WO2020253318A1 - 单层还原氧化石墨烯钴酸锂复合材料及其制备方法和用途 - Google Patents

单层还原氧化石墨烯钴酸锂复合材料及其制备方法和用途 Download PDF

Info

Publication number
WO2020253318A1
WO2020253318A1 PCT/CN2020/082487 CN2020082487W WO2020253318A1 WO 2020253318 A1 WO2020253318 A1 WO 2020253318A1 CN 2020082487 W CN2020082487 W CN 2020082487W WO 2020253318 A1 WO2020253318 A1 WO 2020253318A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene oxide
layer
lithium
reduced graphene
composite material
Prior art date
Application number
PCT/CN2020/082487
Other languages
English (en)
French (fr)
Inventor
沈文卓
晁丹丹
吴宏超
丘海东
孙卫山
Original Assignee
中兴通讯股份有限公司
上海交通大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 中兴通讯股份有限公司, 上海交通大学 filed Critical 中兴通讯股份有限公司
Publication of WO2020253318A1 publication Critical patent/WO2020253318A1/zh

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Definitions

  • This application relates to but not limited to the field of electrochemistry, and specifically relates to but not limited to a single-layer reduced graphene oxide lithium cobalt oxide composite material and its preparation method and application.
  • lithium-ion batteries As an energy storage device with excellent performance, lithium-ion batteries have been widely used in civil products such as electric vehicles, daily electronic products, and static energy storage power stations. However, due to the limitation of key battery materials, most lithium-ion batteries currently cannot fully meet the actual needs of the various devices and devices mentioned above. As one of the key materials of lithium-ion batteries, lithium cobalt oxide cathode materials have major problems in practical applications: low specific energy density and poor charging and discharging performance at high current density.
  • This application provides a method for preparing lithium cobalt oxide composite materials for lithium ion batteries by using single-layer graphene oxide.
  • the method has a simple process.
  • the single-layer reduction oxidation The graphene and lithium cobalt oxide have a high degree of bonding and good uniformity.
  • This application provides a method for preparing a single-layer reduced graphene oxide lithium cobalt oxide composite material, which includes: preparing an aqueous solution of single-layer graphene oxide; adding lithium cobalt oxide to the aqueous solution of single-layer graphene oxide; Spray drying to obtain the composite material.
  • the application also provides a single-layer reduced graphene oxide lithium cobalt oxide composite material, which is prepared by the above method.
  • the application also provides the use of a single-layer reduced graphene oxide lithium cobalt oxide composite material as a positive electrode active material of a lithium ion battery.
  • the present application also provides a lithium ion battery.
  • the positive electrode of the lithium ion battery may include a binder, a conductive agent, and the foregoing single-layer reduced graphene oxide lithium cobalt oxide composite material.
  • the preparation method of the present application can form a complete, continuous and conductive single-layer reduced graphene oxide coating layer on the surface of the lithium cobalt oxide active material with a simple process.
  • the preparation method of the present application cleverly combines the mixing process of single-layer graphene oxide and lithium cobalt oxide with efficient spray drying technology, and is suitable for mass production of single-layer reduced graphene oxide lithium cobalt oxide composite materials.
  • the lithium ion battery prepared in this application has excellent rate discharge performance and cycle stability.
  • FIG. 1 is a field emission scanning electron microscope image of a conventional lithium cobalt oxide cathode active material.
  • FIG. 2 is a field emission scanning electron microscope image of a single-layer reduced graphene oxide lithium cobalt oxide composite material according to an embodiment of the application.
  • Fig. 3 is a cycle performance curve of a lithium-ion battery in a proportion of this application.
  • FIG. 4 is a cycle performance curve of a lithium ion battery according to an embodiment of the application.
  • Figure 5 is a ratio charge and discharge curve of a lithium-ion battery of the present application.
  • FIG. 6 is a rate charge and discharge curve of a lithium ion battery according to an embodiment of the application.
  • the embodiment of the application provides a method for preparing a single-layer reduced graphene oxide lithium cobalt oxide composite material, which includes: preparing an aqueous solution of single-layer graphene oxide; adding lithium cobalt oxide to the aqueous solution of single-layer graphene oxide; mixing uniformly After spray drying, a composite material is obtained.
  • the “reduced graphene oxide” in this application refers to the reduced graphene oxide obtained by partial thermal reduction reaction of a single layer of graphene oxide.
  • the embodiment of the application utilizes the good conductivity anisotropy of single-layer reduced graphene oxide and the structural characteristics of controllable curvature, and uses single-layer graphene oxide to coat the surface of the lithium cobalt oxide active material, and then perform partial thermal reduction on it.
  • a single-layer reduced graphene oxide lithium cobalt oxide composite material with a three-dimensional conductive network structure and good conductivity is constructed.
  • the preparation method of the embodiment of the present application can form a single-layer reduced graphene oxide coating layer with a single operation.
  • the process is simple, and there is no need to add organic solvents, surfactants, and reduction during the formation of the single-layer reduced graphene oxide coating layer.
  • Various additives such as oxidizer and oxidant have low production cost.
  • the preparation method of the embodiment of the present application combines the mixing process of single-layer graphene oxide and lithium cobalt oxide with spray drying technology.
