殼層組分及厚度對(duì)核殼NCM材料性能的影響研究
發(fā)布時(shí)間：2018-09-05 07:20
【摘要】：鋰離子電池正極材料性能的好壞,在很大程度上制約著鋰離子電池的使用壽命和安全性能,所以正極材料的研究是鋰離子電池研究中的重中之重。具有三元層狀結(jié)構(gòu)的LiNixCoy Mn1-x-y O2,集LiNiO2、LiCoO2、LiMnO2三種材料的優(yōu)點(diǎn)于一身,成本低廉、可逆容量較高、循環(huán)性能穩(wěn)定,是一類非常有希望的材料之一。近幾年,Yang-Kook Sun和Argonne實(shí)驗(yàn)室通過利用共沉淀法、高溫固相法成功的制備出了一系列的核殼以及濃度梯度的LiNixCoy Mn1-x-y O2材料,經(jīng)測(cè)試后發(fā)現(xiàn),合成的核殼結(jié)構(gòu)材料能夠彌補(bǔ)非核殼結(jié)構(gòu)材料的循環(huán)性能差、安全性能低的缺點(diǎn)。然而,Y.K.Sun和Argonne實(shí)驗(yàn)室并沒有研究的是:不同殼層組分以及不同殼層厚度對(duì)核殼結(jié)構(gòu)材料性能的影響,也沒有對(duì)核殼結(jié)構(gòu)材料與同成分下的非核殼結(jié)構(gòu)材料進(jìn)行對(duì)比性研究。因此,本論文依據(jù)LiNiO2-LiCoO2-LiMnO2三元相圖,將已經(jīng)商業(yè)化應(yīng)用的LiNi0.5Co0.2Mn0.3O2和LiNi1/3Co1/3Mn1/3O2分別設(shè)計(jì)成同成分下的系列雙核殼結(jié)構(gòu)和系列單核殼結(jié)構(gòu)材料,通過對(duì)比研究系列雙核殼結(jié)構(gòu)材料中殼層組分的不同,來分析殼層組分對(duì)材料性能的影響;通過對(duì)比系列單核殼結(jié)構(gòu)材料中殼層厚度的不同,來分析殼層厚度對(duì)材料性能的影響。在本組實(shí)驗(yàn)中,設(shè)計(jì)核材料時(shí),選擇以高容量的LiNi0.8Co0.1Mn0.1O2作為核材料,以簡(jiǎn)單容易合成并且已經(jīng)商業(yè)化應(yīng)用的Li Ni1/3Co1/3Mn1/3O2為過渡殼層材料,分別以高穩(wěn)定的Li Ni0.4Co0.2Mn0.4O2、LiNi0.45Co0.1Mn0.45O2、LiNi0.475Co0.05Mn0.475O2、LiNi0.5Mn0.5O2為殼材料,將Li Ni0.5Co0.2Mn0.3O2重新設(shè)計(jì)為雙殼結(jié)構(gòu)Li[(Ni0.8Co0.1Mn0.1)core(Ni1/3Co1/3Mn1/3)inter shell(Ni(1-x)/2CoxMn(1-x)/2)shell]O2(x=0、0.05、0.1、0.2)。在本實(shí)驗(yàn)中,首先用共沉淀的方法合成了相應(yīng)的系列雙核殼結(jié)構(gòu)前驅(qū)體,然后將制備的前驅(qū)體與計(jì)量比的Li2CO3混合均勻(Li/M=1.05:1),然后在850°C下焙燒16 h,制備得到雙殼結(jié)構(gòu)的含鋰氧化物。隨后,對(duì)材料的組成、結(jié)構(gòu)、形貌和電化學(xué)性能等進(jìn)行了相應(yīng)的測(cè)試與研究。比較相同成分下核殼結(jié)構(gòu)材料中,不同殼層組分對(duì)核殼結(jié)構(gòu)材料性能的影響。將LiNi1/3Co1/3Mn1/3O2設(shè)計(jì)成核殼結(jié)構(gòu)Li{[NiyCo1-2yMny](1-x)}core{[Ni1/2Mn1/2]x}shell O2(0?x?0.5;6y+3x-6xy=2)。通過共沉淀法合成了具有核殼結(jié)構(gòu)的前驅(qū)體{[NiyCo1-2yMny](1-x)}core{[Ni1/2Mn1/2]x}shell(OH)2,將洗滌、烘干、過篩后的前驅(qū)體與LiOH以一定的計(jì)量比(Li/M=1.05)混勻,經(jīng)800°C高溫煅燒后得到相應(yīng)的含鋰氧化物,然后對(duì)材料的組成、結(jié)構(gòu)、形貌和電化學(xué)性能等進(jìn)行了研究,研究核殼結(jié)構(gòu)中不同殼層厚度對(duì)核殼結(jié)構(gòu)材料性能的影響。通過對(duì)核殼結(jié)構(gòu)LiNi0.5Co0.2Mn0.3O2和LiNi1/3Co1/3Mn1/3O2的研究和與同成分的非核殼結(jié)構(gòu)材料對(duì)比發(fā)現(xiàn),(a)核殼結(jié)構(gòu)能夠提高材料的循環(huán)性能以及熱穩(wěn)定性能;(b)在核殼結(jié)構(gòu)材料中,隨著殼層中Mn元素的增加,材料的循環(huán)性能以及熱穩(wěn)定性能會(huì)相應(yīng)的提高;(c)隨著殼層厚度的增加,材料的循環(huán)性能以及熱穩(wěn)定性能也有一定的提高。
[Abstract]:The performance of lithium-ion battery cathode material to a great extent restricts the service life and safety performance of lithium-ion battery, so the research of cathode material is the most important in the research of lithium-ion battery. LiNixCoy Mn1-x-y O _ 2 with ternary layered structure, which combines the advantages of three kinds of LiNiO2,LiCoO2,LiMnO2 materials, has the advantages of low cost, high reversible capacity and stable cyclic performance. It is one of the most promising materials. In recent years, the Yang-Kook Sun and Argonne laboratories successfully prepared a series of core-shell and concentration gradient LiNixCoy Mn1-x-y O _ 2 materials by means of co-precipitation and high-temperature solid-state method. The synthesized core-shell structure material can make up for the poor cycling performance and low safety performance of the non-core-shell structure material. However, the effect of different shell components and shell thickness on the properties of core-shell