CN115832170A - A kind of preparation method and application of aqueous zinc ion battery negative electrode material - Google Patents
A kind of preparation method and application of aqueous zinc ion battery negative electrode material Download PDFInfo
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Abstract
Description
技术领域technical field
本发明属于锌离子电池技术领域，具体涉及一种水系锌离子电池负极材料的制备方法及其应用。The invention belongs to the technical field of zinc ion batteries, and in particular relates to a preparation method and an application of an aqueous zinc ion battery negative electrode material.
背景技术Background technique
随着世界经济的快速发展，为响应国家节能减排要求，清洁能源(风能、水能、太阳能等)成为人们关注的焦点。然而，清洁能源的使用面临许多问题，如风力的强度、水量以及昼夜时长等。二次电池的出现不仅可以实现化学能和电能的相互转换，而且是一种便携的储能装置。锂离子电池作为可移动且具有高能量密度的二次电池被广泛的使用。但是近些年来，关于锂离子电池的安全事故频发，造成重大经济损失。虽然锂离子电池的使用率呈现逐年增长的趋势，但锂金属的价格也紧随上涨，造成了电池的使用成本更高。因此，寻找高能量密度、高安全性和价格便宜的二次电池具有重要的意义。With the rapid development of the world economy, clean energy (wind energy, water energy, solar energy, etc.) has become the focus of attention in response to national energy conservation and emission reduction requirements. However, the use of clean energy faces many problems, such as the strength of the wind, the amount of water, and the length of day and night. The emergence of secondary batteries can not only realize the mutual conversion of chemical energy and electrical energy, but also is a portable energy storage device. Lithium-ion batteries are widely used as portable secondary batteries with high energy density. However, in recent years, safety accidents about lithium-ion batteries have occurred frequently, causing major economic losses. Although the usage rate of lithium-ion batteries is increasing year by year, the price of lithium metal is also rising, resulting in higher battery usage costs. Therefore, it is of great significance to find secondary batteries with high energy density, high safety and low price.
水系锌离子电池以其高理论容量(820mAh·g-1和5855mAh·cm-3)和高安全性被认为是可以取代锂离子电池的下一代具有良好前景的储能器件。锌离子电池的组装工艺简单，可在大气环境下完成。而且地壳中锌的含量丰富，开采工艺成熟，市售价格便宜。然而水系锌离子电池存在的固有问题严重限制了使用寿命和库伦效率，这使得其无法进行产业化和大规模的使用。如锌负极上存在枝晶生长、析氢和腐蚀等棘手问题，但锌枝晶的生长是最为严重的，很容易引发电池短路失效。在电池的长期循环过程中，局部较强的电场引起锌离子聚集和沉积。产生的锌枝晶进一步形成“尖端放电”，捕获更多的锌离子沉积，加速锌枝晶快速生长。部分枝晶脱落形成“死锌”，造成锌负极可逆性下降，电池容量快速衰减。Aqueous zinc-ion batteries are considered to be promising next-generation energy storage devices that can replace lithium-ion batteries because of their high theoretical capacity (820mAh·g -1 and 5855mAh·cm -3 ) and high safety. The assembly process of zinc-ion batteries is simple and can be completed in an atmospheric environment. Moreover, the content of zinc in the earth's crust is rich, the mining technology is mature, and the market price is cheap. However, the inherent problems of aqueous Zn-ion batteries seriously limit the service life and Coulombic efficiency, which makes it impossible for industrialization and large-scale use. For example, there are thorny problems such as dendrite growth, hydrogen evolution and corrosion on the zinc negative electrode, but the growth of zinc dendrites is the most serious, which can easily cause short-circuit failure of the battery. During the long-term cycling of the battery, the locally strong electric field induces the aggregation and deposition of zinc ions. The generated zinc dendrites further form a "tip discharge" to capture more zinc ion deposition and accelerate the rapid growth of zinc dendrites. Part of the dendrites fall off to form "dead zinc", which causes the reversibility of the zinc negative electrode to decrease, and the battery capacity rapidly decays.
为解决水系锌离子电池锌负极中最严重的锌枝晶生长问题，研究人员通过多种途径进行解决。1.电解质添加剂，在枝晶表面形成静电屏蔽作用，促进锌离子均匀沉积，抑制枝晶生长，如***(Nano Energy 2019,62,275-281.)、CeCl3(Advanced Materials 2022,34(37),2203104.)、乙酸铵(Advanced Energy Materials 2022,12(9),2102982.)等。添加剂的使用会导致能量密度的降低，有些添加剂还会降低锌离子迁移率，甚至部分添加剂还具有一定的毒性以及成本过高等问题。2.官能团隔膜，利用官能团与锌离子的吸附性，调节锌离子的传输，促使其均匀沉积，缓解枝晶快速生长。如壳聚糖改性滤纸的-OH和-NH2(Chemical Engineering Journal 2022,450,137902.)、PVDF@PDA纳米纤维膜的-OH和-NH、PBC@Cellulose-Filter隔膜含N官能团(Electrochimica Acta 2022,430,141129)。隔膜的制备技术工艺相对更高，对环境的污染更大。3.表面改性，提升与电解液的接触，促进锌离子的均匀沉积，阻碍枝晶生长，如CaCO3(Advanced Energy Materials 2018,8(25),1801090.)、Al2O3(Surface and Coatings Technology 2021,427,127813.)、TiO2(AppliedSurface Science 2022,606,154932.)等。但长期循环会降低涂层材料的附着力，导致材料体积膨胀甚至从电极上脱落，引起局部电流密度突然增大，枝晶迅速长大。此外，非导电性质的无机涂层还会影响锌离子的迁移速率。In order to solve the most serious problem of zinc dendrite growth in zinc anodes of aqueous zinc-ion batteries, researchers have solved it in various ways. 1. Electrolyte additives, which form an electrostatic shielding effect on the surface of dendrites, promote the uniform deposition of zinc ions, and inhibit dendrite growth, such as ether (Nano Energy 2019,62,275-281.), CeCl 3 (Advanced Materials 2022,34(37), 2203104.), ammonium acetate (Advanced Energy Materials 2022, 12(9), 2102982.), etc. The use of additives will lead to a decrease in energy density, and some additives will also reduce the mobility of zinc ions, and even some additives have certain toxicity and high cost. 2. The functional group separator utilizes the adsorption of functional groups and zinc ions to regulate the transmission of zinc ions, promote their uniform deposition, and relieve the rapid growth of dendrites. Such as -OH and -NH 2 of chitosan modified filter paper (Chemical Engineering Journal 2022, 450, 137902.), -OH and -NH of PVDF@PDA nanofiber membrane, PBC@Cellulose-Filter membrane containing N functional group (Electrochimica Acta 2022, 430, 141129). The preparation technology of the diaphragm is relatively high, and the pollution to the environment is greater. 3. Surface modification, improve the contact with the electrolyte, promote the uniform deposition of zinc ions, and hinder the growth of dendrites, such as CaCO 3 (Advanced Energy Materials 2018,8(25),1801090.), Al 2 O 3 (Surface and Coatings Technology 2021, 427, 127813.), TiO 2 (Applied Surface Science 2022, 606, 154932.), etc. However, long-term cycling will reduce the adhesion of the coating material, causing the volume of the material to expand or even fall off from the electrode, causing a sudden increase in the local current density and rapid growth of dendrites. In addition, the non-conductive nature of the inorganic coating can also affect the migration rate of zinc ions.
