分鉍離子(Bi3+)之鉍鈦氧陶瓷材料(BTO-S1)之電阻率(logρ)隨溫度變化曲線圖。 [Eighth image] is the resistivity (logρ) of a bismuth titanium oxide ceramic material (BTO-S1) in which a part of cerium ions (Bi 3+ ) is replaced by 10% molar ions (Sr 2+ ) in the embodiment of the present invention. ) A graph of changes with temperature.
[第九圖]係為本發明實施例中，利用10%莫耳鍶離子(Sr2+)取代部分鉍離子(Bi3+)之鉍鈦氧陶瓷材料(BTO-S1)之Seebeck係數隨溫度變化曲線圖。 [Ninth aspect] is a Seebeck coefficient of a bismuth titanium oxide ceramic material (BTO-S1) in which a part of cerium ions (Bi 3+ ) is replaced by 10% molar ions (Sr 2+ ) according to the temperature in the embodiment of the present invention. Change graph.
[第十圖]係為本發明實施例中，利用20%莫耳鍶離子(Sr2+)取代部分鉍離子(Bi3+)，以反應燒結法所製成之鉍鈦氧陶瓷材料(BTO-S2)的SEM顯微圖。 [Tenth Graph] is a tantalum titanium oxide ceramic material (BTO) prepared by a reaction sintering method by using a 20% molar ion (Sr 2+ ) instead of a part of cerium ions (Bi 3+ ) in the embodiment of the present invention. SEM micrograph of -S2).
[第十一圖]係為本發明實施例中，利用20%莫耳鍶離子(Sr2+)取代部分鉍離子(Bi3+)之鉍鈦氧陶瓷材料(BTO-S2)之電阻率(logρ)隨溫度變化曲線圖。 [11th] is a resistivity of a bismuth titanium oxide ceramic material (BTO-S2) in which a part of cerium ions (Bi 3+ ) is replaced by 20% molar ions (Sr 2+ ) in the embodiment of the present invention ( Logρ) as a function of temperature.
[第十二圖]係為本發明實施例中，利用20%莫耳鍶離子(Sr2+)取代部分鉍離子(Bi3+)之鉍鈦氧陶瓷材料(BTO-S2)之Seebeck係數隨溫度變化曲線圖。 [Twelfth] is a Seebeck coefficient of a bismuth titanium oxide ceramic material (BTO-S2) in which a part of cerium ions (Bi 3+ ) is replaced by 20% molar ions (Sr 2+ ) in the embodiment of the present invention. Temperature curve.
綜合上述技術特徵，本發明在鉍鈦氧陶瓷材料添加陽離子以改變材料熱電特性之方法的主要功效將可於下述實施例清楚呈現。 In combination with the above technical features, the main effects of the method of the present invention for adding a cation to a niobium titanate ceramic material to change the thermoelectric properties of the material will be apparent from the following examples.
本發明係依照下列化學計量比例將陽離子添加於一鉍鈦氧陶瓷材料中，該鉍鈦氧陶瓷材料之化學式為Bi4Ti3O12，該化學計量比例為(Bi4-xAx)Ti3O12、Bi4(Ti3-yMy)O12或(Bi4-xAx)(Ti3-yMy)O12，其中A及M均為陽離子，x為小於4的實數，y為小於3的實數。 The present invention adds a cation to a cerium-titanium oxy-ceramic material according to the following stoichiometric ratio, the chemical formula of the cerium-titanium oxy-ceramic material is Bi 4 Ti 3 O 12 , and the stoichiometric ratio is (Bi 4-x A x )Ti 3 O 12 , Bi 4 (Ti 3-y M y )O 12 or (Bi 4-x A x )(Ti 3-y M y )O 12 , wherein A and M are both cations, and x is a real number less than 4. , y is a real number less than 3.
本實施例係使用無煆燒之固態氧化物反應法(即反應燒結法)，製造Bi4Ti3O12基材(簡稱BTO)及Bi4(Ti3-yMy)O12基材，其中M使用鈮離子(Nb5+)，y為0.1，即Bi4(Ti2.9Nb0.1)O12(簡稱BTO-N)。 In this embodiment, a Bi 4 Ti 3 O 12 substrate (abbreviated as BTO) and a Bi 4 (Ti 3-y M y )O 12 substrate are produced by using a solid oxide reaction method (ie, a reaction sintering method) without a bismuth. Wherein M is a cerium ion (Nb 5+ ), and y is 0.1, that is, Bi 4 (Ti 2.9 Nb 0.1 )O 12 (abbreviated as BTO-N).