structure materials has not been studied in Y. K. Sun and Argonne laboratories, nor has a comparative study between core-shell structure materials and non-core-shell structural materials under the same composition been carried out. Therefore, according to the LiNiO2-LiCoO2-LiMnO2 ternary phase diagram, the commercial applications of LiNi0.5Co0.2Mn0.3O2 and LiNi1/3Co1/3Mn1/3O2 have been designed into a series of binocore structure and a series of monocore structure materials under the same composition, respectively. The effects of shell composition on material properties are analyzed by contrasting the difference of shell composition in a series of binuclear shell structure materials, and the difference of shell thickness in a series of monocore shell structure materials is compared. To analyze the influence of shell thickness on material properties. In the design of nuclear materials, high capacity LiNi0.8Co0.1Mn0.1O2 is chosen as nuclear material, Li Ni1/3Co1/3Mn1/3O2, which is simple and easy to synthesize and has been commercialized, is used as transitional shell material, and high stable Li Ni0.4Co0.2Mn0.4O2,LiNi0.45Co0.1Mn0.45O2,LiNi0.475Co0.05Mn0.475O2,LiNi0.5Mn0.5O2 is used as shell material, respectively. Li Ni0.5Co0.2Mn0.3O2 was redesigned as Li [(Ni0.8Co0.1Mn0.1) core (Ni1/3Co1/3Mn1/3) inter shell (Ni (1-x) / 2Co xMn (1-x) / r 2 shell] O 2 (x 0. 05) 0. 1 0. 2). In this experiment, a series of binuclear shell precursors were synthesized by coprecipitation method. Then the precursor was mixed with the stoichiometric Li2CO3 homogeneously (Li/M=1.05:1), and then calcined at 850 擄C for 16 h to prepare the lithium-containing oxide with double shell structure. Then, the composition, structure, morphology and electrochemical properties of the materials were tested and studied. The effects of different shell components on the properties of core-shell structure materials were compared under the same composition. The core-shell structure Li {[NiyCo1-2yMny] (1-x)} core {[Ni1/2Mn1/2] x} shell O _ 2 (0 ~ (10) x ~ (0.5) ~ (6) y 3x-6xy=2 was designed by LiNi1/3Co1/3Mn1/3O2. The precursor {[NiyCo1-2yMny] (1-x)} core {[Ni1/2Mn1/2] x} shell (OH) _ 2 with core-shell structure was synthesized by co-precipitation method. The precursor after washing, drying and sifting was mixed with LiOH at a certain measurement ratio (Li/M=1.05). After calcined at 800 擄C at high temperature, the corresponding lithium-containing oxides were obtained. The influence of different shell thickness on the properties of core-shell structure was studied. Through the study of the core-shell structure LiNi0.5Co0.2Mn0.3O2 and LiNi1/3Co1/3Mn1/3O2 and the comparison with the core-shell structure materials of the same composition, it is found that the core-shell structure of, (a) can improve the cycling performance of the material and the thermal stability of; (b) in the core-shell structure material increases with the increase of the Mn element in the shell layer. The cycle performance and thermal stability of the material will be improved with the increase of shell thickness, and the cycle performance and thermal stability of the material will also be improved with the increase of shell thickness.