针对以上技术问题，为了使水系锌离子电池实现市场化的要求，降低成本，安全环保，且在不降能量密度的情况下，抑制枝晶生长，提高电池的性能，特提出本发明。In view of the above technical problems, in order to meet the requirements of marketization of aqueous zinc-ion batteries, reduce costs, be safe and environmentally friendly, and suppress dendrite growth and improve battery performance without reducing energy density, the present invention is proposed.
发明内容Contents of the invention
本发明的第一目的在于提供一种水系锌离子电池负极材料的制备方法。通过射频磁控溅射方法在锌箔表面沉积得到纯锌多孔隙结构。由于阴影效应和较低的原子迁移率形成了多孔隙和复杂多变的结构，进而增加比表面积，降低有效电流密度，缓解枝晶生长。源于这种结构，增加电极与电解液的直接接触，加快锌离子与电子的交换。因此，可以有效抑制枝晶的生长和提升电池的容量，提高水系锌离子电池的性能，进而向替代锂电池迈出坚实的一步。The first object of the present invention is to provide a method for preparing an anode material for an aqueous zinc-ion battery. The pure zinc porous structure is obtained by depositing on the surface of zinc foil by radio frequency magnetron sputtering. Due to the shadow effect and low atomic mobility, a porous and complex structure is formed, which increases the specific surface area, reduces the effective current density, and alleviates dendrite growth. Due to this structure, the direct contact between the electrode and the electrolyte is increased, and the exchange of zinc ions and electrons is accelerated. Therefore, it can effectively inhibit the growth of dendrites and increase the capacity of the battery, improve the performance of the aqueous zinc-ion battery, and then take a solid step towards replacing lithium batteries.
本发明通过以下技术方案实现：The present invention is realized through the following technical solutions:
第一方面，本发明提供一种水系锌离子电池负极材料的制备方法，包括以下步骤：In a first aspect, the present invention provides a method for preparing an aqueous zinc-ion battery negative electrode material, comprising the following steps:
采用射频磁控溅射方法将锌靶材的锌原子溅射到基底锌箔上得到水系锌离子电池负极材料；The zinc atoms of the zinc target are sputtered onto the base zinc foil by radio frequency magnetron sputtering to obtain the negative electrode material of the aqueous zinc ion battery;
所述溅射的工作参数包括：溅射角度为30～90度、功率密度为1～5W/cm2、溅射时间为1～30min和溅射压强为0.2～5Pa。The working parameters of the sputtering include: a sputtering angle of 30-90 degrees, a power density of 1-5W/cm 2 , a sputtering time of 1-30min and a sputtering pressure of 0.2-5Pa.
进一步地，在本发明较佳的实施例中，上述真空室内溅射前压强为1～10×10-4Pa。Further, in a preferred embodiment of the present invention, the pressure in the vacuum chamber before sputtering is 1˜10×10 −4 Pa.
进一步地，在本发明较佳的实施例中，上述基底锌箔使用前的预处理；锌箔预处理包括：依次采用去离子水、无水乙醇超声清洗锌箔各10～15min。Further, in a preferred embodiment of the present invention, the pretreatment of the above-mentioned base zinc foil before use; the pretreatment of the zinc foil includes: sequentially using deionized water and absolute ethanol to ultrasonically clean the zinc foil for 10-15 minutes each.
进一步地，在本发明较佳的实施例中，上述预处理后的锌箔经过5～25℃冷风干燥得到基底锌箔，所述干燥时间为1～5min。Further, in a preferred embodiment of the present invention, the above-mentioned pretreated zinc foil is dried by cold air at 5-25° C. to obtain the base zinc foil, and the drying time is 1-5 minutes.
进一步地，在本发明较佳的实施例中，上述方法还包括锌靶材使用前的预溅射；所述预溅射时间为5～15min，预溅射功率密度为1～5W/cm2。Further, in a preferred embodiment of the present invention, the above method also includes pre-sputtering before the zinc target is used; the pre-sputtering time is 5-15 minutes, and the pre-sputtering power density is 1-5 W/cm 2 .
进一步地，在本发明较佳的实施例中，上述锌靶材纯度为99.9～99.999％。Further, in a preferred embodiment of the present invention, the purity of the zinc target is 99.9-99.999%.
