WO2017024720A1 - 一种高容量锂离子电池负极材料的制备方法 - Google Patents

一种高容量锂离子电池负极材料的制备方法 Download PDF

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WO2017024720A1
WO2017024720A1 PCT/CN2015/098494 CN2015098494W WO2017024720A1 WO 2017024720 A1 WO2017024720 A1 WO 2017024720A1 CN 2015098494 W CN2015098494 W CN 2015098494W WO 2017024720 A1 WO2017024720 A1 WO 2017024720A1
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ion battery
tin
anode material
preparing
capacity lithium
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田东
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田东
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    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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

  • the invention relates to the field of batteries, in particular to a preparation method of a high-capacity lithium ion battery anode material.
  • lithium-ion batteries have developed rapidly.
  • the successful development of lithium-ion batteries should be attributed to the breakthrough of electrode materials, especially carbon anode materials.
  • graphitized carbon materials are very suitable for the insertion and removal of lithium ions due to their good layered structure.
  • the graphite-lithium intercalation compound Li-GIC has a high specific capacity, close to the theoretical specific capacity of LiC 6 of 372 mAh/g, and has a good charge and discharge voltage platform and a low intercalation and deintercalation potential.
  • Lithium source cathode materials such as LiCoO2, LiNiO2 and LiMn2O4, have good matching properties.
  • the average voltage of the assembled battery is high and the discharge is stable. Therefore, a large number of commercial lithium ion batteries use graphite carbon materials as anode materials.
  • Metal tin has the advantages of high lithium storage capacity (994 mAh/g) and low lithium ion deintercalation platform voltage, and is a non-carbon negative electrode material with great development potential. In recent years, extensive research has been carried out on such materials and some progress has been made. However, in the process of reversible lithium storage, the volume expansion of metallic tin is remarkable, resulting in poor cycle performance and rapid decay of capacity, so it is difficult to meet the requirements of large-scale production. For this reason, by introducing a non-metallic element such as carbon, the metal tin is stabilized by alloying or compounding, and the volume expansion of tin is slowed down.
  • a non-metallic element such as carbon
  • Carbon can prevent direct contact between tin particles, inhibit the agglomeration and growth of tin particles, and act as a buffer layer. These methods can indeed improve the cycle performance of tin to a certain extent, but the degree of improvement is limited, and the cycle performance of the material still cannot meet the needs.
  • the object of the present invention is to provide a method for preparing a high-capacity lithium ion battery anode material, which is directed to a serious volume effect of tin during electrochemical lithium deintercalization, and a sufficient expansion space for tin powder by means of extra-volume compensation;
  • the prepared tin-containing composite material maintains the high specific capacity characteristic of tin, and at the same time controls the volume change of the whole electrode to a reasonable level, increases the cycle stability, and improves the energy density of the negative electrode material of the lithium ion battery, so that the negative electrode material is more than the current
  • Commercially available carbon anode materials commonly used in lithium-ion batteries have higher specific capacity, meeting the increasing energy of various portable electrical equipment for batteries. Volume density requirements.
  • the present invention is implemented by the following technical solutions.
  • a preparation method of a high-capacity lithium ion battery anode material comprising the following steps:
  • micro-expanded graphite the natural flake graphite is oxidized and intercalated with concentrated sulfuric acid and potassium permanganate, and then expanded at a temperature of 800 ° C to 950 ° C for 10 to 30 seconds to obtain micro-expanded graphite;
  • Micro-expanded graphite and nano-tin powder are uniformly dispersed ultrasonically in deionized water, and then the uniformly dispersed suspension is suction filtered and dried to obtain micro-expanded graphite with nano tin powder interposed between layers, that is, powder ;
  • the mass ratio of the natural flake graphite, the concentrated sulfuric acid and the potassium permanganate is 1:1 to 5: 0.01 to 0.2, and the concentration of the concentrated sulfuric acid is 95% to 98%.
  • the expanded volume of the micro-expanded graphite is from 2.0 mL/g to 10 mL/g. If the expansion volume is too small, the graphite layer spacing is insufficiently opened, it is difficult to provide sufficient pre-expansion space; if the expansion volume is too large, the graphite layer spacing is opened. If it is too large, the graphite structure will be seriously damaged, and it is difficult to ensure the stability of the cycle at a later stage.
  • the mass ratio of the micro-expanded graphite to the tin powder is 1:0.05 to 0.2, and the particle size of the tin powder is not more than 100 nm.
  • the mass ratio of the powder to the carbon source precursor is 1:0.05 to 0.2.
  • the carbon source precursor in the present invention is one or more of sucrose, polyacrylonitrile, polyvinyl alcohol, phenol resin, epoxy resin, and pitch.
  • the present invention has the following beneficial effects:
  • the invention adopts ultrasonic dispersion of micro-expanded graphite and nano-tin powder, and then directly extracts and drys, and then mixes the carbon source precursor coating treatment to prepare a tin-carbon composite anode material, which is a lithium ion with good performance.
  • Battery anode material the method has the following advantages: 1.
  • the raw material is economical and environmentally friendly; 2.
  • the material has high specific capacity and cycle stability; 3.
  • the preparation process is simple and easy to industrialize.
  • Embodiment 1 is a cycle performance diagram of Embodiment 1 of the present invention.
  • the electrode material is used as a working electrode
  • the lithium sheet is a counter electrode
  • 1M LiPF 6 /DMC:EC:DEC 1:1:1
  • the solution is an electrolyte
  • the polypropylene microporous membrane is a diaphragm, and assembled into an analog battery to 50 mA.
  • the current density of /g is charged and discharged.
  • the composite had an initial discharge capacity of 479 mAh/g and a capacity retention of 80% after 100 cycles.
  • the cycle performance of the electrode material is shown in Figure 1.
  • micro-expanded graphite was prepared as described in Example 1, and the micro-expanded graphite and the tin powder were ultrasonically dispersed to a uniform mass ratio of 1:0.15, then filtered, dried, and the obtained powder was mixed with 15% of the asphalt.
  • the coating was heated to 1,100 ° C under nitrogen atmosphere, kept for 3 hours, and then cooled to room temperature to finally obtain the tin-carbon composite negative electrode material of the present invention.
  • the electrode material test conditions were as described in Example 1, charged and discharged at a current density of 50 mA/g.
  • the electrode material had an initial discharge capacity of 450 mAh/g and a capacity retention rate of 78% after 100 cycles.

