CN115241457A - Three-dimensional strip-shaped graphene compound conductive paste for metal ion battery - Google Patents

Three-dimensional strip-shaped graphene compound conductive paste for metal ion battery Download PDF

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CN115241457A
CN115241457A CN202210715221.1A CN202210715221A CN115241457A CN 115241457 A CN115241457 A CN 115241457A CN 202210715221 A CN202210715221 A CN 202210715221A CN 115241457 A CN115241457 A CN 115241457A
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CN115241457B (en
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范壮军
林月强
张苏
魏彤
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China University of Petroleum East China
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    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract

The invention provides a high-performance metal ion battery conductive slurry and a preparation method thereof. The method comprises the steps of obtaining three-dimensional banded graphene through a liquid nitrogen quenching method, mixing the three-dimensional banded graphene and conductive carbon black according to a certain proportion, and performing liquid phase ball milling in a dispersing agent to obtain the high-performance metal ion battery conductive slurry. The conductive paste combines a good space cross-linking network of three-dimensional strip graphene with excellent conductivity of conductive carbon black, and a 'surface-point'/'point-point' contact combination is constructed in an electrode, so that a novel conductive electrode system with a long-range bridging conductive network and a three-dimensional ion migration channel is realized, and a good synergistic effect is realized. The conductive paste has the advantages of simple preparation method, low raw material cost, excellent performance and good application value and prospect.

Description

一种用于金属离子电池的三维带状石墨烯复配导电浆料A three-dimensional ribbon graphene composite conductive paste for metal-ion batteries

技术领域technical field

本发明属于金属离子电池导电剂技术领域,具体涉及一种高性能金属离子电池导电浆料及其制备方法。The invention belongs to the technical field of metal ion battery conductive agents, and in particular relates to a high-performance metal ion battery conductive paste and a preparation method thereof.

背景技术Background technique

金属离子电池(锂离子电池、钠离子电池、钾离子电池等)是一种利用可以嵌入金属离子的化合物作为正负极电极材料,金属离子通过电解液来回穿梭实现能量储存与释放的储能装置。金属离子电池主要由正极、负极、隔膜、电解液、集流体和外壳等部分组成,其中正极和负极是整个电池的核心,其性能直接决定电池储能特性的优劣。电池正负极主要由活性物质、导电剂、粘结剂和集流体组成,其中电极中的活性物质主要用于储存金属离子,导电剂用来增强电极的电荷传输能力,促进电子在电极内部的传导,粘结剂将活性物质、导电剂和集流体牢牢粘结在一起以保证电极在充放电过程中的完整性。Metal-ion batteries (lithium-ion batteries, sodium-ion batteries, potassium-ion batteries, etc.) are an energy storage device that uses compounds that can intercalate metal ions as positive and negative electrode materials, and metal ions shuttle back and forth through the electrolyte to achieve energy storage and release. . Metal-ion batteries are mainly composed of positive electrodes, negative electrodes, separators, electrolytes, current collectors and shells. The positive and negative electrodes of the battery are mainly composed of active materials, conductive agents, binders and current collectors. The active materials in the electrodes are mainly used to store metal ions, and the conductive agents are used to enhance the charge transport capacity of the electrodes and promote the electron transfer inside the electrodes. Conductive, the binder firmly bonds the active material, conductive agent and current collector together to ensure the integrity of the electrode during charging and discharging.