进一步地，在本发明较佳的实施例中，上述溅射过程中通入纯度为95～99.999％的氩气，通入氩气后控制压强为0.2～5Pa。Further, in a preferred embodiment of the present invention, argon gas with a purity of 95-99.999% is introduced into the sputtering process, and the pressure is controlled to be 0.2-5 Pa after the argon gas is introduced.
进一步地，在本发明较佳的实施例中，上述锌离子电池负极材料的溅射厚度为70～5000nm，晶粒的直径为20～150nm。Further, in a preferred embodiment of the present invention, the sputtering thickness of the zinc-ion battery negative electrode material is 70-5000 nm, and the grain diameter is 20-150 nm.
第二方面，本发明提供一种水系锌离子电池负极材料。In a second aspect, the present invention provides an anode material for an aqueous zinc-ion battery.
与现有技术相比，本发明至少具有如下技术效果：Compared with the prior art, the present invention has at least the following technical effects:
本发明的水系锌离子电池负极材料的制备方法，通过射频磁控溅射方法在锌箔表面沉积得到纯锌多孔隙结构。相对均匀的表面不仅更有利于锌的均匀剥离和沉积，而且复杂的多孔隙结构增加比表面积，降低有效电流密度，抑制锌枝晶的生长。不仅如此，在这种结构中也增加电极与电解液的直接接触，加快锌离子与电子的交换。因此，全电池的性能得到了提升。The preparation method of the negative pole material of the water-based zinc ion battery of the present invention is to deposit the pure zinc porous structure on the surface of the zinc foil by the radio frequency magnetron sputtering method. The relatively uniform surface is not only more conducive to the uniform exfoliation and deposition of zinc, but also the complex porous structure increases the specific surface area, reduces the effective current density, and inhibits the growth of zinc dendrites. Not only that, the direct contact between the electrode and the electrolyte is also increased in this structure, which accelerates the exchange of zinc ions and electrons. Therefore, the performance of the full battery is improved.
本发明的一种水系锌离子电池负极材料，以“预沉积”锌的方式，增加比表面积降低有效电流密度和活性位点，促进锌离子与电子的交换，抑制锌枝晶的生长，以获得长时间稳定循环的水系锌离子电池。The anode material of a water-based zinc ion battery of the present invention, by "pre-depositing" zinc, increases the specific surface area, reduces the effective current density and active sites, promotes the exchange of zinc ions and electrons, and inhibits the growth of zinc dendrites to obtain Aqueous zinc-ion battery with stable cycle for a long time.
附图说明Description of drawings
图1为本发明实施例1和对比例1的电池材料的X射线衍射(XRD)图谱。FIG. 1 is the X-ray diffraction (XRD) patterns of the battery materials of Example 1 and Comparative Example 1 of the present invention.
图2为本发明实施例1和对比例1的电池材料循环前后的扫描电子显微镜(SEM)形貌表征。FIG. 2 is a scanning electron microscope (SEM) morphology characterization of the battery materials of Example 1 and Comparative Example 1 of the present invention before and after cycling.
图2(a)为本发明实施例1中水系锌离子电池负极材料的形貌；Fig. 2 (a) is the morphology of the negative electrode material of aqueous zinc ion battery in the embodiment of the present invention 1;
图2(b)为本发明实施例1中水系锌离子电池负极材料循环300次之后的形貌；Fig. 2 (b) is the morphology after 300 cycles of the negative electrode material of the aqueous zinc-ion battery in Example 1 of the present invention;
图2(c)为本发明对比例1中裸锌的形貌；Fig. 2 (c) is the morphology of bare zinc in comparative example 1 of the present invention;
图2(d)为本发明对比例1中裸锌循环300次之后的形貌。Figure 2(d) is the morphology of bare zinc after 300 cycles in Comparative Example 1 of the present invention.
图3为本发明实施例1和对比例1的对称电池寿命对比图。FIG. 3 is a comparison chart of symmetrical battery life of Example 1 and Comparative Example 1 of the present invention.
图4为本发明实施例2和对比例2的全电池在不同倍率下的比容量对比图。FIG. 4 is a comparison chart of the specific capacities of the full batteries of Example 2 of the present invention and Comparative Example 2 at different rates.
图5为本发明实施例2和对比例2全电池循环过程中的比容量对比图。Fig. 5 is a comparison chart of specific capacity during full battery cycle of Example 2 of the present invention and Comparative Example 2.
图6为本发明射频磁控溅射设备的工艺流程示意图。Fig. 6 is a schematic diagram of the process flow of the radio frequency magnetron sputtering equipment of the present invention.
具体实施方式Detailed ways
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明的范围，实施例中未注明的具体条件，按照常规条件或者制造商建议的条件进行，所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。Embodiments of the present invention will be described in detail below in conjunction with the examples, but those skilled in the art will understand that the following examples are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention, and are not indicated in the examples The specific conditions were carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.