  • the process is simple and is suitable for the large-scale lithium cobalt oxide composite material of single-layer reduced graphene oxide lithium ion battery. Mass production and manufacturing.
  • the mass ratio of single graphene oxide and water may be 1 ⁇ 10 -5: 1 ⁇ 50 ⁇ 10 -5: 1, for example, may be a 10 ⁇ 10 -5: 1,20 ⁇ 10 - 5 :1, 30 ⁇ 10 -5 :1, 40 ⁇ 10 -5 :1, 45 ⁇ 10 -5 :1, etc.
  • the mass ratio of single-layer graphene oxide to water is in the range of 1 ⁇ 10 -5 :1 ⁇ 50 ⁇ 10 -5 :1, the conductivity of lithium cobalt oxide can be greatly improved, and single-layer graphene oxide It can be uniformly dispersed in water, which is conducive to the full progress of the modification reaction.
  • the mass ratio of the aqueous solution of lithium cobaltate to the monolayer graphene oxide may be 0.01:1 to 0.5:1, for example, may be 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1 etc.
  • the coating layer can be formed well, and the coating layer is not prone to be too thick, which is more beneficial A single layer of reduced graphene oxide coating is formed.
  • mixing can be performed by means such as stirring.
  • the stirring speed may be 60 revolutions/min to 240 revolutions/min, for example, it may be 80 revolutions/min, 100 revolutions/min, 120 revolutions/min, 150 revolutions/min, 180 revolutions/min, 200 revolutions/min. Rotation/min, etc.; the stirring time can be 10min ⁇ 120min, for example, it can be 20min, 30min, 60min, 90min, etc.
  • spray drying can be performed under the condition that the outlet temperature is 150°C to 200°C, for example, it can be 160°C, 170°C, 180°C, 190°C, etc.; the feed flow rate can be 300mL/min ⁇ 800mL /min, for example, 400 mL/min, 500 mL/min, 600 mL/min, 700 mL/min, etc.
  • the outlet temperature of the spray drying process is 150°C to 200°C
  • the monolayer graphene oxide can be moderately thermally reduced, so that the prepared lithium cobalt oxide composite material has good conductivity.
  • the single-layer graphene oxide can be a commercially available single-layer graphene oxide, for example, it can be a single-layer graphene oxide purchased from Shanghai Carbon Source Huigu New Energy Technology Co., Ltd.
  • the single-layer reduced graphene oxide lithium cobalt oxide composite material prepared in the examples of this application has a continuous three-dimensional conductive structure, and the single-layer reduced graphene oxide is coated on the surface of the lithium cobalt oxide, thereby being active in the lithium cobalt oxide positive electrode.
  • a complete, continuous and conductive single-layer reduced graphene oxide coating layer is formed on the surface of the material, and a bridge connection is formed between the lithium cobalt oxide active materials.
  • the thickness of the coated single-layer reduced graphene oxide layer may be, for example, 0.34 nm.
  • the embodiments of the present application provide the use of a single-layer reduced graphene oxide lithium cobalt oxide composite material as a positive electrode active material of a lithium ion battery.
  • the embodiment of the present application provides a lithium ion battery, including: a positive electrode, a negative electrode, a separator, and an electrolyte.
  • the positive electrode includes a binder, a conductive agent, and the foregoing single-layer reduced graphene oxide lithium cobalt oxide composite material;
  • the negative electrode may be a carbon material , Metal oxide, metal or alloy, for example, it can be a metal lithium sheet.
  • the lithium ion battery has excellent rate discharge performance and cycle stability.
  • the binder can be selected from any one or more of various lithium ion battery binders such as polyvinylidene fluoride, sodium carboxymethyl cellulose, styrene-butadiene rubber and the like.
  • the conductive agent can be selected from any one or more of various lithium ion battery conductive agents such as acetylene black, carbon black, graphite, carbon nanotubes, and Ketjen black.
  • the mass ratio of the single-layer reduced graphene oxide lithium cobalt oxide composite material, the binder, and the conductive agent can be 80:10:10.
  • the positive electrode of the lithium-ion battery can be prepared by the following method: the single-layer reduced graphene oxide lithium cobalt oxide composite material, the binder, and the conductive agent are stirred in a solvent in proportion to uniformly form a slurry, and then coated on the surface of the current collector. Vacuum drying and pressing to make a positive electrode.
  • the solvent can be selected from any one or more of various lithium ion battery solvents such as N-methylpyrrolidone, ethylene carbonate, diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate.
  • the current collector can be selected from various lithium ion battery current collectors such as aluminum foil.
  • the vacuum drying time can be 8 hours, 10 hours, 12 hours, 15 hours and so on.
  • the separator can be selected from various lithium ion battery separators such as a microporous polypropylene (Celgard 2300) membrane.
  • the electrolyte can be selected from any one or more of various lithium-ion battery electrolytes such as liquid electrolytes, solid electrolytes, and gel electrolytes, and is preferably composed of lithium hexafluorophosphate (LiPF 6 )/ethylene carbonate (EC), and two Ethyl (DEC) and Methyl Ethyl Carbonate (EMC) are mixed and prepared, and the content of LiPF 6 /EC, DEC, and EMC is preferably 1 mol/L mixed in a volume ratio of 1:1:1.
  • LiPF 6 lithium hexafluorophosphate
  • EC ethylene carbonate
  • EMC Methyl Ethyl Carbonate
  • Lithium-ion batteries can be assembled in a glove box filled with high-purity argon.
  • the single-layer graphene oxide used in the following embodiments was purchased from Shanghai Carbon Source Huigu New Energy Technology Co., Ltd.
  • the single-layer reduced graphene oxide lithium cobalt oxide composite material prepared above is used as the positive electrode active material of the lithium ion battery to prepare a lithium ion battery:
