CN105098143A - Flexible high-sulfur load self-repairing cathode structure for lithium-sulfur battery and preparation method of flexible high-sulfur load self-repairing cathode structure - Google Patents
Flexible high-sulfur load self-repairing cathode structure for lithium-sulfur battery and preparation method of flexible high-sulfur load self-repairing cathode structure Download PDFInfo
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- CN105098143A CN105098143A CN201410208703.3A CN201410208703A CN105098143A CN 105098143 A CN105098143 A CN 105098143A CN 201410208703 A CN201410208703 A CN 201410208703A CN 105098143 A CN105098143 A CN 105098143A
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
本发明公开了一种锂硫电池柔性高硫负载自修复正极结构及其制备方法,属于电化学电池领域。本发明锂硫电池正极结构是由石墨烯/高分子聚合物柔性泡沫、碳/硫活性物质层所构成,其中活性物质为硫,石墨烯/高分子聚合物柔性泡沫提供强度和自修复功能。本发明特点是实现了锂硫电池多组元一体化设计,保证高电化学性能的同时提高了硫的含量,实现电池的高活性物质面密度,得到的锂硫电池具有高比容量与高比能量密度的优势,同时也具有柔性和自修复的特征。本发明制备过程简单、易控,可实现大量、低成本制备,应用价值广阔。The invention discloses a flexible high-sulfur-loaded self-repairing positive electrode structure of a lithium-sulfur battery and a preparation method thereof, belonging to the field of electrochemical batteries. The cathode structure of the lithium-sulfur battery of the present invention is composed of a graphene/polymer flexible foam and a carbon/sulfur active material layer, wherein the active material is sulfur, and the graphene/polymer flexible foam provides strength and self-repairing functions. The feature of the present invention is that the multi-component integrated design of the lithium-sulfur battery is realized, the sulfur content is increased while ensuring high electrochemical performance, and the high active material surface density of the battery is realized, and the obtained lithium-sulfur battery has high specific capacity and high ratio The advantage of energy density is also characterized by flexibility and self-healing. The preparation process of the present invention is simple and easy to control, can realize large-scale and low-cost preparation, and has wide application value.
Description
技术领域technical field
本发明属于电化学电池技术领域,具体涉及一种锂硫电池柔性高硫负载自修复正极结构及其制备方法。The invention belongs to the technical field of electrochemical batteries, and in particular relates to a flexible high-sulfur-loaded self-repairing positive electrode structure of a lithium-sulfur battery and a preparation method thereof.
背景技术Background technique
目前移动电子产品将向着轻薄且具有柔性的方向发展,在不远的未来可能将大规模使用可穿戴性的电子产品。与之相适应,作为下一代柔性电子产品的电源,以柔性锂离子电池为代表的高性能柔性储能器件的研究与开发越来越受到广泛重视。当前商品化锂离子电池主要使用钴酸锂、锰酸锂及磷酸亚铁锂等正极材料,但这些电极材料组装成的锂离子电池质量比能量密度一般低于200Wh/kg。另外,传统锂离子电池无论是从制备工艺还是电池本身都很难以满足柔性要求,这是因为弯折、扭转等变形过程会造成电极材料从集流体上脱落而影响电池性能,甚至可能会将隔膜刺穿,导致电池短路。而锂硫电池具有高达2600Wh/Kg的理论比能量密度和高达1675mAh/g理论比容量,如能同时实现锂硫电池的柔性化,则对柔性电子产品的发展具有重要意义。At present, mobile electronic products will be developed in a thin and flexible direction, and wearable electronic products may be used on a large scale in the near future. Correspondingly, as the power source of next-generation flexible electronic products, the research and development of high-performance flexible energy storage devices represented by flexible lithium-ion batteries have attracted more and more attention. The current commercial lithium-ion batteries mainly use positive electrode materials such as lithium cobaltate, lithium manganate and lithium iron phosphate, but the mass specific energy density of lithium-ion batteries assembled from these electrode materials is generally lower than 200Wh/kg. In addition, it is difficult for traditional lithium-ion batteries to meet the flexibility requirements in terms of the preparation process and the battery itself. This is because deformation processes such as bending and torsion will cause the electrode material to fall off from the current collector and affect battery performance, and may even damage the separator. puncture, causing a short circuit in the battery. Lithium-sulfur batteries have a theoretical specific energy density of up to 2600Wh/Kg and a theoretical specific capacity of up to 1675mAh/g. If the flexibility of lithium-sulfur batteries can be realized at the same time, it will be of great significance to the development of flexible electronic products.