本发明的技术方案为：Technical scheme of the present invention is:
第一方面，本发明提供一种水系锌离子电池负极材料的制备方法，包括以下步骤：In a first aspect, the present invention provides a method for preparing an aqueous zinc-ion battery negative electrode material, comprising the following steps:
采用射频磁控溅射方法将锌靶材的锌原子溅射到基底锌箔上得到水系锌离子电池负极材料；The zinc atoms of the zinc target are sputtered onto the base zinc foil by radio frequency magnetron sputtering to obtain the negative electrode material of the aqueous zinc ion battery;
所述溅射的工作参数包括：溅射角度为30～90度、功率密度为1～5W/cm2、溅射时间为1～30min和溅射压强为0.2～5Pa。采用射频磁控溅射方法的好处是制备工艺简单，易重复，无需进一步加工即可直接使用。溅射角度过低时，溅射得到的水系锌离子电池负极材料厚度偏差会更大，所以扩大溅射角度，有利于溅射得到的水系锌离子电池负极材料厚度更加的均匀。控制溅射功率密度可以获得不同晶粒大小和厚度的水系锌离子电池负极材料，其中溅射功率密度是指溅射功率与锌靶材最上表面积的比值。当溅射功率密度高于5W/cm2时，溅射量过大，锌原子的损失率过高，增加原材料成本，尤其是功率密度越高，代表靶材的温度也会越高，容易将锌靶材融化；当溅射功率密度低于1W/cm2，溅射量太小，不易获得厚度相对均匀的多孔隙结构。The working parameters of the sputtering include: a sputtering angle of 30-90 degrees, a power density of 1-5W/cm 2 , a sputtering time of 1-30min and a sputtering pressure of 0.2-5Pa. The advantage of using the radio frequency magnetron sputtering method is that the preparation process is simple, easy to repeat, and can be used directly without further processing. When the sputtering angle is too low, the thickness deviation of the anode material of the water-based zinc-ion battery obtained by sputtering will be greater. Therefore, expanding the sputtering angle is conducive to a more uniform thickness of the anode material of the water-based zinc-ion battery obtained by sputtering. Anode materials for aqueous zinc-ion batteries with different grain sizes and thicknesses can be obtained by controlling the sputtering power density, where the sputtering power density refers to the ratio of the sputtering power to the uppermost surface area of the zinc target. When the sputtering power density is higher than 5W/ cm2 , the sputtering amount is too large, the loss rate of zinc atoms is too high, and the cost of raw materials will be increased. Especially, the higher the power density, the higher the temperature of the target material, and it is easy to The zinc target melts; when the sputtering power density is lower than 1W/cm 2 , the amount of sputtering is too small, and it is difficult to obtain a porous structure with a relatively uniform thickness.
进一步优选的，上述真空室内溅射前压强为1～10×10-4Pa。锌靶材和锌箔置于真空压强为1～10×10-4Pa，控制真空压强的好处是获得纯度更高的纯锌结构。当抽真空控制一定的真空度时，有利于减少真空室内的气体(例如空气中存在的氮气和氧气等气体)，其中锌和氧气、氮气在溅射过程中容易生成氧化锌和氮化锌，造成样品的纯度较低，无法达到预期效果。Further preferably, the pressure in the vacuum chamber before sputtering is 1˜10×10 −4 Pa. The vacuum pressure of the zinc target and zinc foil is 1-10×10 -4 Pa, and the benefit of controlling the vacuum pressure is to obtain a pure zinc structure with higher purity. When the vacuum is controlled to a certain degree of vacuum, it is beneficial to reduce the gas in the vacuum chamber (such as nitrogen and oxygen in the air), in which zinc, oxygen and nitrogen are easy to generate zinc oxide and zinc nitride during the sputtering process. As a result, the purity of the sample is low, and the expected effect cannot be achieved.
进一步优选的，上述衬底锌箔使用前经过预处理，锌箔预处理包括：依次采用去离子水、无水乙醇超声清洗锌箔各10～15min。上述方式的好处是去除锌箔表面自发形成的氧化层和因工业中残留的油污与其它杂质。Further preferably, the above-mentioned substrate zinc foil is pretreated before use, and the zinc foil pretreatment includes: using deionized water and absolute ethanol to ultrasonically clean the zinc foil for 10-15 minutes each. The advantage of the above method is to remove the spontaneously formed oxide layer on the surface of the zinc foil and the oil and other impurities remaining in the industry.
进一步优选的，上述预处理后的锌箔经过5～25℃冷风干燥得到衬底锌箔，所述干燥的时间为1～5min。上述方式的好处是冷风干燥不改变样品原始的晶相以及减少氧化物的形成，而温度较高则在空气中会较快的氧化。Further preferably, the pretreated zinc foil is dried by cold air at 5-25° C. to obtain the substrate zinc foil, and the drying time is 1-5 minutes. The advantage of the above method is that the cold air drying does not change the original crystal phase of the sample and reduces the formation of oxides, while the higher temperature will oxidize faster in the air.
进一步优选的，上述锌靶材使用前经过预溅射，预溅射时间为5～15min，预溅射功率密度为1～5W/cm2。上述方式的好处是当溅射功率密度较低时延长溅射时间或溅射功率密度较高时溅射时间短，尽可能的去除靶材表面的氧化层或者其它生成物。Further preferably, the zinc target is pre-sputtered before use, the pre-sputtering time is 5-15 min, and the pre-sputtering power density is 1-5 W/cm 2 . The advantage of the above method is that the sputtering time is extended when the sputtering power density is low or the sputtering time is short when the sputtering power density is high, and the oxide layer or other products on the surface of the target are removed as much as possible.
进一步优选的，上述锌靶材纯度为99.9～99.999％。采用上述方式的好处是得到的水系锌离子电池负极材料的纯度更高，有助于电池提升性能。Further preferably, the purity of the zinc target is 99.9-99.999%. The advantage of adopting the above method is that the obtained aqueous zinc-ion battery anode material has higher purity, which helps to improve the performance of the battery.
进一步优选的，上述溅射过程中通入纯度为95～99.999％的氩气，通入氩气后控制压强为0.2～5Pa。采用上述方式的好处是使用纯度更高的氩气有利于获得纯度高的水系锌离子电池负极材料。控制压强，有利于提高沉积速率，较为快速的获得所需厚度的水系锌离子电池负极材料。Further preferably, argon gas with a purity of 95-99.999% is introduced during the sputtering process, and the pressure is controlled to be 0.2-5 Pa after the argon gas is introduced. The advantage of adopting the above method is that the use of higher-purity argon is beneficial to obtain a high-purity water-based zinc-ion battery negative electrode material. Controlling the pressure is conducive to increasing the deposition rate and obtaining the required thickness of the water-based zinc-ion battery negative electrode material relatively quickly.
