WO2023040409A1 - Method for designing high-capacity electrode material by means of surface reconstruction of particles - Google Patents

Method for designing high-capacity electrode material by means of surface reconstruction of particles Download PDF

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WO2023040409A1
WO2023040409A1 PCT/CN2022/101732 CN2022101732W WO2023040409A1 WO 2023040409 A1 WO2023040409 A1 WO 2023040409A1 CN 2022101732 W CN2022101732 W CN 2022101732W WO 2023040409 A1 WO2023040409 A1 WO 2023040409A1
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electrode material
capacity
mixed solution
negative electrode
surface reconstruction
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Chinese (zh)
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姚耀春
高耕
崔丁方
张克宇
杨斌
米如中
戴永年
王倩雯
梁风
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昆明理工大学
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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
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • the invention relates to a method for designing high-capacity electrode materials by particle surface reconstruction, and belongs to the technical field of negative electrode materials for lithium ion batteries.
  • lithium-ion batteries with graphite anodes have been widely used in watches, mobile phones, notebooks, and electric vehicles.
  • the capacity of traditional lithium-ion batteries is difficult to meet the increasingly higher energy density requirements of electronic equipment. Therefore, the development of lithium-ion batteries with high energy density will be an important direction for the development of lithium-ion batteries.
  • the design and manufacture of high-energy lithium-ion batteries are inseparable from the selection of electrode materials.
  • the anode materials of high energy density lithium-ion batteries mainly include Li, Sn, Ge, Si, P and other ultra-high capacity alloy anodes, metal oxides, sulfides, fluorides, and metal oxo acid salts.
  • metal oxo-salts exhibit excellent energy storage potential due to their short preparation process and energy-saving advantages.
  • the Tirado research group was the first to report and reveal the application prospects of materials containing oxometalates in lithium-ion batteries.
  • the object of the present invention is to provide a kind of metal oxo-salt negative electrode material of particle surface reconstruction design high capacity.
  • the present invention is realized through the following technical solutions:
  • Step 1 Disperse the metal oxo acid salt high-capacity negative electrode material in the mixed solution of organic solvent and deionized water to obtain a uniformly dispersed mixed solution; wherein, the mass-to-volume ratio of the metal oxo acid salt to the mixed solution is: 0.1 ⁇ 1g: 50 ⁇ 200ml;
  • Step 2 adding a soluble metal salt to the mixed solution obtained in step 1, reacting at 0-200°C for 5-72 hours, filtering, washing and drying after the reaction is completed, to obtain a surface-reconstructed material containing crystal water;
  • Step 3 Sintering the resurfaced material containing crystal water obtained in step 3 at 200° C. to 350° C. for 4 to 10 hours under vacuum or an inert atmosphere to obtain a surface restructured high-capacity lithium-ion battery negative electrode material.
  • the organic solvent in the step 1 includes one or more combinations of absolute ethanol, ethylene glycol, CTAB, NMP, DMA, DMSO, and DMF.
  • the mixed solution in the step 1 also includes one or more of PDDA, Pss, sulfuric acid, and hydrochloric acid.
  • the soluble metal salt in the step 2 includes one or more of transition metal nitrates, sulfates, and acetates.
  • the molar ratio of the soluble metal salt to the metal oxo acid salt in the step 2 is: 0.01-1:1-0.01.
  • Precise reconstruction of the surface of the metal oxo-salt high-capacity anode material can be achieved through a simple process. While highlighting the advantages of the existing modification means, the method introduces the surface of the reconstructed metal oxo-salt negative electrode material with varying degrees of looseness, high conductivity, and high catalytic activity of metal heteroatoms.
  • the in-situ reconstructed interface contains different atomic components from the original main body, which can fully utilize the reconstructed interfacial metal heteroatoms to further improve the electrochemical performance of the material while giving full play to the performance of the original high-capacity anode material.