锂硫电池的组成包括硫正极、锂负极、集流体、聚合物隔膜、电解液及封装等。其中硫电极是决定锂硫电池电化学性能的关键因素之一,虽然单质硫价格低廉,产量丰富,安全无毒,环境友好,但是其在室温是电子和离子的绝缘体,限制了锂硫电池的大倍率放电并且电化学反应中间产物多硫化物易溶解于电解液而发生穿梭效应,降低硫的利用率、比容量和电池的循环性能。目前通常采用聚合物包覆硫、金属氧化物或碳材料与硫复合等等,来提高锂硫电池性能。但是会造成活性物质硫在整个电极中的质量分数下降,在制成锂硫电池的正极极片后活性物质面密度降低等,进而不能体现其高比容量与高比能量密度的优势,从而限制了锂硫电池的商业化应用。同时相关设计没有考虑锂硫电池在柔性电池中的应用,已报道的锂硫电极制备方法基本上是在金属铝箔上直接涂覆活性物质浆料。电极中活性物质与集流体经反复形变非常容易导致活性物质分离,破坏极片的完整性,因而造成锂硫电池器件性能急剧劣化。The composition of a lithium-sulfur battery includes a sulfur positive electrode, a lithium negative electrode, a current collector, a polymer separator, an electrolyte, and packaging. Among them, the sulfur electrode is one of the key factors that determine the electrochemical performance of lithium-sulfur batteries. Although elemental sulfur is cheap, abundant, safe, non-toxic, and environmentally friendly, it is an insulator of electrons and ions at room temperature, which limits the performance of lithium-sulfur batteries. High-rate discharge and polysulfide, an intermediate product of the electrochemical reaction, are easily dissolved in the electrolyte to cause a shuttle effect, which reduces the utilization rate of sulfur, specific capacity and cycle performance of the battery. At present, polymer-coated sulfur, metal oxides or carbon materials and sulfur composites are usually used to improve the performance of lithium-sulfur batteries. However, it will cause the mass fraction of the active material sulfur in the entire electrode to decrease, and the surface density of the active material will decrease after being made into the positive electrode sheet of the lithium-sulfur battery, etc., and then cannot reflect its advantages of high specific capacity and high specific energy density, thus limiting commercial application of lithium-sulfur batteries. At the same time, the relevant design does not consider the application of lithium-sulfur batteries in flexible batteries. The reported preparation method of lithium-sulfur electrodes is basically to directly coat the active material slurry on the metal aluminum foil. The repeated deformation of the active material and the current collector in the electrode can easily lead to the separation of the active material and damage the integrity of the pole piece, thus causing a sharp deterioration in the performance of the lithium-sulfur battery device.
由此可见,开发一种能够充分发挥锂硫电池能量密度优势并且兼顾柔性器件轻薄柔趋势,能够满足反复变形过程性能不发生变化,同时在发生一定不可逆变形也能够具有自修复功能电极的方法必将极大地推动锂硫电池进一步的商业化以及在柔性电子器件中的应用,具有巨大的工业应用背景和广阔的市场前景。It can be seen that it is necessary to develop an electrode that can give full play to the advantages of the energy density of lithium-sulfur batteries and take into account the trend of thinness and softness of flexible devices, which can meet the performance of repeated deformation without changing, and at the same time have a self-healing function after certain irreversible deformation. It will greatly promote the further commercialization of lithium-sulfur batteries and the application in flexible electronic devices, with a huge industrial application background and broad market prospects.
发明内容Contents of the invention
本发明的目的在于提出一种锂硫电池柔性高硫负载自修复正极及其制备方法。通过对锂硫电池组元分析,提出了一种三维柔性高硫负载自修复正极设计思路,将锂硫电池中正极铝箔集流体替换为石墨烯/高分子聚合物柔性泡沫,并将硫负载在该结构中。将硫/石墨烯/高分子聚合物柔性泡沫用于高能量锂硫二次电池,可提高硫正极中纯硫的含量,有效提高锂硫二次电池的能量密度,其中高分子聚合物提供力学强度和自修复功能,在发生非弹性变形后,虽然发生了分子链断裂,但仍可通过分子链中相关官能团再次发生交联反应而实现自修复的能力。柔性电极的设计也可以进而推动硫电极材料在柔性电子器件中的应用,且本方案具有操作简便、成本低、产率高和易于结构调控的特点。The purpose of the present invention is to propose a flexible high-sulfur-loaded self-repairing positive electrode of a lithium-sulfur battery and a preparation method thereof. Through the analysis of lithium-sulfur battery components, a three-dimensional flexible high-sulfur-loaded self-healing positive electrode design idea is proposed. The positive electrode aluminum foil current collector in lithium-sulfur battery is replaced by graphene/polymer flexible foam, and sulfur is loaded on the in the structure. The use of sulfur/graphene/polymer flexible foam for high-energy lithium-sulfur secondary batteries can increase the content of pure sulfur in the sulfur cathode and effectively increase the energy density of lithium-sulfur secondary batteries, in which the high-molecular polymer provides mechanical Strength and self-healing function. After inelastic deformation, although the molecular chain is broken, the self-repairing ability can still be realized through the cross-linking reaction of the relevant functional groups in the molecular chain. The design of flexible electrodes can also further promote the application of sulfur electrode materials in flexible electronic devices, and this scheme has the characteristics of simple operation, low cost, high yield and easy structure regulation.
本发明的技术方案是:Technical scheme of the present invention is:
一种锂硫电池柔性高硫负载自修复正极结构的制备方法,所述正极结构包括三维连通的石墨烯/高分子聚合物柔性泡沫和碳/硫活性物质层,其中:所述石墨烯/高分子聚合物柔性泡沫是由具有自修复能力的高分子聚合物层包覆三维连通的石墨烯泡沫而形成,所述石墨烯/高分子聚合物柔性泡沫内填充所述碳/硫活性物质层;该正极结构的制备包括如下步骤:A method for preparing a flexible high-sulfur-loaded self-healing positive electrode structure for a lithium-sulfur battery, the positive electrode structure includes a three-dimensionally connected graphene/polymer flexible foam and a carbon/sulfur active material layer, wherein: the graphene/high Molecular polymer flexible foam is formed by covering a three-dimensional interconnected graphene foam with a self-healing polymer layer, and the graphene/polymer flexible foam is filled with the carbon/sulfur active material layer; The preparation of the positive electrode structure comprises the following steps:
(1)高分子聚合物稀释液的配制:将高分子聚合物按照1:(1-50)的体积比例稀释于甲苯或乙酸乙酯得到高分子聚合物稀释液。(1) Preparation of high molecular polymer diluent: dilute the high molecular polymer with toluene or ethyl acetate according to the volume ratio of 1:(1-50) to obtain the high molecular polymer diluent.