  • the single-layer reduced graphene oxide lithium cobalt oxide composite material, the conductive agent carbon black and the binder polyvinylidene fluoride are mixed according to the mass ratio of 80:10:10, and stirred to form a slurry. Coated on the surface of aluminum foil, vacuum-dried for 12 hours, and pressed into a positive electrode sheet with a diameter of 10 mm.
  • Metal lithium is used as the negative electrode
  • the microporous polypropylene (Celgard 2300) membrane is used as the separator
  • 1 mol/L LiPF 6 /EC+DEC+EMC volume ratio 1:1:1 is used as the electrolyte.
  • the CR2025 button cell is assembled. After standing for 12 hours, the electrochemical performance test was performed.
  • the single-layer reduced graphene oxide lithium cobalt oxide composite material prepared above is used as the positive electrode active material of the lithium ion battery to prepare a lithium ion battery:
  • the single-layer reduced graphene oxide lithium cobalt oxide composite material, the conductive agent carbon black and the binder polyvinylidene fluoride are mixed according to the mass ratio of 80:10:10, and stirred to form a slurry. Coated on the surface of the aluminum foil, then vacuum-dried for 12 hours, and pressed into a positive electrode sheet with a diameter of 10 mm.
  • Metal lithium is used as the negative electrode
  • the microporous polypropylene (Celgard 2300) membrane is used as the separator
  • 1 mol/L LiPF 6 /EC+DEC+EMC volume ratio 1:1:1 is used as the electrolyte.
  • the CR2025 button cell is assembled. After standing for 12 hours, the electrochemical performance test was performed.
  • the single-layer reduced graphene oxide lithium cobalt oxide composite material prepared above is used as the positive electrode active material of the lithium ion battery to prepare a lithium ion battery:
  • the single-layer reduced graphene oxide lithium cobalt oxide composite material, the conductive agent carbon black and the binder polyvinylidene fluoride are mixed according to the mass ratio of 80:10:10, and stirred to form a slurry. Coated on the surface of the aluminum foil, then vacuum-dried for 12 hours, and pressed into a positive electrode sheet with a diameter of 10 mm.
  • Metal lithium is used as the negative electrode
  • the microporous polypropylene (Celgard 2300) membrane is used as the separator
  • 1 mol/L LiPF 6 /EC+DEC+EMC volume ratio 1:1:1 is used as the electrolyte.
  • the CR2025 button cell is assembled. After standing for 12 hours, the electrochemical performance test was performed.
  • N-methylpyrrolidone as solvent, mix lithium cobalt oxide cathode material, conductive agent carbon black, and binder polyvinylidene fluoride at a mass ratio of 80:10:10, stir and coat it evenly into a slurry form on the surface of the aluminum foil , And then vacuum-dried for 12 hours, compressed into a positive electrode sheet with a diameter of 10mm.
  • Metal lithium is used as the negative electrode
  • the microporous polypropylene (Celgard 2300) membrane is used as the separator
  • 1 mol/L LiPF 6 /EC+DEC+EMC volume ratio 1:1:1 is used as the electrolyte.
  • the CR2025 button cell is assembled. After standing for 12 hours, the electrochemical performance test was performed.
  • N-methylpyrrolidone as solvent, mix the above-mentioned lithium cobalt oxide composite material, conductive agent carbon black and binder polyvinylidene fluoride with a mass ratio of 80:10:10, stir and coat it into a slurry form on the aluminum foil The surface is then vacuum dried for 12 hours and pressed into a positive electrode sheet with a diameter of 10 mm.
  • Metal lithium is used as the negative electrode
  • the microporous polypropylene (Celgard 2300) membrane is used as the separator
  • 1 mol/L LiPF 6 /EC+DEC+EMC volume ratio 1:1:1 is used as the electrolyte.
  • the CR2025 button cell is assembled. After standing for 12 hours, the electrochemical performance test was performed.
  • N-methylpyrrolidone as solvent, mix the above-mentioned lithium cobalt oxide composite material, conductive agent carbon black and binder polyvinylidene fluoride with a mass ratio of 80:10:10, stir and coat it into a slurry form on the aluminum foil The surface is then vacuum dried for 12 hours and pressed into a positive electrode sheet with a diameter of 10 mm.
  • Metal lithium is used as the negative electrode
  • the microporous polypropylene (Celgard 2300) membrane is used as the separator
  • 1 mol/L LiPF 6 /EC+DEC+EMC volume ratio 1:1:1 is used as the electrolyte.
  • the CR2032 button cell is assembled. After standing for 12 hours, the electrochemical performance test was performed.
  • the lithium cobalt oxide positive active material in Figure 1 can be clearly observed on the surface of the single-layer reduced graphene oxide lithium cobalt oxide composite material in Figure 2
  • the single-layer reduced graphene oxide not only coats the surface of the lithium cobalt oxide, but also forms a bridge connection between the lithium cobalt oxide powders to form a continuous and complete three-dimensional conductive structure, which can effectively improve the conductivity of the lithium ion cathode material.
  • the lithium ion battery of Comparative Example 2 can be cycled about 400 times; the specific discharge capacity at 0.2C and 5C is 170 mAh/g and 60 mAh/g.
  • the lithium ion battery of Comparative Example 3 can be cycled about 450 times; the specific discharge capacity at 0.2C and 5C is 177mAh/g and 71mAh/g.
  • the lithium ion battery of Example 2 can be cycled stably for more than 500 times, and the specific capacity at 0.2C and 5C discharge is about 200.2mAh/g and 89.5mAh/g, respectively.
  • the lithium ion battery of Example 3 can be cycled stably for more than 500 times, and the specific capacity at 0.2C and 5C discharge is about 218.8mAh/g and 96.3mAh/g, respectively.
  • the uneven preparation process is simple in the examples of the application, the cycle performance of the prepared battery is greatly improved, and both can reach more than 500 times, and both the low-rate discharge performance and the high-rate discharge performance are improved.