首先依照化學計量比例將Bi2O3、Nb2O5、TiO2粉末秤好置入球磨罐中，另外添加1wt%CuO降低燒結溫度，以純水和氧化鋯球混合球磨12小時後放入烘箱中，烘乾後經搗磨成粉末，壓成直徑12mm，厚度2mm至3mm之間的生胚，以氧化鋁坩鍋覆蓋，置入高溫爐於900℃至1000℃之間持溫6小時燒結。 First, the Bi 2 O 3 , Nb 2 O 5 , and TiO 2 powders were placed in a ball mill jar according to the stoichiometric ratio. The addition of 1 wt% CuO was used to reduce the sintering temperature, and the mixture was ball milled with pure water and zirconia balls for 12 hours. In the oven, after drying, it is honed into a powder, pressed into a green embryo with a diameter of 12 mm and a thickness of 2 mm to 3 mm, covered with an alumina crucible, placed in a high temperature furnace and held at a temperature of 900 ° C to 1000 ° C for 6 hours. sintering.
參閱第一圖所示，係為本實施例以反應燒結法所製成之BTO的SEM顯微圖，示意BTO的結晶狀態。圖式之A為燒結溫度900℃；圖式之B為燒結溫度950℃；圖式之C為燒結溫度970℃；圖式之D為燒結溫度1000℃。 Referring to the first figure, the SEM micrograph of the BTO prepared by the reaction sintering method of the present embodiment is shown to indicate the crystal state of the BTO. The drawing A is a sintering temperature of 900 ° C; the drawing B is a sintering temperature of 950 ° C; the drawing C is a sintering temperature of 970 ° C; and the drawing D is a sintering temperature of 1000 ° C.
參閱第二圖所示，係為本實施例以反應燒結法所製成之BTO，以兩點探針量測在溫度介於350℃至700℃之間的電阻率(logρ)，鉍鈦氧陶瓷材料的電阻率(logρ)明顯改變並隨溫度降低。 Referring to the second figure, the BTO prepared by the reaction sintering method of the present embodiment is measured by a two-point probe at a resistivity (log ρ) at a temperature between 350 ° C and 700 ° C. The resistivity (logρ) of the ceramic material changes significantly and decreases with temperature.
參閱第三圖所示，係為本實施例以反應燒結法所製成之BTO的Seebeck係數，其中Seebeck係數亦有明顯變化，BTO為p型熱電材料。 Referring to the third figure, the Seebeck coefficient of the BTO produced by the reaction sintering method in the present embodiment, wherein the Seebeck coefficient also has a significant change, and the BTO is a p-type thermoelectric material.
參閱第四圖所示，係為本實施例以反應燒結法所製成之BTO-N的SEM顯微圖，示意摻雜Nb5+的BTO-N陶瓷之結晶狀態。圖式之A為燒結溫度900℃；圖式之B為燒結溫度950℃；圖式之C為燒結溫度970℃；圖式之D為燒結溫度1000℃。 Referring to the fourth figure, the SEM micrograph of BTO-N prepared by the reaction sintering method of the present embodiment is shown in the crystal state of the BTO-N ceramic doped with Nb 5+ . The drawing A is a sintering temperature of 900 ° C; the drawing B is a sintering temperature of 950 ° C; the drawing C is a sintering temperature of 970 ° C; and the drawing D is a sintering temperature of 1000 ° C.
參閱第五圖所示，以兩點探針量測BTO-N在溫度介於400℃至700℃之間的電阻率(logρ)，BTO-N的電阻率(logρ)明顯改變並隨溫度降低。 Referring to Figure 5, the resistivity (logρ) of BTO-N at a temperature between 400 °C and 700 °C is measured by a two-point probe. The resistivity (logρ) of BTO-N changes significantly and decreases with temperature. .
參閱第六圖所示，係BTO-N之Seebeck係數，其中Seebeck係數亦有明顯變化，雖BTO為p型熱電材料，摻雜Nb5+的BTO-N為n型熱電材料。 Referring to the sixth figure, it is the Seebeck coefficient of BTO-N, in which the Seebeck coefficient also changes significantly. Although BTO is a p-type thermoelectric material, BTO-N doped with Nb 5+ is an n-type thermoelectric material.
本實施例再以反應燒結法製備(Bi4-xAx)Ti3O12基材，其中A使用鍶離子(Sr2+)，x為0.1或0.2，即(Bi3.9Sr0.1)Ti3O12與(Bi3.8Sr0.2)Ti3O12(簡稱BTO-S1、BTO-S2)。 In this embodiment, a (Bi 4-x A x )Ti 3 O 12 substrate is prepared by a reaction sintering method, wherein A uses a cerium ion (Sr 2+ ), and x is 0.1 or 0.2, that is, (Bi 3.9 Sr 0.1 )Ti 3 . O 12 and (Bi 3.8 Sr 0.2 )Ti 3 O 12 (abbreviated as BTO-S1, BTO-S2).