(2)石墨烯/高分子聚合物柔性泡沫的制备:首先,将步骤(1)中所述高分子聚合物稀释液通过喷涂、旋涂或提拉浸渍的方式填充到包含金属基体的石墨烯泡沫中,然后在60-120℃条件下,高分子聚合物稀释液中的聚合物单体在石墨烯泡沫的孔隙中发生原位聚合反应,反应时间2h-12h,再去除金属基体后,即得到由具有自修复能力的高分子聚合物层包覆三维连通的石墨烯泡沫的石墨烯/高分子聚合物柔性泡沫,其中:所述的高分子聚合物主要是对石墨烯三维网络进行巩固保护,提高石墨烯三维网络的力学性能并使其具有自修复能力。(2) Preparation of graphene/high molecular polymer flexible foam: first, the high molecular polymer dilution solution described in step (1) is filled into the graphene containing metal matrix by spraying, spin coating or pulling impregnation. In the foam, under the condition of 60-120°C, the polymer monomer in the high molecular polymer diluent undergoes in-situ polymerization reaction in the pores of the graphene foam, the reaction time is 2h-12h, and after removing the metal matrix, that is Obtain the graphene/polymer flexible foam of the three-dimensional connected graphene foam covered by the high molecular polymer layer with self-healing ability, wherein: the high molecular polymer mainly consolidates and protects the graphene three-dimensional network , improve the mechanical properties of graphene three-dimensional network and make it have self-healing ability.
(3)填充碳/硫活性物质层:将碳/硫活性物质浆料采用刮刀均匀涂覆、抽滤或者直接填灌入步骤(2)中所得石墨烯/高分子聚合物柔性泡沫的孔隙中,然后在30-90℃干燥0.5-24h,从而在所述石墨烯/高分子聚合物柔性泡沫中填充碳/硫活性物质层,形成锂硫电池三维柔性高硫负载自修复正极。(3) Filling the carbon/sulfur active material layer: the carbon/sulfur active material slurry is uniformly coated with a scraper, suction filtered or directly filled into the pores of the graphene/polymer flexible foam obtained in step (2) , and then dried at 30-90°C for 0.5-24h, so that the graphene/polymer flexible foam is filled with a carbon/sulfur active material layer to form a three-dimensional flexible high-sulfur-loaded self-healing positive electrode of a lithium-sulfur battery.
步骤(1)中,所述高分子聚合物为甲基双苯基室温硫化硅橡胶、硅苯(联苯)撑硅氧烷聚合物、聚二甲基硅氧烷、正硅酸乙酯、二丁基二月硅酸锡、带有酰氨乙基咪唑啉酮(二酰氨乙基脲或二酰氨基四乙基三脲等)化学基团的氢键自修复聚合物、缺π电子的聚酰亚胺、以富π电子芘基封端的有机π-π堆叠自修复聚合物、乙烯-甲基丙烯酸共聚物、带有多硫基团的环氧化物自修复化合物和带有动态共价键的含有三硫酯单元的聚丙烯酸丁酯等中的一种或两种以上。In the step (1), the high molecular polymer is methyl bisphenyl room temperature vulcanized silicone rubber, silicone phenylene (biphenyl) siloxane polymer, polydimethylsiloxane, ethyl orthosilicate, Dibutyl tin dilaurate, hydrogen bond self-healing polymer with amidoethyl imidazolidinone (diamidoethylurea or diamidotetraethyltriurea, etc.) chemical groups, π-electron deficiency Polyimides, organic π-π stacked self-healing polymers terminated with π-electron-rich pyrenyl groups, ethylene-methacrylic acid copolymers, epoxy self-healing compounds with polysulfide groups, and dynamic copolymers One or more than two types of polybutyl acrylate containing trithioester units with valence bonds.
步骤(2)中,所述包含金属基体的石墨烯泡沫为三维全连通的网络结构,其制备过程为:以多孔金属为模板,采用化学气相沉积方法在金属基体表面生长一层石墨烯薄膜,得到包含金属基体的石墨烯泡沫;化学气相沉积反应过程中:碳源为甲烷、乙烷、乙烯、乙炔、苯、甲苯、环己烷、乙醇、甲醇、丙酮和一氧化碳中的一种或几种,碳源流速为1-100毫升/分钟;载气为氢气,或者载气为氢气与惰性气体的混合气(氢气体积比≥1/10),载气总流速为1-2000毫升/分钟;反应温度为500-1100℃,生长时间为1-60分钟,反应结束后冷却速度为5-600℃/分钟。采用的金属基体为泡沫镍、泡沫铜、泡沫铁或泡沫钴,其孔径分布在50-200PPI,面密度为50-1000g/m2。In step (2), the graphene foam comprising the metal substrate is a three-dimensional fully connected network structure, and its preparation process is: using porous metal as a template, a layer of graphene film is grown on the surface of the metal substrate by chemical vapor deposition, A graphene foam containing a metal matrix is obtained; during the chemical vapor deposition reaction: the carbon source is one or more of methane, ethane, ethylene, acetylene, benzene, toluene, cyclohexane, ethanol, methanol, acetone and carbon monoxide , the carbon source flow rate is 1-100 ml/min; the carrier gas is hydrogen, or the carrier gas is a mixture of hydrogen and inert gas (hydrogen volume ratio ≥ 1/10), and the total flow rate of the carrier gas is 1-2000 ml/min; The reaction temperature is 500-1100° C., the growth time is 1-60 minutes, and the cooling rate after the reaction is 5-600° C./min. The metal matrix used is nickel foam, copper foam, iron foam or cobalt foam, the pore size distribution is 50-200PPI, and the surface density is 50-1000g/m 2 .
步骤(2)中,通过喷涂、旋涂或提拉浸渍在包含金属基体的石墨烯泡沫中填充所述高分子聚合物稀释液。In step (2), the high molecular polymer diluent is filled in the graphene foam containing the metal matrix by spray coating, spin coating or pulling dipping.