Abstract

一种单层还原氧化石墨烯钴酸锂复合材料及其制备方法和用途。制备方法包括：配制单层氧化石墨烯的水溶液；向单层氧化石墨烯的水溶液中加入钴酸锂；混合均匀后进行喷雾干燥，得到该复合材料。该复合材料具有连续的三维导电结构，其中的单层还原氧化石墨烯包覆于钴酸锂表面，并在钴酸锂之间形成架桥连接。该制备方法将单层氧化石墨烯与钴酸锂的混合过程与高效的喷雾干燥技术相结合，工艺简单，适合大批量生产，且无需添加各类添加剂，生产成本低；能够在钴酸锂表面形成完整、连续且导电性良好的单层还原氧化石墨烯包覆层，提高锂离子电池的倍率放电性能和循环稳定性。

Description

单层还原氧化石墨烯钴酸锂复合材料及其制备方法和用途
相关申请的交叉引用
本申请要求享有于2019年6月17日递交的发明名称为“单层还原氧化石墨烯钴酸锂复合材料及其制备方法和用途”的中国专利申请No.201910522453.3的优先权权益，其全部内容在此通过援引全部并入本文。
技术领域
本申请涉及但不限于电化学领域，具体地，涉及但不限于一种单层还原氧化石墨烯钴酸锂复合材料及其制备方法和用途。
背景技术
锂离子电池作为一种性能优异的储能装置，在电动汽车、日用电子产品以及静置式储能电站等民用产品领域得到了广泛的应用。然而，由于受电池关键材料的限制，目前多数锂离子电池还不能完全满足上述各种器件和装置的实际需要。作为锂离子电池关键材料之一的钴酸锂正极材料，在实际应用中存在的主要问题有：比能量密度低，大电流密度充放电性能较差。
由于优良的化学稳定性、良好的电子/离子传导性以及锂离子储存能力，石墨烯在锂离子电池电极活性材料中的应用近年来得到广泛的研究。目前石墨烯多以导电添加剂的形式参与到电化学反应中，简单的物理混合导致石墨烯与电极活性材料的结合力不强，难以充分发挥石墨烯优异的物理化学性质。
发明内容
本申请提供了一种采用单层氧化石墨烯制备锂离子电池钴酸锂复合 材料的方法，该方法工艺简单，在制备得到的单层还原氧化石墨烯钴酸锂复合材料中，单层还原氧化石墨烯与钴酸锂之间结合度高、均匀性好。
本申请提供了一种制备单层还原氧化石墨烯钴酸锂复合材料的方法，包括：配制单层氧化石墨烯的水溶液；向单层氧化石墨烯的水溶液中加入钴酸锂；混合均匀后进行喷雾干燥，得到该复合材料。
本申请还提供了一种单层还原氧化石墨烯钴酸锂复合材料，该复合材料通过上述方法制备得到。
本申请还提供了一种单层还原氧化石墨烯钴酸锂复合材料作为锂离子电池正极活性材料的用途。
本申请还提供了一种锂离子电池，该锂离子电池的正极可以包括粘结剂、导电剂以及上述单层还原氧化石墨烯钴酸锂复合材料。
本申请具有以下有益效果。
(1)本申请的制备方法经一次操作即可在钴酸锂活性材料表面形成完整、连续且导电性良好的单层还原氧化石墨烯包覆层，工艺简单。
(2)在单层还原氧化石墨烯包覆层生成过程中无需添加有机溶剂、表面活性剂、还原剂、氧化剂等各类添加剂，生产成本低。
(3)本申请的制备方法将单层氧化石墨烯与钴酸锂的混合过程与高效的喷雾干燥技术巧妙结合，适于单层还原氧化石墨烯钴酸锂复合材料的大批量生产制造。
(4)本申请制备得到的锂离子电池具有优异的倍率放电性能和循环稳定性。
本申请的其它特征和优点将在随后的说明书中阐述，并且，部分地从说明书中变得显而易见，或者通过实施本申请而了解。本申请的目的和其他优点可通过在说明书、权利要求书以及附图中所特别指出的结构来实现和获得。
附图说明
附图用来提供对本申请技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本申请的技术方案，并不构成对本申请技术方案的限制。
图1为现有的钴酸锂正极活性材料的场发射扫描电镜图。
图2为本申请一实施例的单层还原氧化石墨烯钴酸锂复合材料的场发射扫描电镜图。
图3为本申请一对比例的锂离子电池的循环性能曲线。
图4为本申请一实施例的锂离子电池的循环性能曲线。
图5本申请一对比例的锂离子电池的倍率充放电曲线。
图6为本申请一实施例的锂离子电池的倍率充放电曲线。
具体实施方式
为使本申请的目的、技术方案和优点更加清楚明白，下文中将结合附图对本申请的实施例进行详细说明。需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互任意组合。
为了解决钴酸锂比能量密度低、大电流密度充放电性能较差的问题，可以采用引入功能化新材料对钴酸锂进行包覆处理的手段。然而，目前采用功能化新材料对钴酸锂活性材料进行包覆处理的方法不仅操作步骤繁琐，而且经常需要添加有机溶剂、表面活性剂、还原剂、氧化剂等各类添加剂，导致处理成本较高。
本申请实施例提供了一种制备单层还原氧化石墨烯钴酸锂复合材料的方法，包括：配制单层氧化石墨烯的水溶液；向单层氧化石墨烯的水溶液中加入钴酸锂；混合均匀后进行喷雾干燥，得到复合材料。
本申请中的“还原氧化石墨烯”指的是：单层氧化石墨烯进行部分热还原反应所得到的还原氧化石墨烯。
本申请实施例利用单层还原氧化石墨烯良好的导电各向异性以及曲度可控的结构特性，使用单层氧化石墨烯包覆在钴酸锂活性材料表面，进而 对其进行部分热还原，从而构造出具有三维导电网络结构、导电性良好的单层还原氧化石墨烯钴酸锂复合材料。
本申请实施例的制备方法经一次操作即可形成单层还原氧化石墨烯包覆层，工艺简单，而且在单层还原氧化石墨烯包覆层生成过程中无需添加有机溶剂、表面活性剂、还原剂、氧化剂等各类添加剂，生产成本低。
此外，本申请实施例的制备方法将单层氧化石墨烯与钴酸锂的混合过程与喷雾干燥技术相结合，工艺简单，适于单层还原氧化石墨烯锂离子电池钴酸锂复合材料的大批量生产制造。
