CN108417783B - Niobium manganese modified tin oxide coated nickel cobalt lithium manganate cathode material and preparation method - Google Patents
Niobium manganese modified tin oxide coated nickel cobalt lithium manganate cathode material and preparation method Download PDFInfo
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Abstract
本发明适用于锂电池技术领域，提供一种铌锰改性氧化锡包覆的镍钴锰酸锂正极材料及制备方法，所述方法包括：骤S1、称取氧化锡与铌锰的氧化物，混合后低温处理，得到铌锰氧化锡混合物；步骤S2、按比例称取镍钴锰三元材料，并与所述铌锰氧化锡混合物进行充分混合均匀，得到混合料；步骤S3、将步骤S2得到的混合料装入到匣钵中，进行烧结，得到铌锰改性氧化锡包覆的镍钴锰酸锂正极材料。本发明采用铌锰改性的氧化锡来包覆三元正极材料能有效的保护材料的表面结构，减少Ni2+的产生，有效抑制晶格氧的脱出，提高材料的循环与倍率性能，同时也能有效的降低氧化锡自身材料缺陷所带来的副作用，使材料性能更优异。
The invention is applicable to the technical field of lithium batteries, and provides a nickel-cobalt-manganate lithium manganate positive electrode material coated with niobium-manganese modified tin oxide and a preparation method. The method includes: step S1, weighing the oxides of tin oxide and niobium-manganese oxide. , low-temperature treatment after mixing, to obtain a niobium manganese tin oxide mixture; step S2, weighing the nickel-cobalt-manganese ternary material in proportion, and fully mixing with the niobium-manganese tin oxide mixture to obtain a mixture; step S3, combining the step The mixture obtained in S2 is put into a saggar and sintered to obtain a nickel-cobalt-lithium-manganate cathode material coated with niobium-manganese-modified tin oxide. In the present invention, the niobium-manganese modified tin oxide is used to coat the ternary positive electrode material, which can effectively protect the surface structure of the material, reduce the generation of Ni 2+ , effectively suppress the extraction of lattice oxygen, improve the cycle and rate performance of the material, and at the same time It can also effectively reduce the side effects caused by tin oxide's own material defects, and make the material performance more excellent.
Description
技术领域technical field
本发明属于锂电池技术领域，尤其涉及一种铌锰改性氧化锡包覆的镍钴锰酸锂正极材料及制备方法。The invention belongs to the technical field of lithium batteries, and in particular relates to a nickel-cobalt-manganese-lithium-manganate positive electrode material and a preparation method covered by niobium-manganese-modified tin oxide.
背景技术Background technique
镍钴锰三元锂离子电池正极材料由于具有较高的能量密度及相对较低的成本而广泛应用于新能源电池行业。镍钴锰酸锂(LNCM)尤其是高镍产品的结构稳定性欠佳，在充放电过程中很容易由于Li离子的脱嵌以及Ni、Co、Mn离子价态的变化，引起晶格氧的逸出，造成材料结构的塌陷，对材料的循环寿命及安全性造成极大的危害；同时表面结构容易与电解液发生反应，Ni3+极易被还原成Ni2+惰性价态，其表面Ni2+含量占整个晶体结构内Ni2+的三分之二，从而导致Li+、Ni2+混排，影响产品的首效与循环性能。Nickel-cobalt-manganese ternary lithium-ion battery cathode materials are widely used in the new energy battery industry due to their high energy density and relatively low cost. Lithium nickel cobalt manganate (LNCM), especially high nickel products, has poor structural stability. During the charging and discharging process, it is easy to cause the formation of lattice oxygen due to the deintercalation of Li ions and the change of the valence state of Ni, Co, and Mn ions. Escape, causing the collapse of the material structure, causing great harm to the cycle life and safety of the material; at the same time, the surface structure is easy to react with the electrolyte, and Ni 3+ is easily reduced to an inert valence state of Ni 2+ , and its surface The Ni 2+ content accounts for two-thirds of the Ni 2+ in the entire crystal structure, which leads to the mixed arrangement of Li + and Ni 2+ , which affects the first effect and cycle performance of the product.