步骤(2)中,采用金属基体的溶解液溶解去除多孔金属模板骨架(即金属基体),所述金属基体的溶解液为硫酸、盐酸、硝酸或氯化铁的水溶液,其浓度为0.1-5mol/L;溶解反应温度为20-90℃。In step (2), the porous metal template skeleton (i.e. the metal matrix) is dissolved and removed by the dissolving solution of the metal matrix, the dissolving solution of the metal matrix is an aqueous solution of sulfuric acid, hydrochloric acid, nitric acid or ferric chloride, and its concentration is 0.1-5mol /L; The dissolution reaction temperature is 20-90°C.
步骤(3)中所述碳/硫活性物质浆料是由单质硫、碳材料及粘结剂按照(4-8):(1-5):1的质量比例混合组成。将单质硫、碳材料及粘结剂混合的方式为机械混合、球磨或超声混合。所述碳材料为石墨、膨胀石墨、导电炭黑、中孔碳、微孔碳球、层次孔碳、活性碳、碳纳米管、碳纤维、富勒烯和石墨烯中的一种或几种,所述粘结剂为聚偏二氟乙烯(PVDF)、聚四氟乙烯(PTFE)、羧甲基纤维素钠(CMC)、聚乙烯醇(PVA)和改性丁苯橡胶(SBR)的一种或几种。The carbon/sulfur active material slurry in step (3) is composed of elemental sulfur, carbon material and binder mixed in a mass ratio of (4-8):(1-5):1. The way of mixing elemental sulfur, carbon material and binder is mechanical mixing, ball milling or ultrasonic mixing. The carbon material is one or more of graphite, expanded graphite, conductive carbon black, mesoporous carbon, microporous carbon sphere, hierarchical porous carbon, activated carbon, carbon nanotube, carbon fiber, fullerene and graphene, The binder is a combination of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA) and modified styrene-butadiene rubber (SBR). species or several.
本发明设计原理如下:Design principle of the present invention is as follows:
本发明设计和制备的锂硫电池柔性高硫负载自修复正极,集流体和活性物质实现了一体化,三维集流体可以有效提高与活性电极材料的接触,实现活性物质的高硫负载,并且其具有很强的电解液存储能力,可缩短了离子传输过程,显著提高了电池的综合性能。高分子聚合物保护层的涂覆在使石墨烯保持三维骨架的同时显著提高了整个电极的力学性能,使电极具有很好的柔韧性,并且采用自修复高分子聚合物原位聚合过程也可使得柔性锂硫电极具有一定程度的自修复功能,有效缓解反复变形过程中柔性电极的抗机械损伤能力。该锂硫电池三维柔性高硫负载正极制备过程简单、易控,可实现大量、低成本制备,具有极大的应用价值。The flexible high-sulfur load self-repairing positive electrode of the lithium-sulfur battery designed and prepared by the present invention integrates the current collector and the active material, and the three-dimensional current collector can effectively improve the contact with the active electrode material, realize the high sulfur load of the active material, and its It has a strong electrolyte storage capacity, which can shorten the ion transmission process and significantly improve the overall performance of the battery. The coating of the polymer protective layer can significantly improve the mechanical properties of the entire electrode while maintaining the three-dimensional skeleton of the graphene, so that the electrode has good flexibility, and the in-situ polymerization process of the self-healing polymer can also be used The flexible lithium-sulfur electrode has a certain degree of self-healing function, which can effectively alleviate the mechanical damage resistance of the flexible electrode during repeated deformation. The preparation process of the three-dimensional flexible high-sulfur-loaded positive electrode of the lithium-sulfur battery is simple and easy to control, and it can be prepared in large quantities at low cost, and has great application value.
本发明有益效果如下:The beneficial effects of the present invention are as follows:
1、本发明提出一种锂硫电池三维柔性高硫负载自修复正极及其制备方法。1. The present invention proposes a three-dimensional flexible high-sulfur-loaded self-healing cathode for a lithium-sulfur battery and a preparation method thereof.
2、本发明中石墨烯三维集流体可以有效提高与活性电极材料的接触,实现活性物质的高硫负载,保证锂硫电池高的电化学性能的同时提高了硫正极中纯硫的含量,有效提高了锂硫二次电池的活性物质面密度,展现出锂硫电池高比容量与高比能量密度的优势。2. The graphene three-dimensional current collector in the present invention can effectively improve the contact with the active electrode material, realize the high sulfur loading of the active material, ensure the high electrochemical performance of the lithium-sulfur battery, and increase the content of pure sulfur in the sulfur positive electrode, effectively The surface density of the active material of the lithium-sulfur secondary battery is improved, showing the advantages of high specific capacity and high specific energy density of the lithium-sulfur battery.
3、具有自修复能力高分子聚合物可以对石墨烯三维网络进行巩固保护,同时提高石墨烯三维网络的力学性能,使整个锂硫电池正极具有很好的柔韧性。3. High molecular polymers with self-healing ability can consolidate and protect the graphene three-dimensional network, and at the same time improve the mechanical properties of the graphene three-dimensional network, so that the entire lithium-sulfur battery positive electrode has good flexibility.
4、自修复机制应用于锂硫电池,特别是柔性锂硫电池,具有重要价值。具有一定程度的自我修复能力后,柔性电极在变形过程中,即使发生活性物质与基体材料的分离,其中自修复聚合物仍能够重新将活性物质与基体材料再次发生交联,因此器件的使用性能将会大幅度提高,可有效提高石墨烯柔性电极的可变形特性。4. The self-repair mechanism is of great value when applied to lithium-sulfur batteries, especially flexible lithium-sulfur batteries. With a certain degree of self-healing ability, during the deformation process of the flexible electrode, even if the separation of the active material and the matrix material occurs, the self-healing polymer can still cross-link the active material and the matrix material again, so the performance of the device It will be greatly improved, which can effectively improve the deformable characteristics of graphene flexible electrodes.