在本申请实施例中，单层氧化石墨烯与水的质量比可以为1×10 -5:1～50×10 -5:1，例如可以为10×10 -5:1、20×10 -5:1、30×10 -5:1、40×10 -5:1、45×10 -5:1等。当单层氧化石墨烯与水的质量比在1×10 -5:1～50×10 -5:1范围内时，能够使钴酸锂的导电性得到较大提高，并且单层氧化石墨烯能够均匀地分散在水中，有利于改性反应充分进行。
在本申请实施例中，钴酸锂与单层氧化石墨烯的水溶液的质量比可为0.01:1～0.5:1，例如可以为0.05:1、0.1:1、0.2:1、0.3:1、0.4:1等。当钴酸锂与单层氧化石墨烯的水溶液的质量比在0.01:1～0.5:1范围内时，能够很好的形成包覆层，且不易出现包覆层过厚的情况，更有利于形成单层还原氧化石墨烯的包覆层。
在本申请实施例中，可采用搅拌等方式进行混合。
在本申请实施例中，搅拌速度可为60转/min～240转/min，例如可以为80转/min、100转/min、120转/min、150转/min、180转/min、200转/min等；搅拌时间可为10min～120min，例如可以为20min、30min、60min、90min等。
在本申请实施例中，可以在出口温度为150℃～200℃的条件下进行喷雾干燥，例如可以为160℃、170℃、180℃、190℃等；入料流量可以为300mL/min～800mL/min，例如可以为400mL/min、500mL/min、600mL/min、700mL/min等。当喷雾干燥工序在出口温度为150℃～200℃时，可以对单层氧 化石墨烯进行适度的热还原，从而使制备得到的钴酸锂复合材料获得良好的导电性。
在本申请实施例中，单层氧化石墨烯可以选择市售的单层氧化石墨烯，例如可以是购于上海碳源汇谷新能源科技有限公司的单层氧化石墨烯。
本申请实施例制备得到的单层还原氧化石墨烯钴酸锂复合材料，具有连续的三维导电结构，其中的单层还原氧化石墨烯包覆于钴酸锂表面，从而在钴酸锂正极正极活性材料表面形成完整、连续且导电性良好的单层还原氧化石墨烯包覆层，并在钴酸锂活性材料之间形成架桥连接。
本申请实施例制备得到的单层还原氧化石墨烯钴酸锂复合材料中，包覆的单层还原氧化石墨烯层的厚度例如可以为0.34nm。
本申请实施例提供了一种单层还原氧化石墨烯钴酸锂复合材料作为锂离子电池正极活性材料的用途。
本申请实施例提供了一种锂离子电池，包括：正极、负极、隔膜以及电解液，正极包括粘结剂、导电剂以及上述单层还原氧化石墨烯钴酸锂复合材料；负极可以为碳材料、金属氧化物、金属或合金，例如可以为金属锂片。该锂离子电池具有优异的倍率放电性能和循环稳定性。
粘结剂可以选自聚偏氟乙烯、羧甲基纤维素钠、丁苯橡胶等各种锂离子电池粘结剂中的任意一种或更多种。
导电剂可以选自乙炔黑、炭黑、石墨、碳纳米管、科琴黑等各种锂离子电池导电剂中的任意一种或更多种。
单层还原氧化石墨烯钴酸锂复合材料、粘结剂、导电剂的质量比可以为80:10:10。
锂离子电池的正极可以通过下述方法制备得到：将单层还原氧化石墨烯钴酸锂复合材料、粘结剂、导电剂按比例在溶剂中搅拌均匀成泥浆状，涂覆于集流体表面，真空干燥，压片制成正极。
其中，溶剂可选自N-甲基吡咯烷酮、碳酸乙烯酯、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯等各种锂离子电池溶剂中的任意一种或更多种。
集流体可选自铝箔等各种锂离子电池集流体。
真空干燥时间可以为8小时、10小时、12小时、15小时等。
隔膜可选自微孔聚丙烯(Celgard 2300)膜等各种锂离子电池隔膜。
电解液可选自液体电解液、固体电解质、凝胶电解质等各种锂离子电池电解液中的任意一种或更多种，优选由六氟磷酸锂(LiPF 6)/碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸甲基乙基酯(EMC)混合制成，含量优选为1mol/L的LiPF 6/EC、DEC、EMC以体积比为1:1:1混合。
锂离子电池可在充满高纯氩气的手套箱内组装得到。
以下实施例中所采用的单层氧化石墨烯购买自上海碳源汇谷新能源科技有限公司。
实施例1
制备单层还原氧化石墨烯钴酸锂复合材料：
配制200ml含0.01g单层氧化石墨烯的水溶液；在单层氧化石墨烯的水溶液中加入2g钴酸锂颗粒，在搅拌速度为240转/min的条件下搅拌20min；将反应后的混合溶液在出口温度为180℃、在分散状态下、入料流量为400mL/min的条件下进行喷雾干燥处理，得到单层还原氧化石墨烯钴酸锂复合材料。
采用上述制备的单层还原氧化石墨烯钴酸锂复合材料作为锂离子电池正极活性材料制备锂离子电池：
以N-甲基吡咯烷酮为溶剂，按质量比80:10:10，将单层还原氧化石墨烯钴酸锂复合材料、导电剂炭黑和粘结剂聚偏氟乙稀混合，搅拌均匀成泥浆状涂覆于铝箔表面，真空干燥12小时，压片制成直径为10mm的正极片。
以金属锂作为负极，以微孔聚丙烯(Celgard 2300)膜为隔膜，以1mol/L的LiPF 6/EC+DEC+EMC(体积比为1:1:1)为电解液。
在充满高纯氩气的手套箱内，组装成CR2025扣式电池。静置12小时后进行电化学性能测试。
实施例2
制备单层还原氧化石墨烯钴酸锂复合材料：
配制200ml含0.01g单层氧化石墨烯的水溶液；在单层氧化石墨烯的水溶液中加入100g钴酸锂颗粒，在搅拌速度为120转/min的条件下搅拌120min；将反应后的混合溶液在出口温度为150℃、在分散状态下、入料流量为300mL/min的条件下进行喷雾干燥处理，得到单层还原氧化石墨烯钴酸锂复合材料。
采用上述制备的单层还原氧化石墨烯钴酸锂复合材料作为锂离子电池正极活性材料制备锂离子电池：
以N-甲基吡咯烷酮为溶剂，按质量比80:10:10，将单层还原氧化石墨烯钴酸锂复合材料、导电剂炭黑和粘结剂聚偏氟乙稀混合，搅拌均匀成泥浆状涂覆于铝箔表面，然后真空干燥12小时，压片制成直径为10mm的正极片。