发明内容SUMMARY OF THE INVENTION
鉴于上述问题，本发明的目的在于提供一种铌锰改性氧化锡包覆的镍钴锰酸锂正极材料及制备方法，旨在解决现有镍钴锰酸锂电池循环性能较差的技术问题。In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of nickel-cobalt manganese lithium manganate positive electrode material and preparation method coated with niobium-manganese modified tin oxide, aiming to solve the technical problem of poor cycle performance of existing nickel-cobalt lithium manganate batteries .
所述铌锰改性氧化锡包覆的镍钴锰酸锂正极材料的制备方法包括下述步骤：The preparation method of the niobium-manganese-modified tin oxide-coated nickel-cobalt-manganate-lithium-manganate positive electrode material comprises the following steps:
步骤S1、称取氧化锡与铌锰的氧化物，混合后低温处理，得到铌锰氧化锡混合物；Step S1, weighing the oxides of tin oxide and niobium manganese, and mixing them at a low temperature to obtain a niobium manganese tin oxide mixture;
步骤S2、按比例称取镍钴锰三元材料，并与所述铌锰氧化锡混合物进行充分混合均匀，得到混合料；In step S2, the nickel-cobalt-manganese ternary material is weighed in proportion, and fully mixed with the niobium-manganese-tin oxide mixture to obtain a mixture;
步骤S3、将步骤S2得到的混合料装入到匣钵中，进行烧结，得到铌锰改性氧化锡包覆的镍钴锰酸锂正极材料。In step S3, the mixture obtained in step S2 is put into a saggar, and sintered to obtain a nickel cobalt lithium manganate cathode material coated with niobium manganese modified tin oxide.
进一步的，步骤S1称取的氧化锡与铌锰的氧化物中，锡铌锰的摩尔比Sn：Nb：Mn＝1:(0.1～0.3)：(0.2～0.5)，低温处理的范围为200-500℃。。Further, in the oxide of tin oxide and niobium manganese weighed in step S1, the molar ratio of tin, niobium and manganese is Sn:Nb:Mn=1:(0.1～0.3):(0.2～0.5), and the range of low temperature treatment is 200 -500℃. .
进一步的，步骤S2中，按质量比铌锰氧化锡混合物占镍钴锰三元材料的0.05-0.4％称取镍钴锰三元材料。Further, in step S2, the nickel-cobalt-manganese ternary material is weighed according to the mass ratio of the niobium-manganese-tin oxide mixture accounting for 0.05-0.4% of the nickel-cobalt-manganese ternary material.
进一步的，步骤S3中，烧结过程的烧结温度为600-1000℃，烧结时间为4-12h。Further, in step S3, the sintering temperature in the sintering process is 600-1000° C., and the sintering time is 4-12 h.
另一方面，所述镍钴锰酸锂正极材料采用上述方法制备得到，材料基体为镍钴锰三元材料，材料壳层为氧化锡-锰-铌的复合包覆层。On the other hand, the nickel cobalt lithium manganate cathode material is prepared by the above method, the material matrix is a nickel cobalt manganese ternary material, and the material shell is a composite coating layer of tin oxide-manganese-niobium.
本发明的有益效果是：本发明通过锰改性氧化锡，在材料表面形成氧化锡-锰-铌的复合包覆层，隔绝材料表面结构与电解液的直接接触，同时由于氧化锡的导电性能有效降低内阻，减少充放电过程中的电子残留；另外经铌-锰改性的氧化锡，使得氧化锡在充放电过程中由于铌的加入使其体积膨胀温度提升，使材料的体积膨胀得到有效抑制和减缓，且由于锰的加入，使得铌-锰-氧化锡包覆层的结构更趋向于层状结构与基体有更好的匹配性，降低氧空位，有助于抑制氧缺陷的产生。The beneficial effects of the present invention are: the present invention forms a composite coating layer of tin oxide-manganese-niobium on the surface of the material by modifying the tin oxide with manganese, so as to isolate the direct contact between the surface structure of the material and the electrolyte, and at the same time, due to the electrical conductivity of the tin oxide Effectively reduce the internal resistance and reduce the residual electrons during the charging and discharging process; in addition, the tin oxide modified by niobium-manganese makes the volume expansion temperature of the tin oxide increase due to the addition of niobium during the charging and discharging process, so that the volume expansion of the material is obtained. Effectively inhibit and slow down, and due to the addition of manganese, the structure of the niobium-manganese-tin oxide coating layer tends to have a better match between the layered structure and the matrix, reducing oxygen vacancies and helping to suppress the generation of oxygen defects .