进一步优选的，上述锌离子电池负极材料的溅射厚度为70～5000nm，晶粒的直径为20～150nm。采用上述方式的好处是构建的多孔隙结构增加了比表面积，可以降低有效电流密度，以达到缓解枝晶生长的目的。Further preferably, the sputtering thickness of the zinc-ion battery negative electrode material is 70-5000 nm, and the grain diameter is 20-150 nm. The advantage of using the above method is that the constructed porous structure increases the specific surface area, which can reduce the effective current density to achieve the purpose of alleviating dendrite growth.
第二方面，本发明提供一种由上述方法制备得到的水系锌离子电池负极材料。In the second aspect, the present invention provides an aqueous zinc-ion battery negative electrode material prepared by the above method.
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.
实施例1Example 1
本实施例提供一种水系锌离子电池负极材料的制备方法，包括以下步骤：This embodiment provides a method for preparing an aqueous zinc-ion battery negative electrode material, comprising the following steps:
步骤1：取0.08mm厚的锌箔依次采用去离子水、无水乙醇超声清洗各10min，继续用10～12℃冷风干燥后制得基底锌箔；制备的基底锌箔固定在射频磁控溅射设备的真空室内的样品台上；调节锌靶材的角度螺母，控制溅射角度为30度。Step 1: Take a 0.08mm thick zinc foil and ultrasonically clean it with deionized water and absolute ethanol for 10 minutes each, and then dry it with cold air at 10-12°C to obtain the base zinc foil; the prepared base zinc foil is fixed on a radio frequency magnetron sputtering on the sample stage in the vacuum chamber of the sputtering equipment; adjust the angle nut of the zinc target to control the sputtering angle to be 30 degrees.
步骤2：取纯度为99.9％，厚度为4mm，直径50.8mm的锌靶材置于真空室内的射频磁控溅射靶枪上；用机械泵和分子泵抽真空，真空压强为1～2×10-4Pa。通入99.99％的氩气，控制压强为1Pa。进行预溅射，预溅射时将可调节挡板关闭，设置靶枪的预溅射功率为1.5W/cm2(功率设置为31W，表面积为20.3cm2)，预溅射时间为15min后得到去除氧化物和其它化合物的锌靶材。Step 2: Take a zinc target with a purity of 99.9%, a thickness of 4mm, and a diameter of 50.8mm, and place it on the radio frequency magnetron sputtering target gun in the vacuum chamber; vacuumize with a mechanical pump and a molecular pump, and the vacuum pressure is 1 to 2× 10 -4 Pa. Introduce 99.99% argon gas, and control the pressure to 1Pa. Perform pre-sputtering, close the adjustable baffle during pre-sputtering, set the pre-sputtering power of the target gun to 1.5W/cm 2 (the power is set to 31W, the surface area is 20.3cm 2 ), and the pre-sputtering time is 15 minutes later The resulting zinc target removes oxides and other compounds.
步骤3：Step 3:
预溅射锌靶材完毕后，控制压强为0.2Pa，打开可调节挡板，将锌靶材的锌原子溅射到基底锌箔上，溅射时间为25min，得到水系锌离子电池负极材料1；After pre-sputtering the zinc target, control the pressure to 0.2Pa, open the adjustable baffle, and sputter the zinc atoms of the zinc target onto the base zinc foil. The sputtering time is 25 minutes, and the negative electrode material 1 of the aqueous zinc ion battery is obtained. ;
上述电池材料采用X射线衍射(XRD)表征结构测试，相结构对应的标准卡PDF#65-3358，测试后如图1所示。The above battery materials are characterized by X-ray diffraction (XRD) structure test, and the corresponding standard card PDF#65-3358 of the phase structure is shown in Figure 1 after the test.
本实施例提供一种水系锌离子电池负极材料This embodiment provides a negative electrode material for an aqueous zinc-ion battery
组装对称电池：对称电池测试是一种排除正极材料影响，评估水系锌离子电池负极材料抑制枝晶可行性的方法。Assembling a symmetrical battery: The symmetrical battery test is a method to exclude the influence of the positive electrode material and evaluate the feasibility of dendrite suppression by the negative electrode material of the aqueous zinc-ion battery.
将上述制得的水系锌离子电池负极材料1切割成直径为12mm、溅射厚度为1800nm的水系锌离子电池负极圆片，采用CR-2032型电池壳组装成对称电池；对称电池内部的结构和安装顺序依次为负极壳、水系锌离子电池负极圆片、两片隔膜(直径为16mm)、水系锌离子电池负极圆片、不锈钢垫片(直径为14.5mm、厚度为0.5mm)、不锈钢弹片、正极壳。电池封装压力大小为50GPa。隔膜使用的是Whatman公司生产的玻璃纤维(GF/A)。所使用的电解液为2mol/L硫酸锌溶液，单个电池的电解液使用量为200微升，在放入两片隔膜后添加。The water-based zinc-ion battery negative electrode material 1 prepared above is cut into a water-based zinc-ion battery negative electrode disc with a diameter of 12mm and a sputtering thickness of 1800nm, and a symmetric battery is assembled using a CR-2032 battery case; the internal structure of the symmetrical battery and The order of installation is the negative electrode shell, the negative electrode disc of the aqueous zinc-ion battery, two diaphragms (16mm in diameter), the negative electrode disc of the aqueous zinc-ion battery, the stainless steel gasket (14.5mm in diameter, 0.5mm in thickness), stainless steel shrapnel, Positive shell. The battery packaging pressure is 50GPa. The separator used is glass fiber (GF/A) produced by Whatman Company. The electrolyte used is a 2mol/L zinc sulfate solution, and the amount of electrolyte used in a single battery is 200 microliters, which is added after the two separators are placed.