导电剂虽然在金属离子电池组分中占比很少,但其对改善电池的倍率性能,协助活性材料充分发挥其容量和循环稳定性至关重要。传统导电剂主要为炭黑和乙炔黑。其微观形貌为十几到几十纳米的炭纳米粒子相互交联,在空间形成珊瑚状结构。传统导电剂与活性物质颗粒间主要通过“点-点”接触的方式来提高电极的导电性,充放电过程中易造成活性物质与导电剂间失去电接触,从而造成电极电化学性能的急剧衰减。近年来,新型多维导电剂如碳纳米管(ACS Nano 2021,15,6735-6746)和石墨烯导电剂(Nano Energy 2012,1,429-439;Journal of Energy Chemistry 2019,30,19-26)日益引起人们的关注。相较于传统零维导电剂,新型多维导电剂具有显著优势:1)导电剂与活性材料颗粒间的接触方式由“点-点”接触变为“线-点”(碳纳米管)及“面-点”(石墨烯)接触,增大接触面积,提升导电剂的使用效率;2)线型及面型导电剂有助于导电网络的构筑,提升电子/离子的传输效率。然而,碳纳米管及石墨烯直接用作导电剂时也存在一些关键问题,如碳纳米管的线性结构虽能使其与活性材料颗粒间构筑有效的点/线接触,其纯物理的接触方式使得两者间接触不够充分,导致其对电极的循环稳定性和倍率性能改善不明显;石墨烯的面状结构特性会在一定程度上阻碍金属离子的传输(尤其是在大电流下),影响电极材料的倍率性能。Although conductive agents account for a small proportion of metal-ion battery components, they are crucial for improving the rate performance of batteries and assisting active materials to fully exert their capacity and cycle stability. The traditional conductive agents are mainly carbon black and acetylene black. Its microscopic morphology is that carbon nanoparticles of ten to several tens of nanometers are cross-linked with each other, forming a coral-like structure in space. The traditional conductive agent and the active material particles mainly improve the conductivity of the electrode through "point-to-point" contact. During the charging and discharging process, it is easy to cause the loss of electrical contact between the active material and the conductive agent, resulting in a sharp decline in the electrochemical performance of the electrode. . In recent years, new multi-dimensional conductive agents such as carbon nanotubes (ACS Nano 2021, 15, 6735-6746) and graphene conductive agents (Nano Energy 2012, 1, 429-439; Journal of Energy Chemistry 2019, 30, 19-26) have increasingly attracted people's attention. Compared with the traditional zero-dimensional conductive agent, the new multi-dimensional conductive agent has significant advantages: 1) The contact mode between the conductive agent and the active material particles has changed from "point-point" contact to "line-point" (carbon nanotubes) and " Surface-to-point" (graphene) contact increases the contact area and improves the efficiency of the use of conductive agents; 2) Line-type and surface-type conductive agents contribute to the construction of conductive networks and improve the transmission efficiency of electrons/ions. However, there are also some key problems when carbon nanotubes and graphene are directly used as conductive agents. The contact between the two is insufficient, resulting in the insignificant improvement of the cycle stability and rate performance of the electrode; the planar structure of graphene will hinder the transport of metal ions to a certain extent (especially under high current), affecting the Rate capability of electrode materials.

申请人自研的三维带状石墨烯结构(专利授权号:CN105947973B)由石墨烯纳米条带在空间上交联而成。经本工作研究发现,三维带状石墨烯用作金属离子电池导电剂时,其独特的神经网络状多触角结构能够将活性材料紧紧地包裹在一起,有效防止了充放电过程中电极的“失电”及活性材料的结构粉碎。同时,三维带状结构能够提供连续的三维导电网络,提升电极中电子/离子的传输效率。且相比于石墨烯,组成三维带状石墨烯结构的石墨烯纳米带具有大的长径比,对金属离子的传输位阻大大减小。The three-dimensional ribbon graphene structure (patent authorization number: CN105947973B) developed by the applicant is formed by spatially cross-linking graphene nanoribbons. In this work, it was found that when three-dimensional ribbon graphene is used as a conductive agent for metal-ion batteries, its unique neural network-like multi-antenna structure can tightly wrap the active materials together, effectively preventing the "electrode" during charging and discharging. Loss of electricity” and structural crushing of the active material. At the same time, the three-dimensional ribbon structure can provide a continuous three-dimensional conductive network and improve the electron/ion transport efficiency in the electrode. And compared with graphene, the graphene nanoribbons forming the three-dimensional ribbon graphene structure have a large aspect ratio, and the steric hindrance to the transport of metal ions is greatly reduced.

将三维带状石墨烯结构与传统导电炭黑进行复配构筑高性能金属离子电池导电浆料(图1),将三维带状石墨烯结构良好的空间交联网络与导电炭黑优异的导电性相结合,改变传统导电剂与活性材料间单纯依靠短程“点-点”接触及导电剂利用率不足的劣势,在电极内部构筑“面-点”/“点-点”接触结合,具有长程桥连导电网络和三维离子迁移通道的新型导电电极体系,实现良好的协同效应,从而提升电极中电子/离子的传输效率和电极的稳定性,几种典型的导电剂性能对比如表1所示。The three-dimensional ribbon graphene structure and traditional conductive carbon black are compounded to construct a high-performance metal-ion battery conductive paste (Figure 1). Combined, the disadvantage of simply relying on short-range "point-point" contact and insufficient utilization of conductive agent between traditional conductive agents and active materials is changed, and a "surface-point"/"point-point" contact combination is constructed inside the electrode, with long-range bridges The new conductive electrode system connecting the conductive network and the three-dimensional ion migration channel achieves a good synergistic effect, thereby improving the electron/ion transmission efficiency in the electrode and the stability of the electrode. The performance comparison of several typical conductive agents is shown in Table 1.