附图说明Description of drawings
图1是本发明试验例1和对比例1的充放电循环次数与容量关系图；1 is a graph showing the relationship between the number of charge-discharge cycles and the capacity of Test Example 1 and Comparative Example 1 of the present invention;
图2是本发明试验例2和对比例2的充放电循环次数与容量关系图。FIG. 2 is a graph showing the relationship between the number of charge-discharge cycles and the capacity of Test Example 2 and Comparative Example 2 of the present invention.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.
为了说明本发明所述的技术方案，下面通过具体实施例来进行说明。In order to illustrate the technical solutions of the present invention, the following specific embodiments are used for description.
本发明提供的铌锰改性氧化锡包覆的镍钴锰酸锂正极材料的制备方法包括下属步骤：The preparation method of the nickel-cobalt-manganate lithium manganate positive electrode material coated with niobium-manganese-modified tin oxide provided by the present invention comprises the following steps:
步骤S1、称取氧化锡与铌锰的氧化物，混合后低温处理，得到铌锰氧化锡混合物。In step S1, the oxides of tin oxide and niobium manganese are weighed, mixed and treated at a low temperature to obtain a niobium manganese tin oxide mixture.
本步骤称取的氧化锡与铌锰的氧化物中，锡铌锰的摩尔比Sn：Nb：Mn＝1:(0.1～0.3)：(0.2～0.5)，低温处理的范围为200-500℃。所述氧化锡为一氧化锡或二氧化锡。所述铌锰的氧化物是铌元素和锰元素各种价态氧化物的总称谓，有多种选择，比如氧化铌可以为一氧化铌、二氧化铌、三氧化二铌、五氧化二铌等，氧化锰可以为一氧化锰、二氧化锰等。In the oxides of tin oxide and niobium-manganese weighed in this step, the molar ratio of tin-niobium-manganese is Sn:Nb:Mn=1:(0.1～0.3):(0.2～0.5), and the range of low temperature treatment is 200-500℃ . The tin oxide is tin monoxide or tin dioxide. The oxide of niobium and manganese is the general name of various valence oxides of niobium element and manganese element, and there are many choices. For example, niobium oxide can be niobium monoxide, niobium dioxide, niobium trioxide, and niobium pentoxide. etc., the manganese oxide may be manganese monoxide, manganese dioxide, or the like.
步骤S2、按比例称取镍钴锰三元材料，并与所述铌锰氧化锡混合物进行充分混合均匀，得到混合料。In step S2, the nickel-cobalt-manganese ternary material is weighed in proportion, and fully mixed with the niobium-manganese-tin oxide mixture to obtain a mixture.
本步骤按质量比铌锰氧化锡混合物占镍钴锰三元材料的0.05-0.4％称取镍钴锰三元材料。In this step, the nickel-cobalt-manganese ternary material is weighed according to the mass ratio of the niobium-manganese-tin oxide mixture accounting for 0.05-0.4% of the nickel-cobalt-manganese ternary material.
步骤S3、将步骤S2得到的混合料装入到匣钵中，进行烧结，烧结温度为600-1000℃，烧结时间为4-12h，得到铌锰改性氧化锡包覆的镍钴锰酸锂正极材料。In step S3, the mixture obtained in step S2 is put into a saggar and sintered, the sintering temperature is 600-1000 ° C, and the sintering time is 4-12 h, so as to obtain Nicobal Lithium Manganate Coated with Niobium and Manganese Modified Tin Oxide positive electrode material.