【學(xué)位授予單位】：天津理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB383.4
[Abstract]:The performance of lithium-ion battery cathode material to a great extent restricts the service life and safety performance of lithium-ion battery, so the research of cathode material is the most important in the research of lithium-ion battery. LiNixCoy Mn1-x-y O _ 2 with ternary layered structure, which combines the advantages of three kinds of LiNiO2,LiCoO2,LiMnO2 materials, has the advantages of low cost, high reversible capacity and stable cyclic performance. It is one of the most promising materials. In recent years, the Yang-Kook Sun and Argonne laboratories successfully prepared a series of core-shell and concentration gradient LiNixCoy Mn1-x-y O _ 2 materials by means of co-precipitation and high-temperature solid-state method. The synthesized core-shell structure material can make up for the poor cycling performance and low safety performance of the non-core-shell structure material. However, the effect of different shell components and shell thickness on the properties of core-shell structure materials has not been studied in Y. K. Sun and Argonne laboratories, nor has a comparative study between core-shell structure materials and non-core-shell structural materials under the same composition been carried out. Therefore, according to the LiNiO2-LiCoO2-LiMnO2 ternary phase diagram, the commercial applications of LiNi0.5Co0.2Mn0.3O2 and LiNi1/3Co1/3Mn1/3O2 have been designed into a series of binocore structure and a series of monocore structure materials under the same composition, respectively. The effects of shell composition on material properties are analyzed by contrasting the difference of shell composition in a series of binuclear shell structure materials, and the difference of shell thickness in a series of monocore shell structure materials is compared. To analyze the influence of shell thickness on material properties. In the design of nuclear materials, high capacity LiNi0.8Co0.1Mn0.1O2 is chosen as nuclear material, Li Ni1/3Co1/3Mn1/3O2, which is simple and easy to synthesize and has been commercialized, is used as transitional shell material, and high stable Li Ni0.4Co0.2Mn0.4O2,LiNi0.45Co0.1Mn0.45O2,LiNi0.475Co0.05Mn0.475O2,LiNi0.5Mn0.5O2 is used as shell material, respectively. Li Ni0.5Co0.2Mn0.3O2 was redesigned as Li [(Ni0.8Co0.1Mn0.1) core (Ni1/3Co1/3Mn1/3) inter shell (Ni (1-x) / 2Co xMn (1-x) / r 2 shell] O 2 (x 0. 05) 0. 1 0. 2). In this experiment, a series of binuclear shell precursors were synthesized by coprecipitation method. Then the precursor was mixed with the stoichiometric Li2CO3 homogeneously (Li/M=1.05:1), and then calcined at 850 擄C for 16 h to prepare the lithium-containing oxide with double shell structure. Then, the composition, structure, morphology and electrochemical properties of the materials were tested and studied. The effects of different shell components on the properties of core-shell structure materials were compared under the same composition. The core-shell structure Li {[NiyCo1-2yMny] (1-x)} core {[Ni1/2Mn1/2] x} shell O _ 2 (0 ~ (10) x ~ (0.5) ~ (6) y 3x-6xy=2 was designed by LiNi1/3Co1/3Mn1/3O2. The precursor {[NiyCo1-2yMny] (1-x)} core {[Ni1/2Mn1/2] x} shell (OH) _ 2 with core-shell structure was synthesized by co-precipitation method. The precursor after washing, drying and sifting was mixed with LiOH at a certain measurement ratio (Li/M=1.05). After calcined at 800 擄C at high temperature, the corresponding lithium-containing oxides were obtained. The influence of different shell thickness on the properties of core-shell structure was studied. Through the study of the core-shell structure LiNi0.5Co0.2Mn0.3O2 and LiNi1/3Co1/3Mn1/3O2 and the comparison with the core-shell structure materials of the same composition, it is found that the core-shell structure of, (a) can improve the cycling performance of the material and the thermal stability of; (b) in the core-shell structure material increases with the increase of the Mn element in the shell layer. The cycle performance and thermal stability of the material will be improved with the increase of shell thickness, and the cycle performance and thermal stability of the material will also be improved with the increase of shell thickness.
【學(xué)位授予單位】：天津理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB383.4
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