  • Fig. 1 is a schematic diagram of material surface reconstruction involved in the present invention
  • Fig. 2 is the ferrous oxalate reconstruction interface scanning electron microscope pattern prepared by Example 1 of the present invention and the EDS diagram of Fe, Cu and O elements in the same region;
  • Fig. 3 is the cycle stability curve of the ferrous oxalate restructured interface material prepared in Example 2 of the present invention.
  • a copper atom surface reconstruction strategy to prepare high-capacity ferrous oxalate materials the specific steps are as follows:
  • Step 1 the ferrous oxalate high-capacity negative electrode material is dispersed in the mixed solution that 80ml dehydrated alcohol and 10ml deionized water are formed, obtains the mixed solution that is dispersed uniformly;
  • the ratio of metal oxalate and mixed solution 1g: 90ml;
  • Step 2 Add 0.14 g of copper sulfate pentahydrate to the mixed solution obtained in step 1, and react at 50° C. for 6 hours; after the reaction is completed, filter, wash and dry to obtain a surface-reconstructed material containing crystal water;
  • Step 3 In vacuum or inert atmosphere, sinter the resurfaced material containing crystal water obtained in step 3 at 270° C. for 4 hours to obtain a high-capacity lithium-ion battery negative electrode material with resurfaced copper atoms.
  • the scanning electron microscope pattern of the restructured ferrous oxalate interface on the surface of copper atoms prepared in this example is shown in FIG. 2 .
  • a copper atom surface reconstruction strategy prepares a high-capacity ferrous oxalate lithium-ion battery negative electrode material, and its specific steps are as follows:
  • Step 1 the ferrous oxalate high-capacity negative electrode material is dispersed in the mixed solution that 80ml dehydrated alcohol and 10ml deionized water are formed, obtains the mixed solution that is dispersed uniformly;
  • the ratio of metal oxalate and mixed solution 1g: 90ml;
  • Step 2 Add 0.14 g of copper sulfate pentahydrate to the mixed solution obtained in step 1, and react at 50° C. for 6 hours; after the reaction is completed, filter, wash and dry to obtain a surface-reconstructed material containing crystal water;
  • Step 3 In an inert atmosphere, sinter the surface-reconstructed material containing crystal water obtained in step 3 at 270° C. for 4 hours to obtain a negative electrode material for a copper-atom-resurfaced ferrous oxalate lithium-ion battery.
  • the pole piece In a glove box filled with argon gas, the pole piece can be assembled into a battery with existing commercially available separators, lithium sheets, battery cases and nickel meshes by using general conventional methods.
  • the cycle stability curve of the ferrous oxalate negative electrode material reconstructed by copper atoms can be obtained, as shown in Figure 3.
  • Step 1 Disperse the ferrous oxalate high-capacity negative electrode material in a mixed solution composed of 80ml of absolute ethanol, 10ml of NMP and 10ml of deionized water to obtain a uniformly dispersed mixed solution; wherein, the ratio of the metal oxalate to the mixed solution is: 1g: 100ml;
  • Step 2 Add 0.01g of nickel sulfate hexahydrate and 0.01g of cobalt sulfate heptahydrate to the mixed solution obtained in step 1, and react for 6 hours at 50°C; after the reaction is completed, filter, wash and dry to obtain the combined surface weight of nickel and cobalt atoms Structured ferrous oxalate material containing crystal water;
  • Step 3 In an inert atmosphere, sinter the surface-reconstructed material containing crystal water obtained in step 3 at 300° C. for 4 hours to obtain a high-capacity lithium-ion battery negative electrode material with joint surface restructured nickel and cobalt atoms.