Abstract

一种高容量锂离子电池负极材料的制备方法，以天然鳞片石墨为原料，浓硫酸为插层剂，高锰酸钾为氧化剂，然后在高温下进行膨胀处理，得到微膨胀石墨，然后把不同比例的微膨胀石墨与纳米锡粉混合，超声分散、抽滤、干燥得到层间插有纳米锡粉的微膨胀石墨，再与碳源前躯体按一定比例混合包覆，然后在惰性气体保护下碳化烧结，便可制备出包覆完整的且内部具有足够预留膨胀空间的锡碳复合负极材料。电化学表明，此方法制备的锡碳复合材料具有较高的比容量和循环稳定性，是一种理想的高容量锂离子电池负极材料。

Description

一种高容量锂离子电池负极材料的制备方法 技术领域
本发明涉及电池领域，具体为一种高容量锂离子电池负极材料的制备方法。
背景技术
自从1990年日本索尼公司率先研制成功锂离子电池并将其商品化以来，锂离子电池得到了迅猛发展。如今锂离子电池已经广泛地应用于民用、军用等多个领域。随着科技的不断进步，人们对电池的性能提出了更多更高的要求：电子设备的小型化和个性化发展，需要电池具有更小的体积和更高的比能量输出；航空航天能源要求电池具有循环寿命，更好的低温充放电性能和更高的安全性能；电动汽车需要大容量、低成本、高稳定性和安全性能的电池。
锂离子电池的研制成功，应首先归功于电极材料，特别是碳负极材料的突破，在众多的碳材料中，石墨化碳材料由于具有良好的层状结构，非常适合于锂离子的嵌入和脱嵌，形成的石墨—锂层间化合物Li-GIC具有较高的比容量，接近LiC6的理论比容量372mAh/g；同时具有良好的充放电电压平台和较低的嵌脱锂电位，与提供锂源的正极材料，如LiCoO2、LiNiO2及LiMn2O4等匹配性较好，所组成的电池平均电压高，放电平稳，因此目前商品化锂离子电池大量采用石墨类碳材料作为负极材料。
金属锡具有高的储锂容量(994mAh/g)和低的锂离子脱嵌平台电压等优点，是一种极具发展潜力的非碳负极材料。近年来人们对这类材料开展了广泛的研究，并取得了一定的进展。但在可逆储锂过程中，金属锡体积膨胀显著，导致循环性能变差，容量迅速衰减，因此难以满足大规模生产的要求。为此，通过引入碳等非金属元素，以合金化或复合的方式来稳定金属锡，减缓锡的体积膨胀。碳能够阻止锡颗粒间的直接接触，抑制锡颗粒的团聚和长大，起到缓冲层的作用。这些方法确实能在一定程度上改善锡的循环性能，但改善的程度有限，材料的循环性能依然不能满足需要。
发明内容
本发明的目的是提供一种高容量锂离子电池负极材料的制备方法，该方法针对锡在电化学锂脱嵌时产生的严重体积效应，利用体积外补偿的方式给锡粉足够的膨胀空间；制备的含锡复合材料保持了锡的高比容量特性，同时使整体电极的体积变化控制在合理水平，增加循环稳定性，以提高锂离子电池的负极材料的能量密度，使该负极材料比目前商业上锂离子电池中常用的碳负极材料具有更高的比容量，满足各类便携式用电设备对电池日益提高的能 量密度要求。
为实现上述目的，本发明所采用以下的技术方案来实现。
一种高容量锂离子电池负极材料的制备方法，包括以下步骤：
(1)制备微膨胀石墨：用浓硫酸和高锰酸钾将天然鳞片石墨氧化插层，然后在800℃～950℃的温度下保持10～30秒进行膨胀处理，得到微膨胀石墨；
