WO2013117080A1 - 异质结纳米材料、锂离子电池负极极片及锂离子电池 - Google Patents

异质结纳米材料、锂离子电池负极极片及锂离子电池 Download PDF

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WO2013117080A1
WO2013117080A1 PCT/CN2012/078942 CN2012078942W WO2013117080A1 WO 2013117080 A1 WO2013117080 A1 WO 2013117080A1 CN 2012078942 W CN2012078942 W CN 2012078942W WO 2013117080 A1 WO2013117080 A1 WO 2013117080A1
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ion battery
lithium ion
nanobelt
lithium
negative electrode
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PCT/CN2012/078942
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English (en)
French (fr)
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王兴杰
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华为技术有限公司
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Priority to JP2014555921A priority Critical patent/JP5879640B2/ja
Priority to EP12781020.8A priority patent/EP2639199B1/en
Priority to KR1020147023879A priority patent/KR101586294B1/ko
Priority to US13/720,241 priority patent/US8591773B2/en
Publication of WO2013117080A1 publication Critical patent/WO2013117080A1/zh

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Definitions

  • the invention relates to a rechargeable lithium ion battery technology, in particular to a method for preparing a Mo0 3 nanobelt, a Mo0 3 nanobelt, a heterojunction nanomaterial, a lithium ion battery negative pole piece and a lithium ion battery. Background technique
  • Lithium-ion batteries have become the most important power source for portable electronic products and electric vehicles due to their high energy density and long cycle life.
  • the negative electrode material of a commercial lithium ion battery is a graphite material because the graphite material has high cycle stability in the process of lithium insertion and extraction.
  • graphite materials also encounter many problems in practical applications. For example, the theoretical capacity of graphite materials is only 372 mAhg-l, which is difficult to meet the high energy density requirements of lithium ion batteries.
  • metal oxides are widely used to prepare high capacity, high energy density lithium ion batteries due to their high theoretical reversible specific capacity.
  • the circulation stability of the pool during the metal oxide material is very low.
  • nanomaterials especially the use of one-dimensional nanostructures
  • metal oxide one-dimensional nanostructures are used for the negative electrode of lithium ion batteries, which can also effectively improve the cycle stability of materials.
  • metal oxide materials due to the limitations of metal oxide materials, their reversible specific capacity and cycle stability still do not reach. Commercial lithium ion battery application requirements.
  • the metal oxide is compounded with the carbon material, on the one hand, the reversible specific capacity of the carbon material can be increased; on the other hand, the cycle stability of the metal oxide material can also be improved.
  • the Chinese patent application CN201010291060.5 which combines graphene and tin dioxide, and uses it for the negative electrode of lithium ion battery, and can obtain the material with the first reversible specific capacity of 1000 mAhg-1 or more, after 20 cycles.
  • the specific discharge capacity is still maintained at 600 mAhg-l, which greatly improves the characteristics of a single carbon material and a metal oxide material used as a negative electrode of a lithium ion battery.
  • An embodiment of the present invention provides a method for preparing a MoO 3 nanobelt and a Mo0 3 nanobelt for making the Mo0 3 nanoribbon morphology more regular, thereby improving the reversible specific capacity and circulation of the lithium ion battery. stability.
  • Another aspect of the present invention provides a heterojunction nanomaterial for preparing a negative electrode tab of a lithium ion battery, thereby improving the reversible specific capacity and cycle stability of the lithium ion battery.
  • a method for preparing a negative electrode tab of a lithium ion battery, a negative electrode tab for a lithium ion battery, and a lithium ion battery are provided for improving the reversible specific capacity and cycle stability of the lithium ion battery.
  • a method for preparing a Mo0 3 nanobelt provided by an embodiment of the present invention includes:
  • ammonium molybdate is completely dissolved in deionized water to obtain a mixed solution
  • the Mo0 3 nanobelt was obtained by cooling and washing.