  • a cobalt atom surface reconstruction strategy to prepare a high-capacity copper hydroxide material the specific steps are as follows:
  • Step 1 Disperse the copper hydroxide high-capacity negative electrode material in a mixed solution composed of 80ml absolute ethanol, 10ml deionized water, 0.5gCTAB and 2ml concentrated hydrochloric acid to obtain a uniformly dispersed mixed solution; wherein, the metal oxo acid salt and The ratio of the mixed solution: 1g:90ml;
  • Step 2 Add 6.3 g of cobalt nitrate hexahydrate to the mixed solution obtained in step 1, and react at 80° C. for 24 hours; after the reaction is completed, filter, wash and dry to obtain a surface-reconstructed material containing crystal water;
  • Step 3 In an inert atmosphere, sinter the surface restructured material containing crystal water obtained in step 3 at 300° C. for 4 hours to obtain a high-capacity lithium-ion battery negative electrode material with cobalt atom surface restructured.
  • a manganese atom surface reconstruction strategy to prepare high-capacity ferrous carbonate materials the specific steps are as follows:
  • Step 1 Disperse the ferrous carbonate high-capacity negative electrode material in a mixed solution composed of 30ml absolute ethanol, 60ml deionized water, 1ml concentrated hydrochloric acid, 0.5g Pss, and 2.5g ascorbic acid to obtain a uniformly dispersed mixed solution; wherein, the metal The ratio of oxo acid salt to mixed solution: 1g:90ml;
  • Step 2 Add 5.5 g of ferrous sulfate heptahydrate to the mixed solution obtained in step 1, and react at 80° C. for 24 hours; after the reaction is completed, filter, wash and dry to obtain a surface-reconstructed material containing crystal water;
  • Step 3 In an inert atmosphere, sinter the surface-reconstructed material containing crystal water obtained in step 3 at 300° C. for 4 hours to obtain a high-capacity lithium-ion battery negative electrode material with manganese atom surface-reconstructed.

Abstract

A method for designing a high-capacity electrode material by means of the surface reconstruction of particles. An easily soluble metal salt which is readily available is used for the metal atom substitution of the particle surface of a metal oxysalt (oxalate, carbonate or hydroxide) serving as a negative electrode material of a lithium-ion battery at room temperature so as to achieve the modification of the outer reconstruction interface having a single-component or multi-component crystal structure and being inconsistent in loose degrees. The method can effectively retain the original micro-nano structure of a negative electrode material of a lithium-ion battery, and has a high adaptability to raw materials. According to the method, the interface reconstruction of the surface of a negative electrode material is achieved by utilizing the influence of the high catalytic activity and the atomic size of newly introduced metal atoms on the loose degree of a crystal surface, such that the electrochemical performance of the material is effectively improved, and a high energy storage capacity is achieved.

Description

一种颗粒表面重构设计高容量电极材料的方法A method for particle surface reconstruction to design high-capacity electrode materials 技术领域technical field
本发明涉及一种颗粒表面重构设计高容量电极材料的方法，属于锂离子电池负极材料技术领域。The invention relates to a method for designing high-capacity electrode materials by particle surface reconstruction, and belongs to the technical field of negative electrode materials for lithium ion batteries.
背景技术Background technique
自日本索尼公司推出商业锂离子电池石墨负极以来，以石墨负极的锂离子电池广泛应用于手表、手机、笔记本和电动汽车等领域。但是，随着电子设备的升级换代传统的锂离子电池容量难以满足电子设备对能量密度越来越高的要求。因此，开发能量密度高的锂离子电池将是锂离子电池发展的一个重要方向。Since Japan's Sony Corporation launched graphite anodes for commercial lithium-ion batteries, lithium-ion batteries with graphite anodes have been widely used in watches, mobile phones, notebooks, and electric vehicles. However, with the upgrading of electronic equipment, the capacity of traditional lithium-ion batteries is difficult to meet the increasingly higher energy density requirements of electronic equipment. Therefore, the development of lithium-ion batteries with high energy density will be an important direction for the development of lithium-ion batteries.