本发明采用铌锰改性氧化锡对镍钴锰三元材料进行包覆，内层为镍钴锰三元材料，壳层为氧化锡-锰-铌的复合包覆层。镍钴锰酸锂尤其是高镍产品的结构稳定性欠佳，在充放电过程中很容易由于Li离子的脱嵌以及Ni、Co、Mn离子价态的变化，引起晶格氧的逸出，造成材料结构的塌陷，对材料的循环寿命及安全性造成极大的危害；如果直接采用氧化锡包覆，但氧化锡的缺点是在充放电过程中会产生体积膨胀，再加上基体与氧化锡的物相结构不完全相同，经过一段时间的循环，包覆层会从基体脱落，就失去包覆的效果。本发明氧化锡经铌-锰改性，使得氧化锡在充放电过程中由于铌的加入使其体积膨胀温度提升，使材料的体积膨胀得到有效抑制和减缓，且由于锰的加入，使得铌-锰-氧化锡包覆层的结构更趋向于层状结构与基体有更好的匹配性，降低氧空位，有助于抑制氧缺陷的产生。The invention adopts niobium-manganese modified tin oxide to coat the nickel-cobalt-manganese ternary material, the inner layer is the nickel-cobalt-manganese ternary material, and the shell layer is the composite coating layer of tin oxide-manganese-niobium. Lithium nickel cobalt manganate, especially high nickel products, has poor structural stability. During the charging and discharging process, it is easy to cause the escape of lattice oxygen due to the deintercalation of Li ions and the change of the valence state of Ni, Co, and Mn ions. The collapse of the material structure will cause great harm to the cycle life and safety of the material; if it is directly coated with tin oxide, the disadvantage of tin oxide is that it will generate volume expansion during the charging and discharging process, and the matrix and oxidation The phase structure of tin is not the same. After a period of circulation, the coating layer will fall off from the substrate, and the coating effect will be lost. The tin oxide of the present invention is modified by niobium-manganese, so that the volume expansion temperature of tin oxide is increased due to the addition of niobium during the charging and discharging process, so that the volume expansion of the material is effectively suppressed and slowed down, and the addition of manganese makes the niobium- The structure of the manganese-tin oxide coating layer tends to have better matching between the layered structure and the matrix, reducing oxygen vacancies and helping to suppress the generation of oxygen defects.
下面通过试验例和对比例来验证本材料效果。The effect of this material is verified by test examples and comparative examples below.
试验例1：Test Example 1:
称取二氧化锡、五氧化二铌、一氧化锰，其中锡铌锰的摩尔比Sn：Nb：Mn＝1:0.1：0.2，混合后200℃低温处理，得到铌锰氧化锡混合物，按质量比铌锰氧化锡混合物占0.1％称取NCM811三元材料，并与铌锰氧化锡混合物进行充分混合均匀，得到混合料；将混合料装入到匣钵中，进行烧结烧结温度为650℃，烧结时间为6h，最后得到铌锰改性氧化锡包覆的镍钴锰酸锂正极材料。Weigh tin dioxide, niobium pentoxide and manganese monoxide, wherein the molar ratio of tin, niobium and manganese is Sn:Nb:Mn=1:0.1:0.2, and after mixing, treat at a low temperature of 200°C to obtain a mixture of niobium manganese and tin oxide, according to mass The NCM811 ternary material is weighed and fully mixed with the niobium manganese tin oxide mixture, which accounts for 0.1% of the niobium manganese tin oxide mixture to obtain a mixture; The sintering time is 6h, and finally a nickel-cobalt-manganate lithium-manganate cathode material coated with niobium-manganese-modified tin oxide is obtained.
试验例2：Test Example 2:
称取二氧化锡、五氧化二铌、一氧化锰，其中锡铌锰的摩尔比Sn：Nb：Mn＝1:0.3：0.5混合后350℃低温处理，得到铌锰氧化锡混合物，按质量比铌锰氧化锡混合物占0.25％称取NCM523三元材料，并与铌锰氧化锡混合物进行充分混合均匀，得到混合料；将混合料装入到匣钵中，进行烧结烧结温度为890℃，烧结时间为7.5h，最后得到铌锰改性氧化锡包覆的镍钴锰酸锂正极材料。Weigh tin dioxide, niobium pentoxide, and manganese monoxide, wherein the molar ratio of tin, niobium and manganese is Sn:Nb:Mn=1:0.3:0.5, and then mixed at a low temperature of 350°C to obtain a niobium-manganese-tin oxide mixture. The niobium manganese tin oxide mixture accounts for 0.25%, and the NCM523 ternary material is weighed, and fully mixed with the niobium manganese tin oxide mixture to obtain a mixture; The time is 7.5 h, and finally a Nicobal Lithium Manganate cathode material coated with niobium and manganese modified tin oxide is obtained.
