本文關(guān)鍵詞：新型鋰-氧氣電池雙功能催化劑研究　出處：《中國(guó)科學(xué)院大學(xué)(中國(guó)科學(xué)院物理研究所)》2017年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 鋰-氧氣電池 氧還原反應(yīng)/析氧反應(yīng) 尖晶石 鈣鈦礦

【摘要】：與鋰離子電池相比,鋰-氧氣電池具有更高的能量密度,因此近年來(lái)受到研究人員的廣泛關(guān)注。在鋰-氧氣電池放電過(guò)程中,氧分子在正極表面被還原之后同Li~+生成LiOx化合物;而充電過(guò)程中,催化劑催化分解LiOx,析出氧氣。正極材料需要同時(shí)對(duì)氧還原反應(yīng)(ORR)和析氧反應(yīng)(OER)有催化性能,因此如何從材料設(shè)計(jì)角度提高鋰-氧氣電池充放電效率、降低電池極化是目前鋰-氧氣電池研究的前沿方向。貴金屬作為鋰-氧氣電池正極材料具有良好的性能,但成本較高,并且由于難于將其均勻地分散在碳材料等載體上等因素限制了其商業(yè)化進(jìn)程。相比較而言,采用含有Co、Fe元素的催化劑作為鋰-氧氣電池正極材料,成本低廉易制備,比完全采用貴金屬催化劑具有較大優(yōu)勢(shì)。本論文主要研究了含有Co、Fe元素的尖晶石和鈣鈦礦催化劑作為鋰-氧氣電池正極材料的性能。通過(guò)控制溶劑、溫度以及時(shí)間等條件,利用水熱的方法分別制備了呈現(xiàn)出{100}和{111}晶面的Co_3O_4立方塊和八面體,通過(guò)測(cè)試鋰-氧氣電池性能,對(duì)比充放電極化電壓、電池比容量以及循環(huán)穩(wěn)定性,發(fā)現(xiàn)Co_3O_4八面體對(duì)鋰-氧氣電池性能提高比立方塊更優(yōu)。利用層狀蒙脫石作為模板,在晶體結(jié)構(gòu)層間浸入含有C、N元素的苯胺,在氮?dú)鈿夥障绿蓟笙慈ッ擅撌?得到N摻雜的石墨烯。利用水熱的方法制備了反尖晶石結(jié)構(gòu)的Co[Co,Fe]O_4,該結(jié)構(gòu)中Co、Fe元素同時(shí)占據(jù)尖晶石八面體位置。常溫下采用物理方法將Co[Co,Fe]O_4負(fù)載到N摻雜的石墨烯上,得到Co[Co,Fe]O_4/N-G復(fù)合材料。將該種材料作為鋰-氧氣電池正極材料,測(cè)試電池首周比容量可達(dá)13312 mA h g-1,相比于Super P和商業(yè)Pt/C催化劑作為正極材料的鋰-氧氣電池,充電極化明顯降低,經(jīng)過(guò)110次以上循環(huán)之后性能無(wú)明顯衰減。認(rèn)為是一種優(yōu)良的鋰-氧氣電池正極材料。利用靜電紡絲的方法,制備出鈣鈦礦La_(0.6)Sr_(0.4)Co_(0.2）Fe_(0.8)O_3納米纖維,并通過(guò)化學(xué)方法在其表面負(fù)載了7.4%(wt%)的RuO_2納米顆粒。通過(guò)測(cè)試鋰-氧氣電池性能,發(fā)現(xiàn)RuO_2@LSCF-NFs作為正極催化劑的電池放電電壓提高約120 mV,在2000 mA h g-1下的充電電壓降低283 mV。在電流密度為100 mA g-1、截止容量為1000 mA h g-1下對(duì)兩種材料組裝的電池進(jìn)行循環(huán)穩(wěn)定性測(cè)試發(fā)現(xiàn),70次循環(huán)之后,采用LSCF-NFs作為正極材料的鋰-氧氣電池性能出現(xiàn)明顯下降,在充電比容量為500 mA h g-1下,極化電壓增大了306 mV,而同樣充電比容量下RuO_2@LSCF-NFs極化電壓增大98 mV,表現(xiàn)出良好的充電性能。82次循環(huán)之后采用LSCF-NFs作為正極材料的鋰-氧氣電池放電電壓低于2.0V,認(rèn)為電池已經(jīng)失效;而當(dāng)RuO_2@LSCF-NFs作為電池正極材料時(shí),鋰-氧氣電池循環(huán)120圈性能仍可保持相對(duì)穩(wěn)定,表現(xiàn)出良好的循環(huán)穩(wěn)定性。通過(guò)固相法合成制備了A位非化學(xué)計(jì)量比的鈣鈦礦氧化物Ba_(0.9)Co_(0.7)Fe_(0.2)Nb_(0.1)_O_3-δ。鈣鈦礦材料中A、B位置原子比低于1:1時(shí)會(huì)導(dǎo)致元素變價(jià)、氧空位濃度增大等變化。B_(0.9)CFN作為正極材料的鋰-氧氣電池放電比容量為12970 mA h g-1,放電電壓平臺(tái)在2.66 V左右;但充電電壓較高。通過(guò)ALD的方法在Ba_(0.9)Co_(0.7)Fe_(0.2)Nb_(0.1)_O_3-δ顆粒表面負(fù)載IrO2納米顆粒,改善了電池的性能。在6000 mA h g-1下電池的充電電壓降低560 m V,表明IrO2對(duì)降低電池整體極化有明顯的效果。對(duì)B_(0.9)CFN進(jìn)行變溫中子衍射分析,發(fā)現(xiàn)隨著溫度升高,材料呈現(xiàn)出收縮-擴(kuò)張的“呼吸”特性,對(duì)提高高溫下的ORR性能有較大的促進(jìn)作用。通過(guò)測(cè)試350 h的EIS,顯示B_(0.9)CFN經(jīng)過(guò)長(zhǎng)時(shí)間運(yùn)行之后阻抗增加0.04Ωcm~2,是一種良好的高溫ORR材料。
[Abstract]:Compared with the lithium ion battery, lithium oxygen battery has a higher energy density, so it received extensive attention in recent years. Researchers in lithium oxygen batteries during discharge, oxygen molecules to generate LiOx compounds after the cathode surface is reduced with Li~+; and the charging process, catalyst and catalytic decomposition of LiOx, oxygen precipitation. At the same time to cathode materials for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalytic performance, so how to improve the lithium oxygen battery efficiency from the angle of material design, reduce the cell polarization is a frontier research direction for lithium oxygen batteries. Precious metals as a cathode material lithium oxygen batteries with good performance, but the cost is higher, and due to be uniformly dispersed in carbon materials and other factors such as carrier has limited its commercialization process. In comparison, the catalyst containing Co, Fe elements as lithium electric oxygen Chi Zhengji material, low cost and easy preparation, has more advantages than the full use of precious metal catalysts. This paper mainly studies the containing Co, Fe elements of spinel and perovskite catalyst as a cathode material for lithium battery performance. By controlling the oxygen conditions of solvent, temperature and time, respectively showing {100} and {111} surface