  • the MoO 3 nanobelt prepared by the method for preparing the MoO 3 nanobelt provided by the embodiment of the invention has a more regular morphology, which makes the electrochemical performance superior, and further satisfies the further high reversibility ratio of the lithium ion battery. Capacity and high cycle stability requirements.
  • a heterojunction nanomaterial provided by an embodiment of the invention includes a MoO 3 nanobelt and an alloy-type lithium intercalation metal oxide coated on the surface of the MoO 3 nanobelt.
  • the negative electrode sheet of the lithium ion battery prepared by the method for preparing the negative electrode tab of the lithium ion battery according to the embodiment of the invention can improve the reversible specific capacity and the cycle stability of the lithium ion battery.
  • a lithium ion battery provided with the above negative electrode tab of the lithium ion battery provided by the embodiment of the invention has high reversible specific capacity and high cycle stability.
  • FIG. 1 is a flow chart of a method for preparing a MoO 3 nanobelt according to an embodiment of the present invention
  • FIG. 2A is a schematic diagram of a topography of a Mo0 3 nanobelt provided by an embodiment of the present invention
  • FIG. 2B is a scanning electron micrograph of a Mo0 3 nanobelt provided by an embodiment of the present invention
  • FIG. 3B is a schematic diagram of a morphology of a heterojunction nanomaterial according to an embodiment of the present invention
  • FIG. 3B is a different embodiment of the present invention
  • FIG. 4 is a flow chart of a method for preparing a negative electrode tab of a lithium ion battery according to an embodiment of the present invention.
  • FIG. 1 is a flow chart of a method for preparing a MoO 3 nanobelt provided by an embodiment of the present invention. As shown in FIG. 1, the method for preparing the Mo0 3 nanobelt includes:
  • Step 11 The ammonium molybdate is completely dissolved in deionized water to obtain a mixed solution.
  • 0.5-2 g of ammonium molybdate is completely dissolved in 20-45 ml of deionized water.
  • Step 12 After adding concentrated nitric acid to the mixed solution, it is placed in an autoclave and heated.
  • the autoclave is heated at a temperature of from 100 to 250 ° C for 10-48 hours.
  • Step 13 Cooling and washing to obtain a Mo0 3 nanobelt.
  • ammonium molybdate is dissolved in 20-45 ml of deionized water under stirring with a magnetic stirrer to obtain a mixed solution.
  • 1-15 ml of concentrated nitric acid was added to the above mixed solution, and the mixture was stirred for 2 minutes (min).
  • the solution is then transferred to an autoclave and the autoclave is quickly placed in a furnace and heated at a temperature of 100-250 ° C for 10-48 hours (h). After the completion of the reaction, the autoclave was cooled to a normal temperature, and a powder sample was collected by centrifugal washing to obtain a Mo0 3 nanobelt.
  • the Mo0 3 nanobelt is prepared by ammonium molybdate, concentrated nitric acid, etc., and the obtained Mo0 3 nanobelt is as shown in FIG. 2A and FIG. 2B, and the width of the Mo0 3 nanobelt is about 180 nm, and the morphology is obtained. More regular, the electrochemical performance is superior, to meet the requirements of further high reversible specific capacity and high cycle stability of lithium ion batteries.
  • the present invention provides a heterojunction nano material comprising: a MoO 3 nanobelt and coated on the Mo0, in view of the problem of the reversible specific capacity and the cycle stability of the cathode of the lithium ion battery.
  • the Mo0 3 nanobelt can be prepared by a conventional technique, or can be prepared by the method in the embodiment shown in Fig. 1 above.
  • the heterojunction nanomaterials FIG. 3A, 3B mechanisms alloy lithium metal oxide ( ⁇ ⁇ ⁇ meters to a uniform particle Covered on the surface of the ⁇ 0 3 nanobelt.
  • ⁇ ⁇ - ⁇ 0 3 nanoribbons the heterojunction nanomaterials have a width of about 220 nm, and the surface of the MO x -Mo0 3 nanobelts is very smooth, indicating that the coated MO x material is very uniform. .