对比例1：Comparative Example 1:
称取二氧化锡，按质量比氧化锡占三元材料0.08％称取NCM811三元材料，并与氧化锡进行充分混合均匀，得到混合料；将混合料装入到匣钵中，进行烧结烧结温度为650℃，烧结时间为6h，最后得到氧化锡包覆的镍钴锰酸锂正极材料。Weigh tin dioxide, take NCM811 ternary material according to the mass ratio of tin oxide accounting for 0.08% of the ternary material, and fully mix it with tin oxide to obtain a mixture; put the mixture into a sagger, sintering and sintering The temperature is 650°C, and the sintering time is 6h, and finally a tin oxide-coated nickel cobalt lithium manganate cathode material is obtained.
对比例2：Comparative Example 2:
称取二氧化锡，按质量比氧化锡占三元材料0.14％称取NCM523三元材料，并与氧化锡进行充分混合均匀，得到混合料；将混合料装入到匣钵中，进行烧结烧结温度为890℃，烧结时间为7.5h，最后得到氧化锡包覆的镍钴锰酸锂正极材料。Weigh tin dioxide, take NCM523 ternary material according to the mass ratio of tin oxide accounting for 0.14% of the ternary material, and fully mix with tin oxide to obtain a mixture; put the mixture into a sagger, sintering and sintering The temperature is 890°C, and the sintering time is 7.5h, and finally a tin oxide-coated nickel cobalt lithium manganate cathode material is obtained.
分别以试验例1、2和对比例1、2制备得到的正极材料为正极活性物质，锂片为负极，组装成扣式电池。正极片的组成为m(活性物质)：m(乙炔黑)：m(PVDF)＝80:12:8，采用蓝电测试系统进行测试，充放电电压为2.75～4.3V，在常温环境下进行循环性能测试。充放电循环次数与容量的关系如图1、2所示。The positive electrode materials prepared in Test Examples 1, 2 and Comparative Examples 1 and 2 were used as the positive electrode active material, and the lithium sheet was used as the negative electrode, and a button battery was assembled. The composition of the positive electrode sheet is m (active material): m (acetylene black): m (PVDF) = 80: 12: 8. The blue electricity test system is used for testing, and the charge and discharge voltage is 2.75 ~ 4.3V. Cyclic performance test. The relationship between the number of charge-discharge cycles and the capacity is shown in Figures 1 and 2.
从图1中可知，对比例1氧化锡包覆的正极材料制备的锂电池在70圈左右容量迅速下降，而铌锰改性氧化锡包覆的NCM811正极材料制备的锂电池，在循环至100圈依然是平稳下降的趋势。It can be seen from Figure 1 that the capacity of the lithium battery prepared with the tin oxide-coated cathode material in Comparative Example 1 decreased rapidly at about 70 cycles, while the lithium battery prepared with the NCM811 cathode material coated with niobium-manganese modified tin oxide showed a rapid decrease in the capacity after the cycle to 100 cycles. The circle is still in a steady downward trend.
从图2中可知，对比例2氧化锡包覆的正极材料制备的锂电池在80圈左右容量保持率为98％左右，100圈衰减至95.7％，而使用铌锰改性氧化锡包覆的NCM523正极材料制备的锂电池，材料80圈容量保持率在99.3％，100圈保持率在97.7％。It can be seen from Figure 2 that the lithium battery prepared with the tin oxide-coated cathode material in Comparative Example 2 had a capacity retention rate of about 98% at about 80 cycles, and attenuated to 95.7% at 100 cycles, while the niobium-manganese-modified tin oxide-coated lithium battery The lithium battery prepared with NCM523 cathode material has a capacity retention rate of 99.3% for 80 cycles and 97.7% for 100 cycles.
由此可见，本发明经过铌锰改性氧化锡包覆的镍钴锰酸锂正极材料相较于普通氧化锡包覆的镍钴锰酸锂正极材料，电池循环性能有明显提升。It can be seen that the battery cycle performance of the nickel-cobalt lithium manganate cathode material coated with niobium-manganese modified tin oxide of the present invention is significantly improved compared with the common tin oxide-coated nickel-cobalt lithium manganate cathode material.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.
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