表1不同导电剂的性能对比Table 1 Performance comparison of different conductive agents

Figure BDA0003707531890000021
Figure BDA0003707531890000021

发明内容SUMMARY OF THE INVENTION

本发明的目的之一是构筑一种高性能金属离子电池导电浆料。本发明的目的之二是提供一种高性能金属离子电池导电浆料的制备方法。One of the objectives of the present invention is to construct a high-performance metal ion battery conductive paste. The second purpose of the present invention is to provide a preparation method of a high-performance metal ion battery conductive paste.

本发明的高性能金属离子电池导电浆料由三维带状石墨烯、导电炭黑、液体分散介质和分散助剂混合制备而成。所述导电浆料中固体质量占比为30%~90%,固体中三维带状石墨烯质量比为a,炭黑质量比为b,a+b=100%,5%≤a≤90%。The high-performance metal ion battery conductive paste of the present invention is prepared by mixing three-dimensional ribbon graphene, conductive carbon black, a liquid dispersion medium and a dispersion aid. The mass ratio of solid in the conductive paste is 30% to 90%, the mass ratio of three-dimensional ribbon graphene in the solid is a, and the mass ratio of carbon black is b, a+b=100%, 5%≤a≤90% .

进一步地,所述三维带状石墨烯的制备按照我们已经授权的专利进行(专利授权号:CN105947973B),具体制备参数条件略有调整:采用改进的Hummers法制备氧化石墨烯分散液,溶剂为去离子水,氧化石墨烯分散液浓度为0.3mg/mL,然后将氧化石墨烯分散液喷到液氮中,速率为5mL/min,冷冻干燥并在氮气保护下热处理得到三维带状石墨烯,热处理温度范围为250-1200℃,热处理时间为0.2-10h。Further, the preparation of the three-dimensional ribbon graphene is carried out according to the patent we have authorized (patent authorization number: CN105947973B), and the specific preparation parameters are slightly adjusted: the improved Hummers method is used to prepare the graphene oxide dispersion, and the solvent is to remove Ionized water, the concentration of graphene oxide dispersion is 0.3mg/mL, then the graphene oxide dispersion is sprayed into liquid nitrogen at a rate of 5mL/min, freeze-dried and heat treated under nitrogen protection to obtain three-dimensional ribbon graphene, heat treatment The temperature range is 250-1200℃, and the heat treatment time is 0.2-10h.

进一步地,所述高性能金属离子电池导电浆料的制备方法,首先称取特定比例的三维带状石墨烯和炭黑,将上述三维带状石墨烯和炭黑在溶剂中均匀分散,分散方法可以是高速搅拌、超声处理、液相研磨、高速匀浆中的一种或几种联合使用,其中高速搅拌的分散速度为300~12000转/分钟,超声处理频率为40kHz,超声输出功率为60~600W,液相研磨球料质量比为5:1,分散时间为10-2400分钟,将获得分散液真空抽滤得到预混料,将预混料加入到合适的液体分散介质中并添加一定量的分散助剂,液相球磨10-2400分钟后制得高性能金属离子电池导电浆料。Further, the preparation method of the high-performance metal-ion battery conductive paste is to first weigh a specific proportion of three-dimensional ribbon graphene and carbon black, and uniformly disperse the above three-dimensional ribbon graphene and carbon black in a solvent. It can be used in combination of one or more of high-speed stirring, ultrasonic treatment, liquid phase grinding, and high-speed homogenization, wherein the dispersing speed of high-speed stirring is 300-12000 rpm, the ultrasonic processing frequency is 40 kHz, and the ultrasonic output power is 60 ~600W, the mass ratio of liquid phase grinding balls is 5:1, and the dispersion time is 10-2400 minutes. The obtained dispersion liquid is vacuum filtered to obtain a premix, and the premix is added to a suitable liquid dispersion medium and added to a certain amount. Amount of dispersing aid, liquid phase ball milling for 10-2400 minutes to obtain high-performance metal ion battery conductive paste.