  • the metal in the metal oxide may be Al, Si, Sn, Sb or the like.
  • the above embodiment adopts an alloy type lithium intercalation mechanism of metal oxide and molybdenum oxide nano material.
  • Composite to form heterojunction nanomaterials, in order to improve the reversible specific capacity and cycle stability of lithium ion batteries, heterojunction nanomaterials are used here for the research of lithium ion battery anodes.
  • a method for preparing a negative electrode tab of a lithium ion battery includes:
  • Step 41 mixing the active material, conductive graphite, CMC (Carboxy Methyl Cellulose, hydroxydecyl cellulose) and water.
  • the active material is made of any of the heterojunction nanomaterials provided in the above embodiments.
  • the mixing ratio of the heterojunction nano material, the conductive graphite, the CMC, and the water may be 8:1:1:100.
  • the mixing ratio is the mass ratio of the heterojunction nanomaterial, the conductive graphite, the CMC, and the water.
  • Step 42 The mixture obtained by the mixing is thoroughly mixed with isopropyl alcohol, and uniformly coated on a copper sheet to obtain a smear.
  • Step 43 The smear is vacuum dried and compressed to obtain a negative electrode piece of a lithium ion battery.
  • the process of vacuum drying the smear may include: vacuum drying the smear at 120 ° C for more than 24 hours.
  • conductive graphite: CMC: water 8: 1 : 1 : 100 mass ratio, and adjusted with isopropyl alcohol into a homogenous slurry, all coated on the copper sheet to obtain a smear, will be coated
  • the sheet was dried in a vacuum at 120 ° C for more than 24 hours, and was tableted to prepare a negative electrode sheet for a lithium ion battery. It can improve the reversible specific capacity and cycle stability of lithium ion batteries.
  • the lithium ion battery provided by the embodiment of the present invention includes the lithium ion battery negative electrode piece prepared in the above embodiment shown in Fig. 4. Therefore, the battery provided in the embodiment has high reversible specific capacity and high cycle stability.
  • the pole piece prepared in the embodiment shown in FIG. 4 is used as a working electrode, and the lithium metal piece is used as a counter electrode of the working electrode, and lithium hexafluorophosphate and EC (1 M (mol/L) and a volume ratio of 1:1 are used.
  • 2-ethanediol carbonate, vinyl carbonate) /DMC (Dimethyl carbonate) as a electrolyte
  • celgard 2400 polypropylene porous membrane as a separator, assembled into a 2016-button battery in an inert gas glove box.
  • Table 1 is the prepared ⁇ 1 2 0 3 - ⁇ 0 3 nanobelt, Si0 2 -Mo0 3 nanobelt, SiO-Mo0 3 nanobelt, Sn0 2 -Mo0 3 nanobelt, Sb 2 0 3 - Mo0 3 nanobelt and Mo0
  • Table 2 is the prepared ⁇ 1 2 0 3 - ⁇ 0 3 nanobelt, Si0 2 -Mo0 3 nanobelt, SiO-Mo0 3 nanobelt, Sn0 2 -Mo0 3 nanobelt, Sb 2 0 3 - Mo0 3 nanobelt and Mo0 Under the condition of charge and discharge current of 67 mAg-1 in 3 nanobelts, the discharge specific capacity is relative to the remaining capacity percentage of the second time.
  • the lithium ion battery using the above heterojunction nanomaterial has a reversible specific capacity which is greatly improved compared with the reversible specific capacity of the original metal oxide. From Table 2, it can be seen that the lithium ion battery using the above-mentioned heterojunction nano material has a greatly improved cycle stability as compared with the original metal oxide.