高能量锂离子电池的设计制造离不开电极材料的选择。目前，高能量密度锂离子电池负极材料主要有以Li、Sn、Ge、Si、P等超高容量合金型负极和金属氧化物、硫化物、氟化物，以及金属含氧酸盐。其中，与其它高容量负极相比金属含氧酸盐凭借制备工艺短和节能优势，展现出极佳的储能潜力。Tirado课题组最早报道并揭示含金属氧酸盐材料在锂离子电池的应用前景。随后，国内外课题组分别金属含氧酸盐材料进行储锂性质研究。他们发现金属含氧酸盐材料在储锂过程中虽然展现出高的容量和稳定的循环性能，但是，该材料在储能前期却面临首次循环库伦效率低和差的锂离子电子传导速率。为了克服这些不足，研究者提出形貌结构控制、过渡金属离子掺杂和颗粒表面碳包覆等措施。这些措施出现很大程度上改善了金属含氧酸盐的电化学性能，然而在这些改性手段下材料仍然呈现出不满意的电化学性能。The design and manufacture of high-energy lithium-ion batteries are inseparable from the selection of electrode materials. At present, the anode materials of high energy density lithium-ion batteries mainly include Li, Sn, Ge, Si, P and other ultra-high capacity alloy anodes, metal oxides, sulfides, fluorides, and metal oxo acid salts. Among them, compared with other high-capacity anodes, metal oxo-salts exhibit excellent energy storage potential due to their short preparation process and energy-saving advantages. The Tirado research group was the first to report and reveal the application prospects of materials containing oxometalates in lithium-ion batteries. Subsequently, research groups at home and abroad conducted studies on the lithium storage properties of metal oxo-salt materials. They found that although the metal oxo-salt material exhibited high capacity and stable cycle performance during the lithium storage process, the material faced low first-cycle Coulombic efficiency and poor lithium-ion electron conductivity in the early stage of energy storage. In order to overcome these shortcomings, the researchers proposed measures such as morphology control, transition metal ion doping, and carbon coating on the particle surface. These measures have greatly improved the electrochemical performance of metal oxo-salts, however, the materials still exhibit unsatisfactory electrochemical performance under these modification methods.
发明内容Contents of the invention
本发明的目的在于提供一种颗粒表面重构设计高容量的金属含氧酸盐负极 材料。本发明通过以下技术方案实现：The object of the present invention is to provide a kind of metal oxo-salt negative electrode material of particle surface reconstruction design high capacity. The present invention is realized through the following technical solutions:
步骤1、将金属含氧酸盐高容量负极材料，分散于有机溶剂和去离子水的混合溶液中，得到分散均匀的混合液；其中，金属含氧酸盐与混合溶液的质量体积比为：0.1～1g:50～200ml；Step 1. Disperse the metal oxo acid salt high-capacity negative electrode material in the mixed solution of organic solvent and deionized water to obtain a uniformly dispersed mixed solution; wherein, the mass-to-volume ratio of the metal oxo acid salt to the mixed solution is: 0.1～1g: 50～200ml;
步骤2、向步骤1得到的混合溶液中加入可溶性金属盐，0～200℃条件下反应5～72h，反应完成后过滤、洗涤和干燥，得到含结晶水表面重构的材料； Step 2, adding a soluble metal salt to the mixed solution obtained in step 1, reacting at 0-200°C for 5-72 hours, filtering, washing and drying after the reaction is completed, to obtain a surface-reconstructed material containing crystal water;
步骤3、在真空或惰性氛围下，将步骤3得到的含结晶水表面重构的材料在200℃～350℃下烧结4～10h，得到表面重构的高容量锂离子电池负极材料。Step 3. Sintering the resurfaced material containing crystal water obtained in step 3 at 200° C. to 350° C. for 4 to 10 hours under vacuum or an inert atmosphere to obtain a surface restructured high-capacity lithium-ion battery negative electrode material.
所述步骤1中的有机溶剂包括无水乙醇、乙二醇、CTAB、NMP、DMA、DMSO、DMF中的一种或多种组合。The organic solvent in the step 1 includes one or more combinations of absolute ethanol, ethylene glycol, CTAB, NMP, DMA, DMSO, and DMF.