(2)制备粉体：将微膨胀石墨和纳米锡粉在去离子水中超声分散均匀，然后将分散均匀的悬浮液抽滤、干燥得到层间插有纳米锡粉的微膨胀石墨，即粉体；
(3)制备锡碳复合负极材料：将粉体和碳源前驱体进行混合包覆，然后在900℃～1100℃的惰性气体保护下碳化烧结3～5小时，得到锡碳复合负极材料。
本发明中天然鳞片石墨、浓硫酸和高锰酸钾的质量比为1：1～5:0.01～0.2，所述浓硫酸的浓度为95％～98％。
本发明中微膨胀石墨的膨胀体积为2.0mL/g～10mL/g，若膨胀体积太小，石墨层间距打开不够，则难以提供足够的预膨胀空间；若膨胀体积太大，石墨层间距打开太大，则石墨结构会破坏严重，难以保证后期的循环稳定性。
本发明中微膨胀石墨与锡粉的质量比为1：0.05～0.2，锡粉的粒径不大于100纳米。
本发明中粉体与碳源前驱体的质量比为1：0.05～0.2。
本发明中的碳源前躯体为蔗糖、聚丙烯腈、聚乙烯醇、酚醛树脂、环氧树脂、沥青中的一种或几种。
与现有技术相比，本发明具有以下有益效果：
本发明采用微膨胀石墨与纳米锡粉超声分散，然后直接抽滤、干燥，再混合碳源前躯体包覆处理的方法制备出锡碳复合负极材料，该负极材料是一种性能良好的锂离子电池负极材料。另外，采用这种方法还具有以下优点：1、原料经济环保；2、材料具有较高的比容量和循环稳定性；3、制备工艺简单，易于工业化生产。
附图说明
图1为本发明实施例1的循环性能图。
具体实施方式
为了使本发明的技术手段、创作特征、工作流程、使用方法达成目的与功效易于明白了解，下面进一步阐述本发明。
实施例1
称取一定量的天然鳞片石墨，按石墨：浓硫酸：高锰酸钾＝1:2.5:0.05(质量比)的比例，先加 入浓硫酸搅拌至均匀，然后再缓慢的加入高锰酸钾，加完后继续搅拌30min，再用水洗至中性，然后烘干，在900℃温度的马弗炉中膨胀处理25秒，得到微膨胀石墨，将微膨胀石墨与锡粉按质量比1:0.2混合，再超声分散至均匀，然后抽滤、干燥，再将得到的粉体与13％的沥青混合包覆，在氮气保护下加热至1000℃，保温3小时，然后冷却至室温，最终得到本发明的锡碳复合负极材料，石墨碳层之间分布有纳米锡，锡碳复合负极材料外部由碳包覆层包裹。
将该电极材料作为工作电极，锂片为对电极，1M LiPF6/DMC：EC：DEC＝1：1：1，溶液为电解液，聚丙烯微孔膜为隔膜，组装成模拟电池，以50mA/g的电流密度充放电。该复合材料的首次放电容量达479mAh/g，100次循环后的容量保持率为80％。该电极材料的循环性能图如图1所示。
实施例2
按照实施例1中所述制备出微膨胀石墨，将微膨胀石墨与锡粉按质量比1:0.15混合超声分散至均匀，然后抽滤、干燥，再将得到的粉体与15％的沥青混合包覆，在氮气保护下加热至1100℃，保温3小时，然后冷却至室温，最终得到本发明的锡碳复合负极材料。
该电极材料测试条件如实施例1中所述，以50mA/g的电流密度充放电。该电极材料的首次放电容量达450mAh/g，100次循环后的容量保持率为78％。
以上显示和描述了本发明的基本原理、主要特征及本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明的要求保护范围由所附的权利要求书及其等效物界定。