Abstract

本发明提供一种异质结纳米材料、锂离子电池负极极片及锂离子电池,异质结纳米材料包括MoO3纳米带及包覆在所述MoO3纳米带表面的合金型嵌锂机制的金属氧化物。锂离子电池负极极片釆用该异质结纳米材料作为活性材料,釆用该锂离子电池负极极片的锂离子电池具有高可逆比容量和高循环稳定性。

Description

异质结纳米材料、 鋰离子电池负极极片及鋰离子电池 技术领域
本发明涉及可充电锂离子电池技术, 尤其涉及一种制备 Mo03纳米带 的方法、 Mo03纳米带、 异质结纳米材料、 锂离子电池负极极片及锂离子 电池。 背景技术
锂离子电池由于其较高的能量密度和较长的循环寿命, 已经成为最重 要的便携式电子产品和电动汽车的电源。
通常, 商业锂离子电池的负极材料为石墨材料, 是因为石墨材料在锂 的嵌入和脱出的过程中具有很高的循环稳定性。
但是, 石墨材料在实际应用中也遇到很多问题, 诸如石墨材料的理论 容量仅仅为 372 mAhg-l , 很难适应锂离子电池的高的能量密度的需求。
此外, 金属氧化物由于其高的理论可逆比容量, 也被广泛的用于制备 高容量、 高能量密度的锂离子电池。 但是金属氧化物材料在循环过程中, 池的循环稳定性很低。
近年来, 将材料纳米化, 尤其是一维纳米结构的使用, 大大的提高了 材料在锂的嵌入和脱出过程中的机械强度, 使得材料能够承受更大的应 力, 最大化的保持材料在锂离子充放电过程中的结构完整性, 从而有效地 提高锂离子电池的负极特性。 如, 金属氧化物一维纳米结构用于锂离子电 池的负极, 也可以有效地提高材料的循环稳定性, 但是由于金属氧化物材 料自身的局限性,其可逆比容量和循环稳定性依然没有达到商业锂离子电 池的应用要求。
因此, 需要一种锂离子电池新型负极, 用以提高锂离子电池的的可逆 比容量和循环稳定性。
现有技术釆用将金属氧化物同碳材料复合,一方面可以提高碳材料的 可逆比容量; 另一方面也可以提高金属氧化物材料的循环稳定性。 参见申 请号为 CN201010291060.5的中国专利申请,其将石墨烯和二氧化锡复合, 并将其用于锂离子电池的负极, 可以得到材料首次可逆比容量 1000 mAhg-1 以上, 经 20次循环后放电比容量依然保持在 600mAhg-l , 大大的 提高了单一的碳材料和金属氧化物材料用作锂离子电池负极的特性。
虽然该技术方案在一定程度上提高了锂离子电池的可逆比容量和循 环稳定性, 但是其可逆比容量和循环稳定性依然不高。 发明内容 本发明实施例一方面提供一种制备 Mo03纳米带的方法及 Mo03纳米 带, 以用于使得 Mo03纳米带形貌更加规则, 从而有利于提高锂离子电池 的可逆比容量和循环稳定性。
本发明实施例另一方面提供一种异质结纳米材料, 以用于制备锂离子 电池负极极片, 从而提高锂离子电池的可逆比容量和循环稳定性。
本发明实施例又一个方面提供一种制备锂离子电池负极极片的方法、 锂离子电池负极极片及锂离子电池, 以用于提高锂离子电池的可逆比容量 和循环稳定性。
本发明实施例提供的一种制备 Mo03纳米带的方法, 包括:
将钼酸铵完全溶解在去离子水中, 得到混合溶液;
在所述混合溶液中加入浓硝酸后, 放入高压反应釜并加热;
冷却清洗得到 Mo03纳米带。
本发明实施例提供的一种釆用上述制备 Mo03纳米带的方法制备得到 的 Mo03纳米带, 形貌更加规则, 使得其电化学性能更加优越, 以满足锂 离子电池的进一步的高可逆比容量和高循环稳定性的要求。
本发明实施例提供的一种异质结纳米材料, 包括 Mo03纳米带及包覆 在所述 Mo03纳米带表面的合金型嵌锂机制的金属氧化物。