以金属锂作为负极，以微孔聚丙烯(Celgard 2300)膜为隔膜，以1mol/L的LiPF 6/EC+DEC+EMC(体积比为1:1:1)为电解液。
在充满高纯氩气的手套箱内，组装成CR2025扣式电池。静置12小时后进行电化学性能测试。
实施例3
制备单层还原氧化石墨烯钴酸锂复合材料：
配制200ml含0.003g单层氧化石墨烯的水溶液；在单层氧化石墨烯的水溶液中加入20g钴酸锂颗粒，在搅拌速度为60转/min的条件下搅拌10min；将反应后的混合溶液在出口温度为200℃、在分散状态下、入料流量为800mL/min的条件下进行喷雾干燥处理，得到单层还原氧化石墨烯钴酸锂复合材料。
采用上述制备的单层还原氧化石墨烯钴酸锂复合材料作为锂离子电池正极活性材料制备锂离子电池：
以N-甲基吡咯烷酮为溶剂，按质量比80:10:10，将单层还原氧化石墨烯钴酸锂复合材料、导电剂炭黑和粘结剂聚偏氟乙稀混合，搅拌均匀成泥 浆状涂覆于铝箔表面，然后真空干燥12小时，压片制成直径为10mm的正极片。
以金属锂作为负极，以微孔聚丙烯(Celgard 2300)膜为隔膜，以1mol/L的LiPF 6/EC+DEC+EMC(体积比为1:1:1)为电解液。
在充满高纯氩气的手套箱内，组装成CR2025扣式电池。静置12小时后进行电化学性能测试。
对比例1
以N-甲基吡咯烷酮为溶剂，按质量比80:10:10，将钴酸锂正极材料、导电剂炭黑和粘结剂聚偏氟乙稀混合，搅拌均匀成泥浆状涂覆于铝箔表面，然后真空干燥12小时，压片制成直径为10mm的正极片。
以金属锂作为负极，以微孔聚丙烯(Celgard 2300)膜为隔膜，以1mol/L的LiPF 6/EC+DEC+EMC(体积比为1:1:1)为电解液。
在充满高纯氩气的手套箱内，组装成CR2025扣式电池。静置12小时后进行电化学性能测试。
对比例2
配制200mL含氧化石墨烯0.01g、氯化镁0.1g的混合水溶液。在上述混合水溶液中加入2g钴酸锂，在搅拌速度500转/min条件下搅拌8min。将上述反应后的复合材料经水洗、抽滤，置于压力小于-0.08Mpa的真空干燥箱中真空干燥，得到钴酸锂复合材料。
以N-甲基吡咯烷酮为溶剂，按质量比80:10:10，将上述钴酸锂复合材料、导电剂炭黑和粘结剂聚偏氟乙稀混合，搅拌均匀成泥浆状涂覆于铝箔表面，然后真空干燥12小时，压片制成直径为10mm的正极片。
以金属锂作为负极，以微孔聚丙烯(Celgard 2300)膜为隔膜，以1mol/L的LiPF 6/EC+DEC+EMC(体积比为1:1:1)为电解液。
在充满高纯氩气的手套箱内，组装成CR2025扣式电池。静置12小时后进行电化学性能测试。
对比例3
配制200mL含氧化石墨烯0.005g、硫酸锰1.3g、次磷酸钠3.5g、柠檬酸钠5.8g的混合水溶液。在上述混合水溶液中加入2g钴酸锂，在搅拌速度450转/min条件下搅拌15min。将上述反应后的复合材料经水洗、抽滤，置于压力小于-0.08Mpa的真空干燥箱中真空干燥。得到钴酸锂复合材料。
以N-甲基吡咯烷酮为溶剂，按质量比80:10:10，将上述钴酸锂复合材料、导电剂炭黑和粘结剂聚偏氟乙稀混合，搅拌均匀成泥浆状涂覆于铝箔表面，然后真空干燥12小时，压片制成直径为10mm的正极片。
以金属锂作为负极，以微孔聚丙烯(Celgard 2300)膜为隔膜，以1mol/L的LiPF 6/EC+DEC+EMC(体积比为1:1:1)为电解液。
在充满高纯氩气的手套箱内，组装成CR2032扣式电池。静置12小时后进行电化学性能测试。
性能测试与结果
(1)采用场发射扫描电镜(德国，Zeiss Ultra 55)，测试现有的钴酸锂正极活性材料与实施例1的单层还原氧化石墨烯钴酸锂复合材料的微观形貌，测试结果如图1和图2所示。
图1中的钴酸锂正极活性材料与图2中的单层还原氧化石墨烯钴酸锂复合材料相比，在图2的单层还原氧化石墨烯钴酸锂复合材料表面，可明显观察到单层还原氧化石墨烯不仅包覆于钴酸锂表面，还在钴酸锂粉末之间形成架桥连接，构成连续完整的三维导电结构，该结构能够有效的提高锂离子正极材料的导电性能。
(2)采用蓝电电池测试系统(中国，LAND CT-2001A)对实施例和对比例的锂离子电池以不同充放电倍率(0.2C、0.5C、1C、2C、5C)，在2.5～4.6V电压范围内进行充放电性能测试。
对比例1的锂离子电池循环性能和倍率充放电性能测试结果如图3、图5所示，可以看出对比例1的锂离子电池在循环370次左右容量衰减严重，在0.2C和5C放电时的比容量分别约为140mAh/g和0mAh/g。
对比例2的锂离子电池可循环约为400次；在0.2C和5C的放电比 容量为170mAh/g和60mAh/g。
对比例3的锂离子电池可循环约为450次；在0.2C和5C放电比容量为177mAh/g和71mAh/g。
实施例1的锂离子电池循环性能和倍率充放电性能测试结果如图4、图6所示，可以看出实施例1的锂离子电池可稳定循环500次以上，在0.2C和5C放电时的比容量分别约为228mAh/g和105.7mAh/g。
实施例2的锂离子电池可稳定循环500次以上，在0.2C和5C放电时的比容量分别约为200.2mAh/g和89.5mAh/g。
实施例3的锂离子电池可稳定循环500次以上，在0.2C和5C放电时的比容量分别约为218.8mAh/g和96.3mAh/g。
本申请实施例与对比例相比较，不均制备工艺简单，制备得到的电池循环性能大幅提升，均能达到500次以上，小倍率放电性能和大倍率放电性能均得以改善。
虽然本申请所揭露的实施方式如上，但所述的内容仅为便于理解本申请而采用的实施方式，并非用以限定本申请。任何本申请所属领域内的技术人员，在不脱离本申请所揭露的精神和范围的前提下，可以在实施的形式及细节上进行任何的修改与变化，但本申请的专利保护范围，仍须以所附的权利要求书所界定的范围为准。