本发明主要有以下有益效果:The present invention mainly has the following beneficial effects:

本发明高性能金属离子电池导电浆料改变传统导电剂的短程“点-点”接触模式,在电极内部构筑“面-点”/“点-点”接触结合,具有长程桥连导电网络和三维离子迁移通道的新型导电电极体系。同时具有一定机械强度和韧性的三维带状石墨烯能够有效防止充放电过程中活性材料的“失电”及结构粉碎,提升电极体系的循环稳定性。本发明所提供的高性能金属离子电池导电浆料的制备方法,可实现金属离子电池高性能、长循环构筑,具有很好的应用价值和前景。The high-performance metal ion battery conductive paste of the present invention changes the short-range "point-point" contact mode of the traditional conductive agent, constructs a "surface-point"/"point-point" contact combination inside the electrode, and has a long-range bridging conductive network and a three-dimensional Novel conductive electrode systems for ion transport channels. At the same time, the three-dimensional ribbon-shaped graphene with certain mechanical strength and toughness can effectively prevent the "power loss" and structure crushing of the active material during the charging and discharging process, and improve the cycle stability of the electrode system. The preparation method of the high-performance metal ion battery conductive paste provided by the invention can realize the high performance and long cycle construction of the metal ion battery, and has good application value and prospect.

附图说明Description of drawings

图1高性能金属离子电池导电浆料的扫描电镜照片;Fig. 1 Scanning electron microscope photo of conductive paste for high performance metal ion battery;

图2使用本发明实验和对比例所制得的锂离子电池的循环性能对比图;Fig. 2 uses the cycle performance comparison diagram of the lithium ion battery that the experiment of the present invention and comparative example make;

图3使用本发明实验和对比例所制得的锂离子电池300圈充放电后的电化学阻抗谱对比图。FIG. 3 is a comparison diagram of electrochemical impedance spectra of lithium ion batteries prepared by using the experiment of the present invention and the comparative example after 300 cycles of charging and discharging.

具体实施方式Detailed ways

为了更加清楚地展示本发明的目的、技术方案及优势,下面结合附图及实施例说明本发明的实现过程。应当理解,此处所描述的具体实施例仅用于解释本发明,并不用于限定本发明。In order to more clearly demonstrate the objectives, technical solutions and advantages of the present invention, the implementation process of the present invention is described 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.

实施例1Example 1

使用高性能金属离子电池导电浆料制备Si基负极极片。Preparation of Si-based negative electrode using high-performance metal-ion battery conductive paste.

将10mg三维带状石墨烯和10mg炭黑在20mL乙醇中使用高速剪切匀浆机匀浆混合20min,真空抽滤并冷冻干燥,得到预混料,将上述预混料分散在5mL去离子水中并在500转/分钟的转速下液相球磨1h,制作成高性能金属离子电池导电浆料(图1)。将60mg纳米Si(颗粒直径分布区间为30~100nm),20mg海藻酸钠加入到上述制备的高性能金属离子电池导电浆料中,经过混浆/制浆/调浆/打浆过程制得电极浆料,再通过涂布、烘烤、辊压、模切工序制得Si基负极极片。在手套箱中将Si基负极极片与正负极壳、垫片、弹片、锂片、隔膜、电解液组装成扣式半电池并静置12h以保证电池内部充分浸润。Mix 10mg three-dimensional ribbon graphene and 10mg carbon black in 20mL of ethanol using a high-speed shear homogenizer for 20min, vacuum filter and freeze-dry to obtain a premix, which is dispersed in 5mL of deionized water. And liquid-phase ball milling at 500 r/min for 1 h to make a high-performance metal-ion battery conductive paste (Figure 1). 60mg of nano-Si (particle diameter distribution range is 30-100nm) and 20mg of sodium alginate are added to the conductive paste for high-performance metal ion batteries prepared above, and the electrode paste is prepared through the process of mixing/slurrying/mixing/beating Then, the Si-based negative pole piece is prepared through the processes of coating, baking, rolling and die-cutting. In the glove box, the Si-based negative electrode plate and the positive and negative electrode shell, gaskets, shrapnel, lithium plate, diaphragm, and electrolyte were assembled into a button-type half-cell and left for 12 hours to ensure that the inside of the battery was fully infiltrated.