同樣的，依照化學計量比例將Bi2O3、SrCO3、TiO2粉末秤好置入球磨罐中，另外添加1wt%CuO降低燒結溫度，以純水和氧化鋯球混合球磨12小時後放入烘箱中，烘乾後經搗磨成粉末，壓成直徑12mm，厚度2mm至3mm之間的生胚，以氧化鋁坩鍋覆蓋，置入高溫爐於900℃至1000℃之間持溫6小時燒結。 Similarly, the Bi 2 O 3 , SrCO 3 , and TiO 2 powders were scaled into a ball mill tank according to the stoichiometric ratio, and 1 wt% CuO was additionally added to lower the sintering temperature, and the mixture was ball milled with pure water and zirconia balls for 12 hours. In the oven, after drying, it is honed into a powder, pressed into a green embryo with a diameter of 12 mm and a thickness of 2 mm to 3 mm, covered with an alumina crucible, placed in a high temperature furnace and held at a temperature of 900 ° C to 1000 ° C for 6 hours. sintering.
參閱第七圖所示，係為本實施例以反應燒結法所製成之BTO-S1的SEM顯微圖，示意BTO-S1的結晶狀態。圖式之A為燒結溫度900℃；圖式之B為燒結溫度950℃；圖式之C為燒結溫度970℃；圖式之D為燒結溫度1000℃。 Referring to the seventh embodiment, the SEM micrograph of BTO-S1 produced by the reaction sintering method of the present embodiment is shown to indicate the crystal state of BTO-S1. The drawing A is a sintering temperature of 900 ° C; the drawing B is a sintering temperature of 950 ° C; the drawing C is a sintering temperature of 970 ° C; and the drawing D is a sintering temperature of 1000 ° C.
參閱第八圖所示，以兩點探針量測BTO-S1在溫度介於350℃至700℃之間的電阻率(logρ)。圖中顯示，添加鍶離子(Sr2+)取代部分鉍離子(Bi3+)時，BTO-S1的電阻率(logρ)明顯比第二圖之BTO電阻率為低。 Referring to Figure 8, the resistivity (log ρ) of BTO-S1 at a temperature between 350 ° C and 700 ° C is measured with a two-point probe. The figure shows that when ytterbium ion (Sr 2+ ) is added to replace part of ytterbium ion (Bi 3+ ), the resistivity (log ρ) of BTO-S1 is significantly lower than that of BTO of the second graph.
參閱第九圖所示，係以反應燒結法所製成之BTO-S1之Seebeck係數，其值比第三圖之未摻雜的BTO之Seebeck係數略高且變異性更小，添加鍶離子(Sr2+)後的BTO-S1均為p型熱電材料。 Referring to the ninth figure, the Seebeck coefficient of BTO-S1 produced by the reaction sintering method is slightly higher than the Seebeck coefficient of the undoped BTO of the third figure and has less variability, and added erbium ions ( The BTO-S1 after Sr 2+ ) is a p-type thermoelectric material.
參閱第十圖所示，係為本實施例以反應燒結法所製成之BTO-S2的SEM顯微圖，示意BTO-S2的結晶狀態。圖式之A為燒結溫度900℃；圖式之B為燒結溫度950℃；圖式之C為燒結溫度970℃；圖式之D為燒結溫度1000℃。 Referring to the tenth figure, the SEM micrograph of BTO-S2 produced by the reaction sintering method of the present embodiment is shown in the crystal state of BTO-S2. The drawing A is a sintering temperature of 900 ° C; the drawing B is a sintering temperature of 950 ° C; the drawing C is a sintering temperature of 970 ° C; and the drawing D is a sintering temperature of 1000 ° C.
參閱第十一圖所示，以兩點探針量測BTO-S2在溫度介於350℃至700℃之間的電阻率(logρ)。圖中顯示，添加鍶離子(Sr2+)取代部分鉍離子(Bi3+)時，BTO-S2的電阻率(logρ)明顯比第二圖之BTO電阻率為低。 Referring to Figure 11, the resistivity (log ρ) of BTO-S2 at a temperature between 350 ° C and 700 ° C is measured with a two-point probe. The figure shows that when ytterbium ion (Sr 2+ ) is added to replace part of yttrium ion (Bi 3+ ), the resistivity (log ρ) of BTO-S2 is significantly lower than that of BTO of the second figure.
參閱第十二圖所示，係以反應燒結法所製成之BTO-S2之Seebeck係數，其值比第三圖之未摻雜的BTO之Seebeck係數略高且變異性更小，且仍為p型熱電材料。 Referring to Figure 12, the Seebeck coefficient of BTO-S2 produced by the reaction sintering method is slightly higher than the Seebeck coefficient of the undoped BTO of the third figure and the variability is smaller, and still P-type thermoelectric material.
綜合上述實施例之說明，當可充分瞭解本發明之操作、使用及本發明產生之功效，惟以上所述實施例僅係為本發明之較佳實施例，當不能以此限定本發明實施之範圍，即依本發明申請專利範圍及發明說明內容所作簡單的等效變化與修飾，皆屬本發明涵蓋之範圍內。 In view of the foregoing description of the embodiments, the operation and the use of the present invention and the effects of the present invention are fully understood, but the above described embodiments are merely preferred embodiments of the present invention, and the invention may not be limited thereto. Included within the scope of the present invention are the scope of the present invention.
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