上述组装后的电池进行性能测试，测试方法如下：The above-mentioned assembled battery is subjected to a performance test, and the test method is as follows:
对称电池循环稳定性测试在室温条件下进行，电池的测试设备使用的是深圳新威测试***。测试程序设置依次为静置、恒流放电、恒流充电、循环和结束。静置时间为2h，恒流放电和恒流充电时间设置为10min。循环一次包括一次恒流放电和一次恒流充电，通过循环程序进行统计，测试过程中可随时停止测试，得到对称电池循环时间(循环一次的时间为20min)。对于每个电池负极圆片的电流密度设置为0.5、1.0和2.0mA/cm2，对称电池循环寿命如图3所示。The cycle stability test of the symmetrical battery is carried out at room temperature, and the battery test equipment uses the Shenzhen Xinwei test system. The test program settings are in turn static, constant current discharge, constant current charge, cycle and end. The rest time is 2h, and the constant current discharge and constant current charge time are set to 10min. One cycle includes one constant current discharge and one constant current charge. Statistics are carried out through the cycle program. The test can be stopped at any time during the test to obtain the symmetrical battery cycle time (the time for one cycle is 20 minutes). For the current density of the negative electrode disc of each battery is set to 0.5, 1.0 and 2.0 mA/cm 2 , the cycle life of the symmetrical battery is shown in FIG. 3 .
在该测试过程中，水系锌离子电池负极材料的循环寿命依次可达1900h(5700次)、1693h(5079次)和1000h(3000次)。During the test, the cycle life of the anode material of the aqueous zinc-ion battery can reach 1900h (5700 times), 1693h (5079 times) and 1000h (3000 times) successively.
采用扫描电子显微镜(SEM)对水系锌离子电池负极材料循环前后进行形貌表征，如图2所示。Scanning electron microscopy (SEM) was used to characterize the morphology of the anode material of the aqueous zinc-ion battery before and after cycling, as shown in Figure 2.
在图2(a)中，水系锌离子电池负极材料的表面有较多的孔隙，孔径为10～150nm，晶粒大小为20～150nm。图2(b)是水系锌离子电池负极材料组装的对称电池在电流密度为1.0mA/cm2下，循环300次之后，形貌呈现的是平面结构，不同于裸锌的散乱局部堆积，表明具备抑制枝晶生长的能力。In Fig. 2(a), the surface of the negative electrode material of the aqueous zinc-ion battery has many pores, the pore diameter is 10-150nm, and the grain size is 20-150nm. Figure 2(b) is a symmetrical battery assembled with the negative electrode material of the aqueous zinc-ion battery. After 300 cycles at a current density of 1.0mA/cm 2 , the morphology presents a planar structure, which is different from the scattered local accumulation of bare zinc, indicating that Possesses the ability to inhibit dendrite growth.
实施例2Example 2
本实施例提供一种水系锌离子电池负极材料的制备方法，包括以下步骤：This embodiment provides a method for preparing an aqueous zinc-ion battery negative electrode material, comprising the following steps:
步骤1：取0.08mm厚的锌箔依次采用去离子水、无水乙醇超声清洗各15min，继续用20℃冷风干燥后制得基底锌箔；制备的基底锌箔固定在射频磁控溅射设备的真空室内的样品台上；调节锌靶材的角度螺母，控制溅射角度为90度；Step 1: Take a 0.08mm thick zinc foil and ultrasonically clean it with deionized water and absolute ethanol for 15 minutes each, and then dry it with cold air at 20°C to obtain the base zinc foil; the prepared base zinc foil is fixed on the radio frequency magnetron sputtering equipment On the sample stage in the vacuum chamber; adjust the angle nut of the zinc target to control the sputtering angle to 90 degrees;
步骤2：取纯度为99.999％、厚度为6mm、直径为50.8mm的锌靶材置于真空室内的磁控溅射靶枪上；用机械泵和分子泵抽真空，真空压强为9×10-4Pa。通入99.99％的氩气，控制压强为1Pa。进行预溅射。预溅射时将可调节挡板关闭，设置靶枪的溅射功率为4.5W/cm2(功率设置为91W，表面积为20.3cm2)，预溅射时间为5min后得到去除氧化物和其它化合物的锌靶材；Step 2: Take a zinc target with a purity of 99.999%, a thickness of 6mm, and a diameter of 50.8mm and place it on the magnetron sputtering target gun in the vacuum chamber; vacuumize with a mechanical pump and a molecular pump, and the vacuum pressure is 9×10 - 4Pa . Introduce 99.99% argon gas, and control the pressure to 1Pa. Perform pre-sputtering. Close the adjustable baffle during pre-sputtering, set the sputtering power of the target gun to 4.5W/cm 2 (the power is set to 91W, and the surface area is 20.3cm 2 ), and the oxide and other compound zinc target;
步骤3：预溅射锌靶材完毕后，控制压强为1Pa，打开可调节挡板，将锌靶材的锌原子溅射到基底锌箔上，溅射时间为3min，得到水系锌离子电池负极材料2。Step 3: After pre-sputtering the zinc target, control the pressure to 1Pa, open the adjustable baffle, and sputter the zinc atoms of the zinc target onto the base zinc foil for 3 minutes to obtain the negative electrode of the water-based zinc-
本实施例提供一种水系锌离子电池负极材料This embodiment provides a negative electrode material for an aqueous zinc-ion battery
将上述制得的水系锌离子电池负极材料2作为负极材料，二氧化锰(α型)作为正极材料组装成全电池，进行测试。The
二氧化锰(α型)电极制备：Manganese dioxide (α-type) electrode preparation:
将1.52g硫酸锰(MnSO4·H2O)和0.95g高锰酸钾(KMnO4)分别溶解在60毫升的去离子水中，混合两种溶液并且搅拌15min。随后转移至200毫升反应釜中，在烘箱中120℃保温12h，冷却至室温。取出沉淀物进行抽滤清洗，分别使用去离子水和无水乙醇冲洗三次。再转移至烘箱中80℃干燥1h，充分研磨获得二氧化锰(α型)粉末。将140mg二氧化锰(α型)粉末和40mg炭黑AB研磨10min，再加入20mg的聚四氟乙烯(PTFE，10wt％)溶液，加入无水乙醇继续研磨混合均匀，干燥3min，滴加无水乙醇压制成片，再次干燥30～60min，切割成直径为8mm的二氧化锰(α型)电极圆片。正极片中的二氧化锰的负载量为1.5-4mg。1.52 g of manganese sulfate (MnSO 4 ·H 2 O) and 0.95 g of potassium permanganate (KMnO 4 ) were respectively dissolved in 60 ml of deionized water, and the two solutions were mixed and stirred for 15 min. Then it was transferred to a 200ml reactor, kept in an oven at 120°C for 12h, and cooled to room temperature. The precipitate was taken out and cleaned by suction filtration, and washed three times with deionized water and absolute ethanol respectively. Then transfer to an oven for drying at 80° C. for 1 h, and grind thoroughly to obtain manganese dioxide (α-type) powder. Grind 140mg of manganese dioxide (α-type) powder and 40mg of carbon black AB for 10min, then add 20mg of polytetrafluoroethylene (PTFE, 10wt%) solution, add absolute ethanol and continue to grind and mix evenly, dry for 3min, add anhydrous Ethanol was pressed into sheets, dried again for 30-60 minutes, and cut into manganese dioxide (α-type) electrode discs with a diameter of 8 mm. The loading amount of manganese dioxide in the positive electrode sheet is 1.5-4 mg.
SP82(炭黑)集流体的制备：Preparation of SP82 (carbon black) current collector:
使用160mg的super P和40mg的聚四氟乙烯(PTFE，10wt％)与无水乙醇研磨15min，使其混合均匀，压制成片，在烘箱中60℃进行干燥60min，切割成直径为10mm的SP82圆片。Use 160mg of super P and 40mg of polytetrafluoroethylene (PTFE, 10wt%) and absolute ethanol to grind for 15min, make it evenly mixed, press into a tablet, dry in an oven at 60°C for 60min, and cut into SP82 with a diameter of 10mm. wafer.
组装全电池：全电池性能测试是一种直接评估水系锌离子电池负极材料可行性的检测方式。将上述制得的溅射厚度为5000nm的水系锌离子电池负极材料2切割成直径为12mm的水系锌离子电池负极圆片，采用CR-2032型电池壳组装成全电池；全电池内部的结构和安装顺序依次为负极壳、水系锌离子电池负极圆片、两片隔膜(直径为16mm)、二氧化锰(α型)电极圆片、SP82圆片(直径10mm)、钛网(直径12mm，500目)、不锈钢垫片(直径14.5mm，厚度0.5mm)、不锈钢弹片、正极壳。电池封装压力大小为50GPa。隔膜使用的是Whatman公司生产的玻璃纤维(GF/A)。所使用的电解液为2mol/L硫酸锌加0.2mol/L硫酸锰的混合溶液，单个电池的电解液使用量为200微升，在放入两片隔膜后添加。Assemble the full battery: The performance test of the full battery is a detection method to directly evaluate the feasibility of the anode material of the aqueous zinc-ion battery. The water-based zinc-ion battery
上述组装后的电池进行倍率性能测试，测试方法如下：The above-mentioned assembled battery is tested for rate performance, and the test method is as follows:
组装后的全电池的倍率性能测试在室温条件下测试，测试设备使用的是武汉蓝电测试***。测试程序设置依次为静置、恒流放电、恒流充电、循环和结束。静置时间为2h，恒流放电的截止电压为1.0V，恒流充电的截止电压为1.85V，循环一次包括一次恒流放电和一次恒流充电，通过循环程序进行统计，测试过程中可随时停止测试或者单个测试电流密度循环为5次，共计30个循环之后仪器自动结束测试；测试结果如图4所示。The rate performance test of the assembled full battery is tested at room temperature, and the test equipment uses the Wuhan Landian test system. The test program settings are in turn static, constant current discharge, constant current charge, cycle and end. The rest time is 2h, the cut-off voltage of constant current discharge is 1.0V, and the cut-off voltage of constant current charge is 1.85V. One cycle includes one constant current discharge and one constant current charge. Statistics are made through the cycle program. Stop the test or cycle the current density of a single test for 5 times, and the instrument will automatically end the test after a total of 30 cycles; the test results are shown in Figure 4.
测试电流密度依次为0.2、0.5、1.0、1.5、2.0和3.0A/g。在不同的电流密度下的比容量依次为265.5、215.4、152.2、123.8、112.9和101.3mAh/g。The test current densities were 0.2, 0.5, 1.0, 1.5, 2.0 and 3.0A/g in sequence. The specific capacities at different current densities are 265.5, 215.4, 152.2, 123.8, 112.9 and 101.3mAh/g.
上述电池进行循环稳定性测试：测试方法如下：The above battery is tested for cycle stability: the test method is as follows:
组装后的全电池在室温条件下测试。电池的测试设备使用的是深圳新威测试***。测试程序设置依次为静置、恒流放电、恒流充电、循环和结束。静置时间为2h，恒流放电的截止电压为1.0V，恒流充电的截止电压为1.85V，循环一次包括一次恒流放电和一次恒流充电，通过循环程序进行统计，测试过程中可随时停止测试或者测试循环次数800次之后仪器自动结束测试。测试电流密度为2A/g。结果如图5所示。The assembled full cells were tested at room temperature. The battery test equipment uses Shenzhen Xinwei test system. The test program settings are in turn static, constant current discharge, constant current charge, cycle and end. The rest time is 2h, the cut-off voltage of constant current discharge is 1.0V, and the cut-off voltage of constant current charge is 1.85V. One cycle includes one constant current discharge and one constant current charge. Statistics are made through the cycle program. The instrument automatically ends the test after the test is stopped or the number of test cycles is 800 times. The test current density is 2A/g. The result is shown in Figure 5.