所述步骤1中的混合溶液还包括PDDA、Pss、硫酸、盐酸中的一种或多种。The mixed solution in the step 1 also includes one or more of PDDA, Pss, sulfuric acid, and hydrochloric acid.
所述步骤2中的可溶性金属盐包括过渡金属硝酸盐、硫酸盐、醋酸盐中的一种或几种。The soluble metal salt in the step 2 includes one or more of transition metal nitrates, sulfates, and acetates.
所述步骤2中的可溶性金属盐与金属含氧酸盐的摩尔比为：0.01～1：1～0.01。The molar ratio of the soluble metal salt to the metal oxo acid salt in the step 2 is: 0.01-1:1-0.01.
与现有技术相比，本发明的有益效果是：Compared with prior art, the beneficial effect of the present invention is:
通过简单的工艺流程即可实现对金属含氧酸盐高容量负极材料表面实现精准重构。该方法在突出现有改性手段的优势的同时，引入了具备松散程度不一的、含有高电导率、高催化活性金属杂原子重构金属含氧酸盐负极材料表面。原位重构的界面与原有主体内部含有不同的原子成分，可在充分发挥原有高容量负极材料性能的同时，充分利用重构界面金属杂原子进一步提升材料电化学性能。Precise reconstruction of the surface of the metal oxo-salt high-capacity anode material can be achieved through a simple process. While highlighting the advantages of the existing modification means, the method introduces the surface of the reconstructed metal oxo-salt negative electrode material with varying degrees of looseness, high conductivity, and high catalytic activity of metal heteroatoms. The in-situ reconstructed interface contains different atomic components from the original main body, which can fully utilize the reconstructed interfacial metal heteroatoms to further improve the electrochemical performance of the material while giving full play to the performance of the original high-capacity anode material.
附图说明Description of drawings
图1是本发明涉及的材料表面重构示意图；Fig. 1 is a schematic diagram of material surface reconstruction involved in the present invention;
图2本发明实施例1制备的草酸亚铁重构界面扫描电镜图样和相同区域Fe、 Cu和O元素EDS图；Fig. 2 is the ferrous oxalate reconstruction interface scanning electron microscope pattern prepared by Example 1 of the present invention and the EDS diagram of Fe, Cu and O elements in the same region;
图3是本发明实施例2制备的草酸亚铁重构界面材料循环稳定性曲线。Fig. 3 is the cycle stability curve of the ferrous oxalate restructured interface material prepared in Example 2 of the present invention.
具体实施方式Detailed ways
下面结合附图和具体实施方式，对本发明作进一步说明。The present invention will be further described below in combination with the accompanying drawings and specific embodiments.
实施例1Example 1
一种铜原子表面重构策略制备高容量的草酸亚铁材料，其具体步骤如下：A copper atom surface reconstruction strategy to prepare high-capacity ferrous oxalate materials, the specific steps are as follows:
步骤1、将草酸亚铁高容量负极材料，分散于80ml无水乙醇与10ml去离子水构成的混合溶液，得到分散均匀的混合液；其中，金属含氧酸盐与混合溶液的比例：1g:90ml；Step 1, the ferrous oxalate high-capacity negative electrode material is dispersed in the mixed solution that 80ml dehydrated alcohol and 10ml deionized water are formed, obtains the mixed solution that is dispersed uniformly; Wherein, the ratio of metal oxalate and mixed solution: 1g: 90ml;
步骤2、向步骤1得到的混合溶液中加入0.14g五水合硫酸铜，50℃条件下反应6h；反应完成后过滤、洗涤和干燥，得到含结晶水表面重构的材料； Step 2. Add 0.14 g of copper sulfate pentahydrate to the mixed solution obtained in step 1, and react at 50° C. for 6 hours; after the reaction is completed, filter, wash and dry to obtain a surface-reconstructed material containing crystal water;
步骤3、在真空或惰性氛围下，将步骤3得到的含结晶水表面重构的材料在270℃下烧结4h，得到铜原子表面重构的高容量锂离子电池负极材料。Step 3. In vacuum or inert atmosphere, sinter the resurfaced material containing crystal water obtained in step 3 at 270° C. for 4 hours to obtain a high-capacity lithium-ion battery negative electrode material with resurfaced copper atoms.