附图说明Description of drawings
图1为本发明石墨烯/高分子聚合物柔性泡沫的照片及其电子显微镜表征,图中:(a)具有自修复能力的石墨烯/高分子聚合物柔性泡沫的照片;(b)具有自修复能力的石墨烯/高分子聚合物柔性泡沫在弯曲状态下的照片;(c)低倍下具有自修复能力的石墨烯/高分子聚合物柔性泡沫的扫描电镜照片;(d)高倍下具有自修复能力的石墨烯/高分子聚合物柔性泡沫的扫描电镜照片。Fig. 1 is the photograph of graphene/high molecular polymer flexible foam of the present invention and its electron microscopy characterization, among the figure: (a) has the photo of the graphene/high molecular polymer flexible foam of self-healing ability; (b) has self-healing ability The photo of the graphene/polymer flexible foam with self-healing ability in the bending state; (c) the scanning electron micrograph of the graphene/polymer flexible foam with self-healing ability at low magnification; (d) the SEM image with self-healing ability at high magnification SEM image of self-healing graphene/polymer flexible foam.
图2为本发明锂硫电池三维柔性高硫负载自修复正极的照片及其电子显微镜表征,图中:(a)锂硫电池三维柔性高硫负载自修复正极的照片;(b)锂硫电池三维柔性高硫负载自修复正极在弯曲状态下的照片;(c)锂硫电池三维柔性高硫负载自修复正极的扫描电镜照片;(d)锂硫电池三维柔性高硫负载自修复正极截面的扫描电镜照片。Figure 2 is a photo of the three-dimensional flexible high-sulfur-loaded self-healing positive electrode of the lithium-sulfur battery of the present invention and its electron microscope characterization, in the figure: (a) a photo of the three-dimensional flexible high-sulfur-loaded self-healing positive electrode of the lithium-sulfur battery; (b) a lithium-sulfur battery The photo of the three-dimensional flexible high-sulfur loaded self-healing cathode in the bent state; (c) the scanning electron microscope photo of the three-dimensional flexible high-sulfur loaded self-healing cathode of the lithium-sulfur battery; (d) the cross-section of the three-dimensional flexible high-sulfur loaded self-healing cathode of the lithium-sulfur battery SEM photo.
图3为将本发明所得具有自修复能力的石墨烯/高分子聚合物柔性泡沫替换为商业用铝箔作为集流体,涂敷了活性物质(硫:导电炭黑:粘结剂重量比例为7:2:1)后的极片照片。Fig. 3 is that the Graphene/macromolecular polymer flexible foam with self-healing ability obtained by the present invention is replaced by commercial aluminum foil as current collector, coated with active material (sulfur: conductive carbon black: binder weight ratio is 7: 2:1) pole piece photo.
图4为使用本发明锂硫电池三维柔性高硫负载自修复正极在22000次弯曲拉伸下的电导率变化。Fig. 4 shows the change in conductivity of the three-dimensional flexible high-sulfur-loaded self-healing positive electrode of the lithium-sulfur battery of the present invention under 22,000 bending stretches.
图5为使用本发明所得锂硫电池三维柔性高硫负载自修复正极组装形成的锂硫电池结构示意图(1-电池壳顶盖;第一石墨烯薄膜层;2-泡沫镍;3-锂片;4-石墨烯薄膜层与聚合物层(Celegard2400)组成的复合薄膜;5-锂硫电池三维柔性高硫负载自修复正极;6-电池壳底盖)。5 is a schematic diagram of the structure of a lithium-sulfur battery formed by using the three-dimensional flexible high-sulfur load self-repairing positive electrode of the lithium-sulfur battery obtained in the present invention (1-the top cover of the battery case; the first graphene film layer; 2-nickel foam; 3-lithium sheet ; 4-composite film composed of graphene film layer and polymer layer (Celegard2400); 5-three-dimensional flexible high-sulfur loading self-healing positive electrode of lithium-sulfur battery; 6-battery case bottom cover).
图6为本发明所得锂硫电池三维柔性高硫负载自修复正极在不同电流密度下倍率性能曲线。Fig. 6 is the rate performance curve of the three-dimensional flexible high-sulfur-loaded self-healing cathode of the lithium-sulfur battery obtained in the present invention at different current densities.
图7为本发明所得锂硫电池三维柔性高硫负载自修复正极(实施例1,纯硫面密度为3.3mg/cm2)用于锂硫电池的500次循环性能曲线。Fig. 7 is a 500-cycle performance curve of the three-dimensional flexible high-sulfur-loaded self-healing positive electrode of the lithium-sulfur battery obtained in the present invention (Example 1, the areal density of pure sulfur is 3.3 mg/cm 2 ) used in the lithium-sulfur battery.
图8为本发明所得锂硫电池三维柔性高硫负载自修复正极(实施例2,纯硫面密度为6.1mg/cm2)用于锂硫电池的500次循环性能曲线。Fig. 8 is the 500-cycle performance curve of the three-dimensional flexible high-sulfur-loaded self-healing positive electrode of the lithium-sulfur battery obtained in the present invention (Example 2, the areal density of pure sulfur is 6.1 mg/cm 2 ) used in the lithium-sulfur battery.
具体实施方式Detailed ways
下面结合附图及实施例详述本发明。The present invention will be described in detail below in conjunction with the accompanying drawings and embodiments.