在图5中，采用本实施例方法制备得到的水系锌离子电池负极材料组装的全电池的初始比容量为119.3mAh/g，循环800次之后的比容量为91.4mAh/g，容量保留率为76.6％。In Fig. 5, the initial specific capacity of the full battery assembled with the negative electrode material of the aqueous zinc-ion battery prepared by the method of this example is 119.3mAh/g, and the specific capacity after 800 cycles is 91.4mAh/g, and the capacity retention is 76.6%.
对比例1Comparative example 1
取0.08mm厚的锌箔依次采用去离子水、无水乙醇超声清洗各10min，10℃冷风干燥后得到裸锌；Take a 0.08mm thick zinc foil and use deionized water and absolute ethanol to ultrasonically clean it for 10 minutes each, and dry it with cold air at 10°C to obtain bare zinc;
采用X射线衍射(XRD)表征裸锌相结构，相结构对应的标准卡PDF#65-3358，测试后如图1所示。X-ray diffraction (XRD) was used to characterize the bare zinc phase structure, and the phase structure corresponds to the standard card PDF#65-3358, as shown in Figure 1 after the test.
裸锌对称电池组装，组装方式同实施例1相同，将实施例1制得的水系锌离子电池负极材料替换为裸锌。并且采用实施例1的测试方法对裸锌电池进行对称电池的循环稳定性进行测试。对于每个负极圆片的电流密度设置为0.5、1.0和2.0mA/cm2，对称电池寿命如图3所示。The bare zinc symmetrical battery is assembled, and the assembly method is the same as that of Example 1, and the negative electrode material of the aqueous zinc ion battery prepared in Example 1 is replaced with bare zinc. And the cycle stability of the symmetrical battery was tested on the bare zinc battery by using the test method in Example 1. For the current density setting of each negative electrode disc at 0.5, 1.0 and 2.0 mA/cm 2 , the symmetrical battery life is shown in FIG. 3 .
在该测试过程中，裸锌对称电池的寿命依次为150(450次)、170(510次)和140(420次)h。During the test, the lifespan of the bare zinc symmetric battery was 150 (450 cycles), 170 (510 cycles) and 140 (420 cycles) h.
采用扫描电子显微镜(SEM)对裸锌循环前后的形貌进行表征，如图2所示。The morphology of bare zinc before and after cycling was characterized by scanning electron microscopy (SEM), as shown in Figure 2.
图2(c，d)为裸锌作为对称电池电极片进行充放电前后的SEM表面形貌图。测试前的裸锌表面存在凹凸不平的地方，分布也不均匀。裸锌组装的对称电池在1mA/cm2的电流密度下循环300次之后，从图2(d)可以看到局部的片状锌的聚集，尤其是存在突起的片状枝晶，这种结构继续生长极易造成电池的短路和失效。Figure 2(c, d) is the SEM surface topography of bare zinc as a symmetrical battery electrode sheet before and after charging and discharging. The bare zinc surface before the test has unevenness, and the distribution is not uniform. After 300 cycles of the bare zinc-assembled symmetric battery at a current density of 1mA/cm 2 , it can be seen from Figure 2(d) that the local flaky zinc aggregates, especially the protruding flaky dendrites, this structure Continued growth can easily cause short circuit and failure of the battery.
对比例2Comparative example 2
取0.08mm厚的锌箔依次采用去离子水、无水乙醇超声清洗各10min，12℃冷风干燥后得到裸锌；Take a 0.08mm thick zinc foil and ultrasonically clean it with deionized water and absolute ethanol for 10 minutes each, and dry it with cold air at 12°C to obtain bare zinc;
采用实施例2中制备得到的二氧化锰(α型)电极作为正极材料，安装顺序同实施例2相同，将实施例2制得的水系锌离子电池负极材料替换为裸锌。并且采用实施例2的测试方法对组装后的全电池进行倍率性能测试和循环稳定性测试，测试结果如图4和5所示。The manganese dioxide (α-type) electrode prepared in Example 2 was used as the positive electrode material, the installation sequence was the same as in Example 2, and the negative electrode material of the aqueous zinc ion battery prepared in Example 2 was replaced with bare zinc. In addition, the rate performance test and cycle stability test of the assembled full battery were carried out by using the test method of Example 2, and the test results are shown in FIGS. 4 and 5 .
在图4中，测试电流密度依次为0.2、0.5、1.0、1.5、2.0和3.0A/g，在不同的电流密度下的比容量依次为259.1、194.1、117、97.7、90.8和81.7mAh/g。In Figure 4, the test current densities are 0.2, 0.5, 1.0, 1.5, 2.0 and 3.0A/g in sequence, and the specific capacities at different current densities are 259.1, 194.1, 117, 97.7, 90.8 and 81.7mAh/g in sequence .
在图5中，裸锌组装的全电池的初始比容量为105mAh/g，循环800圈之后的比容量为69.3mAh/g。比容量保留率为66.0％。In Figure 5, the initial specific capacity of the bare zinc-assembled full battery is 105 mAh/g, and the specific capacity after 800 cycles is 69.3 mAh/g. The specific capacity retention rate was 66.0%.
最后应说明的是：以上所述仅为本发明的较佳的实施例而已，并不用于限制本发明的保护范围。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。Finally, it should be noted that: the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.
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| CN110444730A (en) * | 2019-08-19 | 2019-11-12 | 中南大学 | A kind of preparation method and application of tridimensional network nanometer layer zinc load |
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