Claims (8)

  1. 一种高容量锂离子电池负极材料的制备方法，其特征是：包括以下步骤：
    (1)制备微膨胀石墨：用浓硫酸和高锰酸钾将天然鳞片石墨氧化插层，然后在800℃～950℃的温度下保持10～30秒进行膨胀处理，得到微膨胀石墨；
    (2)制备粉体：将微膨胀石墨和纳米锡粉在去离子水中超声分散均匀，然后将分散均匀的悬浮液抽滤、干燥得到层间插有纳米锡粉的微膨胀石墨，即粉体；
    (3)制备锡碳复合负极材料：将粉体和碳源前驱体进行混合包覆，然后在900℃～1100℃的惰性气体保护下碳化烧结3～5小时，得到锡碳复合负极材料。
  2. 根据权利要求1所述的一种高容量锂离子电池负极材料的制备方法，其特征是：步骤(1)中所述天然鳞片石墨、浓硫酸和高锰酸钾的质量比为1：1～5：0.01～0.2。
  3. 根据权利要求1或2所述的一种高容量锂离子电池负极材料的制备方法，其特征是：步骤(1)中所述浓硫酸的浓度为95％～98％。
  4. 根据权利要求1所述的一种高容量锂离子电池负极材料的制备方法，其特征是：步骤(2)中所述微膨胀石墨与锡粉的质量比为1：0.05～0.2。
  5. 根据权利要求1或4所述的一种高容量锂离子电池负极材料的制备方法，其特征是：步骤(2)中所述微膨胀石墨的膨胀体积为2.0mL/g～10mL/g。
  6. 根据权利要求1或4所述的一种高容量锂离子电池负极材料的制备方法，其特征是：步骤(2)中所述锡粉的粒径不大于100纳米。
  7. 根据权利要求1所述的一种高容量锂离子电池负极材料的制备方法，其特征是：步骤(3)中所述粉体与碳源前驱体的质量比为1：0.05～0.2。
  8. 根据权利要求1或7所述的一种高容量锂离子电池负极材料的制备方法，其特征是：步骤(3)中所述碳源前躯体为蔗糖、聚丙烯腈、聚乙烯醇、酚醛树脂、环氧树脂、沥青中的一种或几种。
PCT/CN2015/098494 2015-08-07 2015-12-23 一种高容量锂离子电池负极材料的制备方法 WO2017024720A1 (zh)

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CN111211290A (zh) * 2020-02-24 2020-05-29 福建翔丰华新能源材料有限公司 一种高性能兼顾快充石墨锂离子电池负极及其制备方法
CN113036122A (zh) * 2021-03-09 2021-06-25 中南大学 一种膨胀石墨正极材料及其制备方法、电极和铝离子电池
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