以下实施例中,采用CVD方法制备包含金属基体的石墨烯材料,具体如下:In the following examples, adopt CVD method to prepare the graphene material that comprises metal matrix, specifically as follows:
将泡沫金属放置于水平反应炉中,在氢气和氩气的气氛中加热至1000℃(加热过程中氢气和氩气流速分别为200和500毫升/分钟,升温速度为33℃/分钟),待炉温升至1000℃后热处理10分钟;热处理完成后通入甲烷、氢气和氩气的混合气体(气体流速分别为甲烷5毫升/分钟,氢气200毫升/分钟,氩气500毫升/分钟),开始生长石墨烯,生长时间为5分钟,生长结束后100℃/分钟的速度快速冷却,得到表面包覆石墨烯的泡沫镍。The metal foam is placed in a horizontal reaction furnace and heated to 1000°C in an atmosphere of hydrogen and argon (during the heating process, the flow rates of hydrogen and argon are 200 and 500 ml/min, respectively, and the heating rate is 33°C/min). Furnace temperature rises to 1000 ℃ after heat treatment for 10 minutes; Pass into the mixed gas of methane, hydrogen and argon after heat treatment is finished (gas flow rate is respectively methane 5 milliliters/minute, hydrogen 200 milliliters/minute, argon 500 milliliters/minute), Start to grow graphene, the growth time is 5 minutes, after the growth is finished, it is cooled rapidly at a speed of 100° C./min to obtain the nickel foam whose surface is coated with graphene.
实施例1:Example 1:
首先,将泡沫镍为模板(75毫米×75毫米×1.9毫米,其孔径分布约为110PPI,面密度约为300g/m2),采用CVD方法,得到表面包覆石墨烯的泡沫镍,生长石墨烯薄膜的平均厚度约为100nm。First, nickel foam is used as a template (75 mm × 75 mm × 1.9 mm, the pore size distribution is about 110PPI, and the surface density is about 300g/m 2 ), and the nickel foam coated with graphene on the surface is obtained by CVD method to grow graphite. The average thickness of the olefin film is about 100 nm.
然后,再将聚二甲基硅氧烷与二丁基二月硅酸锡固化剂按照(10:1)的体积比例稀释于乙酸乙酯得到高分子聚合物稀释液。通过提拉浸渍的方法将高分子聚合物稀释液涂覆于包覆石墨烯的泡沫镍上,放在80℃的烘箱里烘干固化6h。然后放入3mol/L盐酸溶液中,在80℃温度下反应12小时以溶解泡沫镍模板,最终得到具有自修复能力的石墨烯/高分子聚合物柔性泡沫。通过宏观照片可以看出,所得的石墨烯/高分子聚合物完整复制了泡沫金属模板的形貌与结构,如图1(a)所示,尺寸为75毫米×75毫米×1毫米,密度约为7.6mg/cm3,电导率约为416S/m。获得的石墨烯/高分子聚合物具有非常好的柔性,如图1(b)所示。通过扫描电子显微镜观察表明石墨烯/高分子聚合物结构连续完整无破损,高分子聚合物均匀地涂覆在石墨烯的表面,对石墨烯骨架起到了支撑作用,如图1(c)-1(d)所示。Then, the polydimethylsiloxane and the dibutyltin dilaurate curing agent were diluted in ethyl acetate according to the volume ratio of (10:1) to obtain a polymer diluent. The high molecular polymer dilution was coated on the graphene-coated nickel foam by pulling and impregnating, and dried and cured in an oven at 80°C for 6 hours. Then put it into 3mol/L hydrochloric acid solution, react at 80°C for 12 hours to dissolve the foamed nickel template, and finally obtain a graphene/polymer flexible foam with self-healing ability. It can be seen from the macroscopic photos that the obtained graphene/polymer completely replicates the morphology and structure of the metal foam template, as shown in Figure 1(a), with a size of 75 mm × 75 mm × 1 mm and a density of about It is 7.6mg/cm 3 , and the conductivity is about 416S/m. The obtained graphene/polymer has very good flexibility, as shown in Fig. 1(b). Observation by scanning electron microscopy shows that the graphene/polymer structure is continuous and intact, and the polymer is evenly coated on the surface of graphene, which supports the graphene skeleton, as shown in Figure 1(c)-1 (d) shown.
把硫:导电炭黑:粘结剂(聚偏二氟乙烯)以7:2:1重量比例混合形成的碳/硫活性物质浆料灌注于具有自修复能力的石墨烯/高分子聚合物柔性泡沫,在70℃下真空干燥,干燥的时间为12h,获得的锂硫电池三维柔性高硫负载自修复正极见图2(a),活性物质硫的面密度为3.3mg/cm2。填灌碳/硫活性物质后的锂硫电池正极仍具有很好的柔性,如图2(b)。从图2(c)-2(d)扫描电子显微照片可以看出,碳/硫活性物质均匀地分散在具有自修复能力的石墨烯/高分子聚合物柔性泡沫内。The carbon/sulfur active material slurry formed by mixing sulfur: conductive carbon black: binder (polyvinylidene fluoride) in a weight ratio of 7:2:1 is poured into the flexible graphene/polymer polymer with self-healing ability. The foam was vacuum-dried at 70°C for 12 hours. The three-dimensional flexible high-sulfur-loaded self-healing positive electrode of the obtained lithium-sulfur battery is shown in Figure 2(a). The surface density of the active material sulfur is 3.3mg/cm 2 . The lithium-sulfur battery positive electrode filled with carbon/sulfur active materials still has good flexibility, as shown in Figure 2(b). From the scanning electron micrographs in Fig. 2(c)-2(d), it can be seen that the carbon/sulfur active species are uniformly dispersed in the graphene/polymer flexible foam with self-healing ability.