Claims (9)

  1. 一种制备单层还原氧化石墨烯钴酸锂复合材料的方法，包括：
    配制单层氧化石墨烯的水溶液；
    向所述单层氧化石墨烯的水溶液中加入钴酸锂；
    混合均匀后进行喷雾干燥，得到所述复合材料。
  2. 根据权利要求1所述的方法，其中，所述单层氧化石墨烯与水的质量比为1×10 -5:1～50×10 -5:1。
  3. 根据权利要求1或2所述的方法，其中，所述钴酸锂与所述单层氧化石墨烯的水溶液的质量比为0.01:1～0.5:1。
  4. 根据权利要求1至3任一项所述的方法，其中，所述混合采用搅拌的方式，搅拌速度为60转/min～240转/min，搅拌时间为10min～120min。
  5. 根据权利要求1至4任一项所述的方法，其中，在出口温度为150℃～200℃、入料流量为300mL/min～800mL/min的条件下进行所述喷雾干燥。
  6. 一种单层还原氧化石墨烯钴酸锂复合材料，所述复合材料通过权利要求1-5中任一项所述的方法制备得到。
  7. 根据权利要求6所述的复合材料，其具有连续的三维导电结构，其中，单层还原氧化石墨烯包覆于钴酸锂表面，并在所述钴酸锂之间形成架桥连接。
  8. 权利要求6或7所述的单层还原氧化石墨烯钴酸锂复合材料，作为锂离子电池正极活性材料的用途。
  9. 一种锂离子电池，所述锂离子电池的正极包括粘结剂、导电剂以及权利要求6或7所述的单层还原氧化石墨烯钴酸锂复合材料。
PCT/CN2020/082487 2019-06-17 2020-03-31 单层还原氧化石墨烯钴酸锂复合材料及其制备方法和用途 WO2020253318A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910522453.3 2019-06-17
CN201910522453.3A CN112103477A (zh) 2019-06-17 2019-06-17 单层还原氧化石墨烯钴酸锂复合材料及其制备方法和用途