本实施例制备的铜原子表面重构草酸亚铁重构界面扫描电镜图样，如图2所示。The scanning electron microscope pattern of the restructured ferrous oxalate interface on the surface of copper atoms prepared in this example is shown in FIG. 2 .
实施例2Example 2
一种铜原子表面重构策略制备高容量的草酸亚铁锂离子电池负极材料，其具体步骤如下：A copper atom surface reconstruction strategy prepares a high-capacity ferrous oxalate lithium-ion battery negative electrode material, and its specific steps are as follows:
步骤1、将草酸亚铁高容量负极材料，分散于80ml无水乙醇与10ml去离子水构成的混合溶液，得到分散均匀的混合液；其中，金属含氧酸盐与混合溶液的比例：1g:90ml；Step 1, the ferrous oxalate high-capacity negative electrode material is dispersed in the mixed solution that 80ml dehydrated alcohol and 10ml deionized water are formed, obtains the mixed solution that is dispersed uniformly; Wherein, the ratio of metal oxalate and mixed solution: 1g: 90ml;
步骤2、向步骤1得到的混合溶液中加入0.14g五水合硫酸铜，50℃条件下反应6h；反应完成后过滤、洗涤和干燥，得到含结晶水表面重构的材料； Step 2. Add 0.14 g of copper sulfate pentahydrate to the mixed solution obtained in step 1, and react at 50° C. for 6 hours; after the reaction is completed, filter, wash and dry to obtain a surface-reconstructed material containing crystal water;
步骤3、在惰性氛围下，将步骤3得到的含结晶水表面重构的材料在270℃下烧结4h，得到铜原子表面重构草酸亚铁锂离子电池负极材料。Step 3. In an inert atmosphere, sinter the surface-reconstructed material containing crystal water obtained in step 3 at 270° C. for 4 hours to obtain a negative electrode material for a copper-atom-resurfaced ferrous oxalate lithium-ion battery.
称取0.1g本实施例制备得到表面重构草酸亚铁、0.01g乙炔黑、0.02g碳纳米管、0.05g聚偏氟乙烯(PVDF)，放入研钵，加入1.8ml N～甲基～2～吡咯烷酮溶液，研磨、搅拌40min，将浆料均匀分散涂布与铜箔上，然后在60℃条件下热空气氛围中干燥30min，随后转移至60℃的真空烘箱中持续干燥12h后，剪裁直径为13.5mm极片。Weigh 0.1g of the surface-reconstructed ferrous oxalate prepared in this example, 0.01g of acetylene black, 0.02g of carbon nanotubes, and 0.05g of polyvinylidene fluoride (PVDF), put them into a mortar, and add 1.8ml of N~methyl~ 2～Pyrrolidone solution, grind and stir for 40 minutes, evenly disperse the slurry and coat it on the copper foil, then dry it in a hot air atmosphere at 60°C for 30 minutes, then transfer it to a vacuum oven at 60°C for 12 hours, and then cut The pole piece is 13.5mm in diameter.
在充满氩气的手套箱中利用一般的常规方法即可将极片以现有商业可购买的隔膜、锂片、电池壳和镍网组装成电池。通过新威电池测试柜，即可得到通过铜原子重构的草酸亚铁负极材料循环稳定性曲线，如图3所示。In a glove box filled with argon gas, the pole piece can be assembled into a battery with existing commercially available separators, lithium sheets, battery cases and nickel meshes by using general conventional methods. Through the Xinwei battery test cabinet, the cycle stability curve of the ferrous oxalate negative electrode material reconstructed by copper atoms can be obtained, as shown in Figure 3.