在1秒/次的弯曲频率下测试其电导率的变化,经过22000次的弯曲,锂硫电池三维柔性高硫负载自修复正极的电导率非常稳定,一直维持在125S/m左右,如图4所示,显示出该电极结构在弯曲的情况下仍具有很好的电化学性能。The change in conductivity was tested at a bending frequency of 1 second per time. After 22,000 times of bending, the conductivity of the three-dimensional flexible high-sulfur load self-healing positive electrode of the lithium-sulfur battery is very stable and has been maintained at around 125S/m, as shown in Figure 4 As shown, it is shown that the electrode structure still has good electrochemical performance in the case of bending.
使用该电极结构设计组装形成的锂硫电池结构如图5所示。The lithium-sulfur battery structure formed by using this electrode structure design and assembly is shown in Figure 5.
图6为锂硫电池三维柔性高硫负载自修复正极在不同电流密度下倍率性能曲线,在300mA·g-1的电流密度下,首次放电容量可达1360mAh·g-1,在6000mA·g-1电流密度下放电容量超过550mAh·g-1,显示出了优越的倍率性能,经过倍率测试后继续在750mA·g-1电流密度下的容量仍然接近1100mAh·g-1,显示出了良好的电化学稳定性。在1500mA·g-1电流密度下循环500次后容量接近650mAh·g-1(见图7)显示出非常优异的循环性能。Figure 6 shows the rate performance curve of the three-dimensional flexible high-sulfur loaded self-healing positive electrode of lithium-sulfur battery at different current densities. At the current density of 300mA·g -1 , the initial discharge capacity can reach 1360mAh·g -1 , and at 6000mA ·g -1 1 The discharge capacity at the current density exceeds 550mAh·g -1 , showing excellent rate performance. After the rate test, the capacity at the current density of 750mA·g -1 is still close to 1100mAh·g -1 , showing good electrochemical stability. The capacity is close to 650mAh·g -1 after 500 cycles at a current density of 1500mA·g-1 ( see Figure 7), showing very excellent cycle performance.
实施例2Example 2
与实施例1不同之处在于:将硫:导电炭黑:粘结剂(聚偏二氟乙烯)以7:2:1重量比例混合形成的碳/硫活性物质浆料灌注于具有自修复能力的石墨烯/高分子聚合物柔性泡沫内,在70℃下真空干燥,干燥的时间为12h,获得的锂硫电池三维柔性高硫负载自修复正极见图2(a),活性物质硫的面密度提高为6.1mg/cm2。从锂硫电池三维柔性高硫负载自修复正极在不同电流密度下倍率性能曲线(图6),在300mA·g-1的电流密度下,首次放电容量可达1200mAh·g-1,在各个电流密度下的放电容量见图6,在6000mA·g-1电流密度下放电容量超过500mAh·g-1,显示出了优越的倍率性能,经过倍率测试后继续在750mA·g-1电流密度下的容量仍然接近1100mAh·g-1,显示出了良好的电化学稳定性。在1500mA·g-1电流密度下循环500次后容量仍然超过600mAh·g-1(见图8)显示出非常优异的循环性能。The difference from Example 1 is that the carbon/sulfur active material slurry formed by mixing sulfur: conductive carbon black: binder (polyvinylidene fluoride) in a weight ratio of 7:2:1 is poured into the The graphene/polymer flexible foam was vacuum-dried at 70°C for 12 hours. The three-dimensional flexible high-sulfur-loaded self-healing positive electrode of the lithium-sulfur battery was obtained as shown in Figure 2(a). The surface of the active material sulfur The density increase was 6.1 mg/cm 2 . From the rate performance curves of three-dimensional flexible high-sulfur-loaded self-healing cathodes of lithium-sulfur batteries at different current densities (Figure 6), at a current density of 300mA·g -1 , the initial discharge capacity can reach 1200mAh·g -1 , at each current density The discharge capacity under density is shown in Figure 6. The discharge capacity exceeds 500mAh·g -1 at a current density of 6000mA·g -1 , showing excellent rate performance. The capacity is still close to 1100mAh·g -1 , showing good electrochemical stability. The capacity still exceeds 600mAh·g -1 after 500 cycles at a current density of 1500mA·g-1 ( see Figure 8), showing very excellent cycle performance.
对比例1Comparative example 1
与实施例2不同之处在于:将具有自修复能力的石墨烯/高分子聚合物柔性泡沫替换为商业用铝箔,将硫:导电炭黑:粘结剂(聚偏二氟乙烯)以7:2:1重量比例混合形成的碳/硫活性物质浆料刮涂在铝箔上,使活性物质硫的面密度为6.2mg/cm2,在70℃下真空干燥12h,发现碳/硫活性物质层在铝箔上开裂,如图3所示。The difference from Example 2 is: the graphene/polymer flexible foam with self-healing ability is replaced with commercial aluminum foil, and sulfur: conductive carbon black: binder (polyvinylidene fluoride) is replaced by 7: The carbon/sulfur active material slurry formed by mixing 2:1 weight ratio was scraped on the aluminum foil, so that the surface density of the active material sulfur was 6.2mg/cm 2 , and dried in vacuum at 70°C for 12h, and the carbon/sulfur active material layer was found Crack on aluminum foil, as shown in Figure 3.