对比例1Comparative Example 1

使用炭黑作为导电剂制备Si基负极极片。The Si-based negative pole piece was prepared using carbon black as the conductive agent.

将60mg纳米Si(颗粒直径分布区间为30~100nm),20mg炭黑和20mg海藻酸钠混合均匀并在5mL去离子水中以500转/分钟的转速液相球磨1h,经过混浆/制浆/调浆/打浆过程制得电极浆料,再通过涂布、烘烤、辊压、模切工序制得对比例Si基负极极片。在手套箱中将对比例Si基负极极片与正负极壳、垫片、弹片、锂片、隔膜、电解液组装成纽扣半电池并静置12h以保证电池内部充分浸润。Mix 60mg of nano-Si (with a particle diameter distribution range of 30-100nm), 20mg of carbon black and 20mg of sodium alginate and ball-milled in 5mL of deionized water at a speed of 500 rpm for 1h. The electrode slurry was prepared by the slurry mixing/beating process, and then the Si-based negative pole piece of the comparative example was prepared through the processes of coating, baking, rolling and die-cutting. In a glove box, the comparative Si-based negative electrode piece and the positive and negative electrode shell, gasket, shrapnel, lithium piece, diaphragm, and electrolyte were assembled into a button half-cell and left for 12 hours to ensure that the inside of the battery was fully infiltrated.

实施例2Example 2

使用高性能金属离子电池导电浆料制备磷酸铁锂基正极极片。Lithium iron phosphate-based positive electrode sheets were prepared using high-performance metal-ion battery conductive paste.

将5mg三维带状石墨烯和5mg炭黑在10mL乙醇中使用高速剪切匀浆机匀浆混合20min,真空抽滤并冷冻干燥,得到预混料,将上述预混料分散在5mL N-甲基吡咯烷酮(NMP)中并在500转/分钟的转速下液相球磨1h,制作成高性能金属离子电池导电浆料。将80mg磷酸铁锂,10mg聚偏氟乙烯(PVDF)加入到上述制备的高性能金属离子电池导电浆料中,经过混浆/制浆/调浆/打浆过程制得电极浆料,再通过涂布、烘烤、辊压、模切工序制得磷酸铁锂基正极极片。在手套箱中将磷酸铁锂基正极极片与正负极壳、垫片、弹片、锂片、隔膜、电解液组装成扣式半电池并静置12h以保证电池内部充分浸润。5mg three-dimensional ribbon graphene and 5mg carbon black were mixed in 10mL ethanol using a high-speed shear homogenizer for 20min, vacuum filtered and freeze-dried to obtain a premix, and the above premix was dispersed in 5mL N-formaldehyde. pyrrolidone (NMP) and liquid-phase ball milling at 500 r/min for 1 h to make a high-performance metal-ion battery conductive paste. 80mg of lithium iron phosphate and 10mg of polyvinylidene fluoride (PVDF) were added to the above-prepared conductive paste for high-performance metal ion batteries, and the electrode paste was prepared through the process of mixing/slurrying/sizing/beating, and then by coating The process of cloth, baking, rolling and die-cutting obtains the lithium iron phosphate-based positive pole piece. In the glove box, the lithium iron phosphate-based positive electrode piece and the positive and negative electrode shell, gasket, shrapnel, lithium piece, diaphragm, and electrolyte were assembled into a button-type half-cell and left for 12 hours to ensure that the inside of the battery was fully infiltrated.

对比例2Comparative Example 2

使用炭黑作为导电剂制备磷酸铁锂基正极极片。Lithium iron phosphate-based positive electrode sheets were prepared using carbon black as a conductive agent.