Co_3O_4 cube and eight surface were prepared by hydrothermal method, the performance test for lithium oxygen batteries, battery charging and discharging polarization voltage comparison, specific capacity and cycling stability, Co_3O_4 eight surface of lithium battery box to improve the performance of oxygen than better. Using layered montmorillonite as template, containing C in crystal structure the interlayer in aniline N element, after carbonization under nitrogen atmosphere from montmorillonite, graphene doped N. Anti spinel Co[Co prepared by hydrothermal method for the Fe]O_4. In the structure of Co, Fe elements simultaneously occupy eight positions. The spinel at room temperature by physical methods Co[Co, Fe]O_4 load to graphene doped N, Co[Co, Fe]O_4/N-G. This kind of composite material as cathode materials for lithium oxygen batteries, testing battery capacity of up to 13312 mA than the first week of H g-1, compared to Super P and commercial Pt/C catalyst as a cathode material for lithium oxygen batteries, charging polarization decreased significantly after 110 cycles without obvious performance degradation. That is an excellent oxygen lithium battery cathode material. Using electrospinning method, preparation of perovskite La_ (0.6) Sr_ (0.4) Co_ (0.2) Fe_ (0.8) O_3 nanofibers, and by chemical methods on the surface load of 7.4% (wt%) RuO_2 nano particles. By the test for lithium oxygen battery, discovered that RuO_2@LSCF-NFs acts as a battery discharge voltage anode catalyst is improved by about 120 mV, The charging voltage at 2000 mA h under g-1 reduction of 283 mV. at a current density of 100 mA g-1, by the capacity of the two materials assembled 1000 mA h under the g-1 cell cycle stability tests showed that, after 70 cycles, using LSCF-NFs as cathode material for lithium oxygen battery performance is decreased, in charge specific capacity of 500 mA h g-1, polarization voltage is increased by 306 mV, while the same charge ratio RuO_2@LSCF-NFs polarization voltage capacity increased by 98 mV, showing good charging performance after.82 cycles using LSCF-NFs as cathode material for lithium oxygen batteries discharge voltage is lower than 2.0V, that the battery has been failure; and when the battery RuO_2@LSCF-NFs cathode material, lithium battery oxygen 120 cycles performance still remain relatively stable, showing good cycling stability. Through the synthesis of solid phase method preparation of perovskite A non stoichiometric ratio The oxide Ba_ (0.9) Co_ (0.7) Fe_ (0.2) Nb_ (0.1) _O_3- 8. In perovskite A, B atomic ratio less than 1:1 will cause the element valence oxygen vacancy concentration increases, changes in.B_ (0.9) CFN as cathode material for lithium oxygen batteries discharge capacity of 12970 mA h g-1, discharge voltage is about 2.66 V; but the charging voltage is higher. By the method of ALD in Ba_ (0.9) Co_ (0.7) Fe_ (0.2) Nb_ (0.1) _O_3- delta particle surface loaded IrO2 nanoparticles, to improve the performance of the battery. A reduction of 560 m V 6000 mA h g-1 in the charging voltage of batteries, show that IrO2 has obvious effect on reducing overall cell polarization. The B_ (0.9) CFN neutron diffraction analysis of temperature, with increasing temperature, the material showing a contraction expansion "breathing" characteristics, to improve the performance of ORR high temperature have a greater role in promoting. Through the test of 350 H EIS, B_ (0.9) CFN after a long time. After the line, the impedance increased by 0.04 Omega cm~2, which is a good high temperature ORR material.

【學(xué)位授予單位】：中國(guó)科學(xué)院大學(xué)(中國(guó)科學(xué)院物理研究所)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36;TM911.41

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