本发明实施例提供的一种制备锂离子电池负极极片的方法, 其中, 活 性材料釆用上述异质结纳米材料, 包括:
将所述活性材料、 导电石墨、 羟曱基纤维素 CMC及水混合; 用异丙醇将所述混合得到的混合物调匀, 并均勾涂布在铜片上, 得到 涂片; 将所述涂片真空干燥、 压片, 得到锂离子电池负极极片。
本发明实施例提供的一种釆用上述制备锂离子电池负极极片的方法 制备得到的锂离子电池负极极片, 能够提高锂离子电池的可逆比容量和循 环稳定性。
本发明实施例提供的一种设置有上述锂离子电池负极极片的锂离子 电池, 具有高可逆比容量和高循环稳定性。 附图说明
实施例或现有技术描述中所需要使用的附图作一简单地介绍, 显而易见 地, 下面描述中的附图是本发明的一些实施例, 对于本领域普通技术人员 来讲, 在不付出创造性劳动的前提下, 还可以根据这些附图获得其他的附 图。
图 1为本发明实施例提供的制备 Mo03纳米带的方法的流程图; 图 2A为本发明实施例提供的 Mo03纳米带的形貌示意图;
图 2B为本发明实施例提供的 Mo03纳米带的的扫描电子显微镜图; 图 3 A为本发明实施例提供的异质结纳米材料的形貌示意图; 图 3B为本发明实施例提供的异质结纳米材料的扫描电子显微镜图; 图 4 为本发明实施例提供的制备锂离子电池负极极片的方法的流程 图。 具体实施方式 为使本发明实施例的目的、 技术方案和优点更加清楚, 下面将结合本 发明实施例中的附图, 对本发明实施例中的技术方案进行清楚、 完整地描 述,显然, 所描述的实施例是本发明一部分实施例, 而不是全部的实施例。 基于本发明中的实施例, 本领域普通技术人员在没有作出创造性劳动前提 下所获得的所有其他实施例, 都属于本发明保护的范围。
图 1为本发明实施例提供的制备 Mo03纳米带的方法的流程图。 如图 1所示, 制备 Mo03纳米带的方法包括:
步骤 11、 将钼酸铵完全溶解在去离子水中, 得到混合溶液。 如, 将 0.5-2g钼酸铵完全溶解在 20-45ml的去离子水中。
步骤 12、 在所述混合溶液中加入浓硝酸后, 放入高压反应釜并加热。 如将所述高压反应釜在 100-250°C的温度下加热 10-48小时。
步骤 13、 冷却清洗得到 Mo03纳米带。
具体地, 如将 0.5-2g钼酸铵在磁力搅拌器的搅拌下溶解在 20-45ml的 去离子水中, 得到混合溶液。 等待钼酸铵完全溶解后, 在上述混合溶液中 加入 l-15ml的浓硝酸, 搅拌 2分钟( min ) 。 然后将溶液转移到高压反应 釜中, 并快速地将高压反应釜放入到炉子中, 在 100-250°C的温度下加热 10-48小时(h ) 。 反应结束后, 待高压反应釜冷却到常温, 釆用离心清洗 的方法, 收集粉末样品, 得到 Mo03纳米带。
本实施例中, Mo03纳米带由钼酸铵、浓硝酸等制备获得,得到的 Mo03 纳米带如图 2A、 图 2B所示, 可以得知 Mo03纳米带的宽度约为 180nm, 形貌更加规则, 使得其电化学性能更加优越, 以满足锂离子电池的进一步 的高可逆比容量和高循环稳定性的要求。
针对目前锂离子电池负极面临的可逆比容量和循环稳定性的问题, 本 发明实施例提供一种异质结纳米材料, 该异质结纳米材料包括: Mo03纳 米带及包覆在所述 Mo03纳米带表面的合金型嵌锂机制的金属氧化物。
其中, Mo03纳米带可通过传统技术制备得到, 也可釆用上述图 1 所 示实施例中的方法制备得到。