实施例3Example 3
与实施例1不同之处在于:The difference from Example 1 is:
将聚二甲基硅氧烷与二丁基二月硅酸锡替换为聚酰胺-聚酯共聚物以增强三维石墨烯网络的柔性并赋予一定的自修复特性。反应过程如下:二聚酸首先与二乙烯三胺混合,得到反应物末端为NH2的低聚物。然后低聚物(M-NH2t)与尿素反应,控制尿素的加入量和反应时间,将其用甲苯稀释后,通过喷涂的方法将稀释液涂覆于包覆石墨烯的泡沫镍上,放在80℃的烘箱里烘干固化10h。然后放入3mol/L盐酸溶液中,在80℃温度下反应12小时以溶解泡沫镍模板,可得到带有动态氢键的自修复的石墨烯/高分子聚合物柔性泡沫。Polydimethylsiloxane and dibutyltin dilaurate were replaced by polyamide-polyester copolymers to enhance the flexibility of the three-dimensional graphene network and impart certain self-healing properties. The reaction process is as follows: the dimer acid is first mixed with diethylenetriamine to obtain an oligomer with NH at the end of the reactant. Then the oligomer (M-NH 2 t) reacts with urea, controls the addition of urea and the reaction time, after it is diluted with toluene, by the method for spraying, diluent is coated on the nickel foam of coating graphene, Dry and cure in an oven at 80°C for 10 hours. Then put it into 3mol/L hydrochloric acid solution, and react at 80°C for 12 hours to dissolve the foamed nickel template, and a self-healing graphene/polymer flexible foam with dynamic hydrogen bonds can be obtained.
实施例4Example 4
与实施例1不同之处在于:将硫:导电炭黑:粘结剂(聚偏二氟乙烯)以7:2:1重量比例混合形成的碳/硫活性物质浆料灌注于具有自修复能力的石墨烯/高分子聚合物柔性泡沫内,在70℃下真空干燥,干燥的时间为12h,获得的锂硫电池三维柔性高硫负载自修复正极见图2(a),活性物质硫的面密度提高为9.1mg/cm2。从锂硫电池三维柔性高硫负载自修复正极在不同电流密度下倍率性能曲线(图6),在300mA·g-1的电流密度下,首次放电容量可达1450mAh·g-1,在各个电流密度下的放电容量见图6,在6000mA·g-1电流密度下放电容量超过450mAh·g-1,显示出了优越的倍率性能,经过倍率测试后继续在750mA·g-1电流密度下的容量仍然接近1100mAh·g-1,显示出了良好的电化学稳定性。The difference from Example 1 is that the carbon/sulfur active material slurry formed by mixing sulfur: conductive carbon black: binder (polyvinylidene fluoride) in a weight ratio of 7:2:1 is poured into the The graphene/polymer flexible foam was vacuum-dried at 70°C for 12 hours. The three-dimensional flexible high-sulfur-loaded self-healing positive electrode of the lithium-sulfur battery was obtained as shown in Figure 2(a). The surface of the active material sulfur The density increase was 9.1 mg/cm 2 . From the rate performance curves of three-dimensional flexible high-sulfur loaded self-healing cathodes of lithium-sulfur batteries at different current densities (Figure 6), at a current density of 300mA·g -1 , the initial discharge capacity can reach 1450mAh·g -1 , at each current density The discharge capacity under density is shown in Figure 6. The discharge capacity exceeds 450mAh·g -1 at a current density of 6000mA·g -1 , showing excellent rate performance. The capacity is still close to 1100mAh·g -1 , showing good electrochemical stability.
电化学性能测试:Electrochemical performance test:
分别将以上实施例的电极切片压片冲压成直径12mm的圆片后作为锂硫电池正极材料。所有电极片在惰性气氛手套箱中装配成2025型扣式电池,金属锂片为对电极,电解液为1mol/LLiTFSI/DOL+DME(其中,DOL和DME的体积比1:1,LiTFSI为双三氟甲基磺酸酰亚胺锂,DOL为1,3-二氧戊环,DME为乙二醇二甲醚),隔膜为石墨烯薄膜层与聚合物层(Celegard2400)组成的复合薄膜。电化学性能测试在武汉蓝电公司LandBT-1型测试仪对电池性能进行测试。本发明将活性物质-锂半电池中锂离子在活性材料中的嵌入过程称为充电,而锂离子在活性材料中的脱嵌过程称为放电。The electrode slices and pressed sheets of the above embodiments were respectively punched into discs with a diameter of 12 mm to be used as positive electrode materials for lithium-sulfur batteries. All the electrode sheets were assembled into a 2025-type button battery in an inert atmosphere glove box. Lithium trifluoromethanesulfonate imide, DOL is 1,3-dioxolane, DME is ethylene glycol dimethyl ether), and the diaphragm is a composite film composed of a graphene film layer and a polymer layer (Celegard2400). Electrochemical performance test The battery performance was tested on the LandBT-1 tester of Wuhan Landian Company. In the present invention, the intercalation process of lithium ions in the active material in the active material-lithium half battery is called charging, and the deintercalation process of lithium ions in the active material is called discharge.
上述结果表明,本发明锂硫电池正极设计用在锂硫电池中,实现了锂硫电池多组元一体化设计,制备过程简单高效。在保证锂硫电池优异的循环稳定性和倍率性能的同时提高了硫正极中纯硫的含量,有效提高了锂硫二次电池的活性物质面密度,展现出比容量与高比能量密度的优势,推进了锂硫电池的商业化应用,同时设计出具有自修复功能的柔性电极必将极大地推动锂硫电池在柔性电子器件中的应用,具有巨大的工业应用背景和广阔的市场前景。The above results show that the positive electrode of the lithium-sulfur battery of the present invention is designed to be used in the lithium-sulfur battery, realizing the multi-component integrated design of the lithium-sulfur battery, and the preparation process is simple and efficient. While ensuring the excellent cycle stability and rate performance of lithium-sulfur batteries, the content of pure sulfur in the sulfur cathode is increased, which effectively increases the active material surface density of lithium-sulfur secondary batteries, showing the advantages of specific capacity and high specific energy density. , promote the commercial application of lithium-sulfur batteries, and design flexible electrodes with self-healing function will greatly promote the application of lithium-sulfur batteries in flexible electronic devices, with a huge industrial application background and broad market prospects.
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