将80mg磷酸铁锂,10mg炭黑和10mg聚偏氟乙烯(PVDF)混合均匀并在5mL N-甲基吡咯烷酮(NMP)中以500转/分钟的转速液相球磨1h,经过混浆/制浆/调浆/打浆过程制得电极浆料,再通过涂布、烘烤、辊压、模切工序制得对比例磷酸铁锂基正极极片。在手套箱中将对比例磷酸铁锂基负极极片与正负极壳、垫片、弹片、锂片、隔膜、电解液组装成纽扣半电池并静置12h以保证电池内部充分浸润。80mg lithium iron phosphate, 10mg carbon black and 10mg polyvinylidene fluoride (PVDF) were mixed uniformly and ball-milled in 5mL N-methylpyrrolidone (NMP) at 500 rpm for 1h in liquid phase, after mixing/slurrying Electrode slurry was prepared in the process of mixing/sizing/beating, and then through the processes of coating, baking, rolling, and die-cutting to prepare a lithium iron phosphate-based positive electrode piece of comparative example. In the glove box, the comparative lithium iron phosphate-based negative pole piece and the positive and negative pole shell, gasket, shrapnel, lithium piece, diaphragm, and electrolyte were assembled into a button half-cell and left for 12 hours to ensure that the inside of the battery was fully infiltrated.

将上述四种纽扣半电池进行电化学性能测试,具体测试步骤及结果如下所述:The electrochemical performance tests of the above four button half-cells are carried out, and the specific test steps and results are as follows:

对实施例和对比例所制得的纽扣式半电池进行电化学循环性能测试,先在0.5A/g电流密度下激活5圈,再在1A/g电流密度下进行循环性能测试,电化学循环性能对比结果如图2所示。发现在1A/g下充放电循环300圈后,对比例1的容量保持率只有24.3%,而实施例1的容量保持率高达69.3%,且300圈充放电后电极容量仍高达1031.4mAh/g。通过研究电极在300圈充放电后的电化学阻抗(EIS)谱,我们发现300圈循环后实施例1电极仍然保持了较低的界面电阻和良好的电子/离子传输性能,相反对比例1电极在循环后界面电阻变大,电子/离子传输性能变差。我们认为三维带状石墨烯包裹活性Si颗粒的结构避免了Si颗粒与电解液的直接接触,降低了界面副反应的产生,同时三维带状石墨烯的加入有助于在其表面形成一层质薄且稳定的固体电解质(SEI)膜,避免了传统纯炭黑电极中形成的厚SEI膜对电子/离子传输的影响和对电解液的持续消耗。The electrochemical cycle performance test was carried out on the button-type half-cells prepared in the examples and comparative examples. First, they were activated for 5 cycles at a current density of 0.5A/g, and then the cycle performance test was carried out at a current density of 1A/g. The performance comparison results are shown in Figure 2. It was found that after 300 cycles of charge and discharge at 1A/g, the capacity retention rate of Comparative Example 1 was only 24.3%, while that of Example 1 was as high as 69.3%, and the electrode capacity was still as high as 1031.4mAh/g after 300 cycles of charge and discharge. . By studying the electrochemical impedance (EIS) spectrum of the electrode after 300 cycles of charge and discharge, we found that the electrode of Example 1 still maintained a low interfacial resistance and good electron/ion transport performance after 300 cycles of cycling, on the contrary to the electrode of Comparative Example 1. The interfacial resistance becomes larger after cycling, and the electron/ion transport performance deteriorates. We believe that the structure of 3D ribbon-shaped graphene-wrapped active Si particles avoids the direct contact between Si particles and the electrolyte and reduces the generation of interfacial side reactions, and the addition of 3D ribbon-shaped graphene helps to form a layer of quality The thin and stable solid electrolyte (SEI) film avoids the influence of thick SEI film formed in conventional pure carbon black electrodes on electron/ion transport and continuous consumption of electrolyte.

表2放电比容量和循环性能结果对比Table 2 Comparison of discharge specific capacity and cycle performance results

项目project 首圈容量(mAh/g)First lap capacity (mAh/g) 300圈循环后容量保持率(%)Capacity retention rate after 300 cycles (%) 实施例1Example 1 21172117 6969 对比例1Comparative Example 1 18241824 24twenty four 实施例2Example 2 173173 98%98% 对比例2Comparative Example 2 169169 94%94%

特别说明,本领域的技术人员应该认识到,以上实施例仅用于说本发明,并不用于限定本发明。只要在本发明说明的范围内,对以上实施例的变化、变形都将属于本发明的保护范围。In particular, those skilled in the art should realize that the above embodiments are only used to illustrate the present invention, but not to limit the present invention. As long as they are within the scope of the description of the present invention, changes and modifications to the above embodiments will fall within the protection scope of the present invention.