当釆用图 1所示实施例的方法制备得到 Mo03纳米带时, 异质结纳米 材料如图 3A、 图 3B所示, 合金型嵌锂机制的金属氧化物 (ΜΟχ ή米颗粒 均匀地包覆在 Μο03纳米带的表面。 ΜΟχ-Μο03纳米带即异质结纳米材料 的宽度约为 220nm, 并且 MOx-Mo03纳米带表面很光滑,表明包覆的 MOx 材料很均匀。
所述金属氧化物中的金属可为 Al、 Si、 Sn、 Sb等。
为了将合金型嵌锂机制的金属氧化物(MOx, M = A1、 Si、 Sn、 Sb等) 均匀的包覆在 Mo03纳米带的表面, 可釆用水热法、 溅射法、 化学气相沉 积、 物理气相沉积等方法, 合成得到这种异质结纳米材料, 这里是异质结 纳米带。
上述实施例通过将合金型嵌锂机制的金属氧化物同氧化钼纳米材料 复合, 使其形成异质结纳米材料, 为了提高锂离子电池的可逆比容量和循 环稳定性, 这里将异质结纳米材料用于锂离子电池负极的研究。
图 4 为本发明实施例提供的制备锂离子电池负极极片的方法的流程 图。 如图 4所示, 制备锂离子电池负极极片的方法包括:
步骤 41、将所述活性材料、导电石墨、 CMC( Carboxy Methyl Cellulose, 羟曱基纤维素)及水混合。 其中, 活性材料釆用上述实施例提供的任一种 异质结纳米材料。 所述异质结纳米材料、 导电石墨、 CMC 及水的混合比 例可为 8: 1 : 1 : 100。 该混合比例为异质结纳米材料、 导电石墨、 CMC及水 的质量比例。
步骤 42、 用异丙醇将所述混合得到的混合物调匀, 并均匀涂布在铜片 上, 得到涂片。
步骤 43、 将所述涂片真空干燥、 压片, 得到锂离子电池负极极片。 将 所述涂片真空干燥的过程, 可包括: 对所述涂片进行 120 °C真空干燥 24 小时以上。
例如, 按照活性材料: 导电石墨: CMC: 水 = 8: 1 : 1 : 100的质量比例 混合, 并用异丙醇调成均勾浆料, 均勾涂布在铜片上, 得到涂片, 将涂片 置于 120°C真空中干燥 24h以上, 压片, 制备成锂离子电池负极极片。 能够提高锂离子电池的可逆比容量和循环稳定性。
本发明实施例提供的锂离子电池包括上述图 4所示实施例制备的锂离 子电池负极极片, 因此, 本实施例提供的电池具有高可逆比容量和高循环 稳定性。
下面通过测试一险证。
首先组装锂离子电池。 具体地, 将图 4所示实施例中制备的极片作为 工作电极, 金属锂片作为该工作电极的对电极, 将 1M ( mol/L )且体积比 为 1 : 1的六氟磷酸锂和 EC ( 1,2-ethanediol carbonate, 碳酸乙烯脂 ) /DMC ( Dimethyl carbonate , 碳酸二曱脂)作为电解液, celgard2400聚丙烯多孔 膜作为隔膜, 在充满惰性气体的手套箱中装配成 2016-纽扣电池。
然后, 釆用 LAND-CT2001A电池程序控制仪, 对 2016-纽扣电池进行 恒电流充放电测试, 电压范围 0.01-2.75V, 充放电电流为 67mAg-l。 测试结果如表 1、 表 2所示。 表 1 Mo03以及异质结纳米带循环 30次后的可逆比容量
Figure imgf000007_0001
表 2 Mo03以及异质结纳米带的循环稳定性
Figure imgf000007_0002
表 1分别为制备的 Α1203-Μο03纳米带、 Si02-Mo03纳米带、 SiO-Mo03 纳米带、 Sn02-Mo03纳米带、 Sb203- Mo03纳米带和 Mo03纳米带在 67 mAg-1的充放电电流的条件下循环 30之后的放电比容量。
表 2分别为制备的 Α1203-Μο03纳米带、 Si02-Mo03纳米带、 SiO-Mo03 纳米带、 Sn02-Mo03纳米带、 Sb203- Mo03纳米带和 Mo03纳米带在 67 mAg-1 的充放电电流的条件下, 放电比容量相对第二次的剩余容量百分 比。