Publications (1)

Publication Number Publication Date
WO2020253318A1 true WO2020253318A1 (zh) 2020-12-24

Family

ID=73749317

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/082487 WO2020253318A1 (zh) 2019-06-17 2020-03-31 单层还原氧化石墨烯钴酸锂复合材料及其制备方法和用途

Country Status (2)

Country Link
CN (1) CN112103477A (zh)
WO (1) WO2020253318A1 (zh)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103035922A (zh) * 2011-10-07 2013-04-10 株式会社半导体能源研究所 蓄电装置
CN107316976A (zh) * 2017-05-27 2017-11-03 广东烛光新能源科技有限公司 一种锂离子电池正极材料及其制备方法
CN107919475A (zh) * 2016-10-09 2018-04-17 上海中聚佳华电池科技有限公司 一种石墨烯改性的锂离子电池正极材料及制备方法和应用
CN109244448A (zh) * 2018-10-10 2019-01-18 国联汽车动力电池研究院有限责任公司 一种石墨烯改性锂镍钴锰氧化物正极材料及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103515587A (zh) * 2012-06-19 2014-01-15 海洋王照明科技股份有限公司 钛酸锂-石墨烯复合材料、锂离子电池的制备方法
CN103500826B (zh) * 2013-09-30 2015-11-18 山东聊城鲁西化工集团有限责任公司 一种石墨烯—锂电池正极复合材料的制备方法
CN107383518B (zh) * 2016-05-16 2020-01-07 中国石油天然气股份有限公司 聚乙烯-石墨烯复合物的制备方法
CN106784654A (zh) * 2016-11-28 2017-05-31 荆门市格林美新材料有限公司 一种石墨烯包覆钴酸锂材料的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103035922A (zh) * 2011-10-07 2013-04-10 株式会社半导体能源研究所 蓄电装置
CN107919475A (zh) * 2016-10-09 2018-04-17 上海中聚佳华电池科技有限公司 一种石墨烯改性的锂离子电池正极材料及制备方法和应用
CN107316976A (zh) * 2017-05-27 2017-11-03 广东烛光新能源科技有限公司 一种锂离子电池正极材料及其制备方法
CN109244448A (zh) * 2018-10-10 2019-01-18 国联汽车动力电池研究院有限责任公司 一种石墨烯改性锂镍钴锰氧化物正极材料及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHAO, DANDAN ET AL.: "Effects of the lateral sizes and basal plane structure of graphene on the electrochemical properties of LiCoO2.", JOURNAL OF ALLOYS AND COMPOUNDS., vol. 785, 12 January 2019 (2019-01-12), pages 557 - 562, XP085621111, ISSN: 0925-8388 *

Also Published As

Publication number Publication date
CN112103477A (zh) 2020-12-18

Similar Documents

Publication Publication Date Title
CN104009210B (zh) 一种多孔硅/碳复合材料、制备方法及用途
CN104934579B (zh) 一种多孔石墨掺杂与碳包覆石墨负极材料的制备方法
CN103682327B (zh) 基于氮掺杂碳层包裹的空心多孔氧化镍复合材料的锂离子电池及其制备方法
CN114122391B (zh) 一种高功率石墨复合材料及其制备方法
CN111725515A (zh) 稳定锂粉及其制备方法和应用
WO2017008615A1 (zh) 一种气相沉积制备改性硅基负极材料的方法
WO2018059180A1 (zh) 一种高功率高能量化学电源及其制备方法
WO2023124025A1 (zh) 一种石墨复合负极材料及其制备方法和应用
CN111029547A (zh) 一种多孔硅碳复合材料的制备方法
CN114122372A (zh) 一种锂离子电池所用低膨胀硅碳负极材料及其制备方法
CN106711428A (zh) 一种富锂三元复合材料及其制备方法
CN113594459B (zh) 一种具有多层结构的复合负极材料及其制备方法和应用
CN114497508A (zh) 一种功率型人造石墨复合材料及其制备方法
CN113675389A (zh) 一种石墨复合电极材料及其制备方法
CN112520732A (zh) 一种硅碳复合负极材料及其制备方法
CN103268939A (zh) 硅酸亚铁锂正极复合材料的制备方法
CN110707290A (zh) 一种具有类三明治结构柔性锂离子电池负极电极的制备方法
WO2020253318A1 (zh) 单层还原氧化石墨烯钴酸锂复合材料及其制备方法和用途
CN115566167A (zh) 一种气态雾化法制备硅基复合材料及制备方法
CN112467138B (zh) 一种铝掺杂多孔硅碳复合材料的制备方法、锂离子电池
CN114105133A (zh) 一种石墨-硅/硅氧化物-碳复合材料及其制备方法和应用
WO2020253285A1 (zh) 多孔石墨烯钴酸锂复合材料及其制备方法和用途
CN113206213A (zh) 一种硅基复合电极及其制备方法和应用
CN111170294A (zh) 一种低成本磷酸铁锂复合材料的制备方法
CN112467123B (zh) 一种高容量锂离子电池负极材料及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20825610

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20825610

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 25/05/2022)

122 Ep: pct application non-entry in european phase

Ref document number: 20825610

Country of ref document: EP

Kind code of ref document: A1