Claims (3)

1. A high-performance metal ion battery conductive paste is characterized in that: the graphene material is prepared by mixing three-dimensional banded graphene, conductive carbon black, a liquid dispersion medium and a dispersion auxiliary agent.
2. The high-performance metal-ion battery conductive paste of claim 1, wherein: the mass ratio of the solid is 30-90%, the mass ratio of the three-dimensional strip graphene in the solid is a, the mass ratio of the conductive carbon black is b, a + b =100%, and a is more than or equal to 5% and less than or equal to 90%; the conductive carbon black is one or more of commercially available conductive acetylene black, super P conductive carbon black and Ketjen black; the liquid dispersion medium consists of a solvent and a dispersion auxiliary agent, wherein the solvent can be one or more of deionized water, N-methyl pyrrolidone, N-dimethyl amide and dimethyl sulfoxide for combined use, the dispersion auxiliary agent is one or more of polyvinylpyrrolidone, polyacrylamide, sodium dodecyl sulfate and ethanol for combined use, and the mass percentage of the dispersion auxiliary agent in the liquid dispersion medium is 0-2.0%.
3. A preparation method of high-performance metal ion battery conductive slurry is characterized by comprising the following steps: 1) Obtaining three-dimensional strip-shaped graphene through a liquid nitrogen quenching method and heat treatment, wherein the three-dimensional strip-shaped graphene is formed by spatially crosslinking graphene strips, the length range of the graphene strips is 0.1-200 mu m, the width range of the graphene strips is 0.01-1 mu m, the heat treatment temperature range is 250-1200 ℃, and the heat treatment time is 0.2-10h; 2) Weighing three-dimensional strip graphene and conductive carbon black in a specific ratio; 3) Uniformly dispersing the three-dimensional banded graphene and the conductive carbon black in a solvent, wherein the dispersion method can be one or more of high-speed stirring, ultrasonic treatment and liquid-phase grinding, the high-speed stirring dispersion speed is 300-12000 r/min, the ultrasonic treatment frequency is 40kHz, the ultrasonic output power is 60-600W, and the liquid-phase grinding ball material mass ratio is 5:1, dispersing for 10-2400 minutes; 4) And carrying out vacuum filtration on the obtained dispersion liquid to obtain a premix, adding the premix into a proper liquid dispersion medium, adding a certain amount of dispersing auxiliary agent, and carrying out liquid phase ball milling for 10-2400 minutes to obtain the high-performance metal ion battery conductive slurry.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105932287A (en) * 2016-05-24 2016-09-07 宁波墨西科技有限公司 Graphene composite conductive agent and preparation method thereof
CN105947973A (en) * 2016-06-16 2016-09-21 哈尔滨工程大学 Tentacle-type graphene nanostructure unit, graphene-based composite material with topological structure and preparation method
CN106784827A (en) * 2016-12-19 2017-05-31 中国科学院电工研究所 Mesoporous graphene conductive slurry and Preparation method and use
CN109903931A (en) * 2019-02-25 2019-06-18 天津艾克凯胜石墨烯科技有限公司 A kind of preparation method of high dispersive graphene composite conductive slurry
CN110391418A (en) * 2018-04-18 2019-10-29 常州墨之萃科技有限公司 A kind of High-performance graphene composite conducting slurry and preparation method thereof
CN112331380A (en) * 2020-11-03 2021-02-05 松山湖材料实验室 Composite conductive slurry and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105932287A (en) * 2016-05-24 2016-09-07 宁波墨西科技有限公司 Graphene composite conductive agent and preparation method thereof
CN105947973A (en) * 2016-06-16 2016-09-21 哈尔滨工程大学 Tentacle-type graphene nanostructure unit, graphene-based composite material with topological structure and preparation method
CN106784827A (en) * 2016-12-19 2017-05-31 中国科学院电工研究所 Mesoporous graphene conductive slurry and Preparation method and use
CN110391418A (en) * 2018-04-18 2019-10-29 常州墨之萃科技有限公司 A kind of High-performance graphene composite conducting slurry and preparation method thereof
CN109903931A (en) * 2019-02-25 2019-06-18 天津艾克凯胜石墨烯科技有限公司 A kind of preparation method of high dispersive graphene composite conductive slurry
CN112331380A (en) * 2020-11-03 2021-02-05 松山湖材料实验室 Composite conductive slurry and preparation method and application thereof

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