其中, Α1203-Μο03纳米带、 Si02-Mo03纳米带、 SiO-Mo03纳米带、 Sn02-Mo03纳米带、 Sb203- Mo03纳米带和 Mo03纳米带均为上述实施例 提供的异质结纳米材料。
由表 1可以看出釆用上述异质结纳米材料的锂离子电池, 其可逆比容 量相比于原有的金属氧化物的可逆比容量都有很大的提高。 由表 2可以看 出釆用上述异质结纳米材料的锂离子电池, 其循环稳定性相比于原有的金 属氧化物的循环稳定性都有很大的提高。
最后应说明的是: 以上各实施例仅用以说明本发明的技术方案, 而非 对其限制; 尽管参照前述各实施例对本发明进行了详细的说明, 本领域的 普通技术人员应当理解: 其依然可以对前述各实施例所记载的技术方案进 行修改, 或者对其中部分或者全部技术特征进行等同替换; 而这些修改或 者替换, 并不使相应技术方案的本质脱离本发明各实施例技术方案的范 围。

Claims

权利要求书
1、 一种制备 ΜοΟ^ή米带的方法, 其特征在于, 包括:
将钼酸铵完全溶解在去离子水中, 得到混合溶液;
在所述混合溶液中加入浓硝酸后, 放入高压反应釜并加热;
冷却清洗得到 Μο03纳米带。
2、 根据权利要求 1所述的制备 Μο03纳米带的方法, 其特征在于, 将 钼酸铵完全溶解在去离子水中的过程, 包括:
将 0.5-2g钼酸铵完全溶解在 20-45ml的去离子水中。
3、根据权利要求 1或 2所述的制备 ΜοΟ^ή米带的方法,其特征在于, 放入高压反应釜并加热的过程, 包括:
将所述高压反应釜在 100-250°C的温度下加热 10-48小时。
4、一种釆用上述权利要求 1-3任一项所述的制备 Mo03纳米带的方法 制备得到的 ΜοΟ^ή米带。
5、 一种异质结纳米材料, 其特征在于, 包括 Μο03纳米带及包覆在所 述 Μο03纳米带表面的合金型嵌锂机制的金属氧化物。
6、 根据权利要求 5 所述的异质结纳米材料, 其特征在于, 所述金属 氧化物中的金属为 Al、 Si、 Sn、 Sb。
7、 根据权利要求 5或 6所述的异质结纳米材料, 其特征在于, 所述 Mo03纳米带为上述权利要求 4所述的 Mo03纳米带。
8、 一种制备锂离子电池负极极片的方法, 其特征在于, 活性材料釆 用上述权利要求 5-7任一项所述的异质结纳米材料, 包括:
将所述活性材料、 导电石墨、 羟曱基纤维素 CMC及水混合; 用异丙醇将所述混合得到的混合物调匀, 并均勾涂布在铜片上, 得到 涂片;
将所述涂片真空干燥、 压片, 得到锂离子电池负极极片。
9、 根据权利要求 8 所述的制备锂离子电池负极极片的方法, 其特征 在于,所述异质结纳米材料、导电石墨、 CMC及水的混合比例为 8: 1 : 1 : 100。
10、 根据权利要求 8或 9所述的制备锂离子电池负极极片的方法, 其 特征在于, 将所述涂片真空干燥的过程, 包括:
对所述涂片进行 120 °C真空干燥 24小时以上。
1 1、一种釆用上述权利要求 8-10任一项所述的制备锂离子电池负极极 片的方法制备得到的锂离子电池负极极片。
12、 一种设置有上述权利要求 1 1 所述的锂离子电池负极极片的锂离 子电池。
PCT/CN2012/078942 2012-02-09 2012-07-20 异质结纳米材料、锂离子电池负极极片及锂离子电池 WO2013117080A1 (zh)

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