实施例3Example 3
一种镍、钴原子联合表面重构策略制备高容量的草酸亚铁材料，其具体步骤如下：A joint surface reconstruction strategy of nickel and cobalt atoms to prepare high-capacity ferrous oxalate materials, the specific steps are as follows:
步骤1、将草酸亚铁高容量负极材料，分散于80ml无水乙醇、10mlNMP与10ml去离子水构成的混合溶液，得到分散均匀的混合液；其中，金属含氧酸盐与混合溶液的比例：1g:100ml；Step 1. Disperse the ferrous oxalate high-capacity negative electrode material in a mixed solution composed of 80ml of absolute ethanol, 10ml of NMP and 10ml of deionized water to obtain a uniformly dispersed mixed solution; wherein, the ratio of the metal oxalate to the mixed solution is: 1g: 100ml;
步骤2、向步骤1得到的混合溶液中加入0.01g六水合硫酸镍和0.01g七水合硫酸钴，50℃条件下反应6h；反应完成后过滤、洗涤和干燥，得到镍、钴原子联合表面重构的含结晶水的草酸亚铁材料； Step 2. Add 0.01g of nickel sulfate hexahydrate and 0.01g of cobalt sulfate heptahydrate to the mixed solution obtained in step 1, and react for 6 hours at 50°C; after the reaction is completed, filter, wash and dry to obtain the combined surface weight of nickel and cobalt atoms Structured ferrous oxalate material containing crystal water;
步骤3、在惰性氛围下，将步骤3得到的含结晶水表面重构的材料在300℃下烧结4h，得到镍、钴原子联合表面重构的高容量锂离子电池负极材料。Step 3. In an inert atmosphere, sinter the surface-reconstructed material containing crystal water obtained in step 3 at 300° C. for 4 hours to obtain a high-capacity lithium-ion battery negative electrode material with joint surface restructured nickel and cobalt atoms.
实施例4Example 4
一种钴原子表面重构策略制备高容量的氢氧化铜材料，其具体步骤如下：A cobalt atom surface reconstruction strategy to prepare a high-capacity copper hydroxide material, the specific steps are as follows:
步骤1、将氢氧化铜高容量负极材料，分散于80ml无水乙醇与10ml去离子水和0.5gCTAB和2ml浓盐酸构成的混合溶液，得到分散均匀的混合液；其中，金属含氧酸盐与混合溶液的比例：1g:90ml；Step 1. Disperse the copper hydroxide high-capacity negative electrode material in a mixed solution composed of 80ml absolute ethanol, 10ml deionized water, 0.5gCTAB and 2ml concentrated hydrochloric acid to obtain a uniformly dispersed mixed solution; wherein, the metal oxo acid salt and The ratio of the mixed solution: 1g:90ml;
步骤2、向步骤1得到的混合溶液中加入6.3g六水合硝酸钴，80℃条件下反应24h；反应完成后过滤、洗涤和干燥，得到含结晶水表面重构的材料； Step 2. Add 6.3 g of cobalt nitrate hexahydrate to the mixed solution obtained in step 1, and react at 80° C. for 24 hours; after the reaction is completed, filter, wash and dry to obtain a surface-reconstructed material containing crystal water;
步骤3、在惰性氛围下，将步骤3得到的含结晶水表面重构的材料在300℃下烧结4h，得到钴原子表面重构的高容量锂离子电池负极材料。Step 3. In an inert atmosphere, sinter the surface restructured material containing crystal water obtained in step 3 at 300° C. for 4 hours to obtain a high-capacity lithium-ion battery negative electrode material with cobalt atom surface restructured.
实施例5Example 5
一种锰原子表面重构策略制备高容量的碳酸亚铁材料，其具体步骤如下：A manganese atom surface reconstruction strategy to prepare high-capacity ferrous carbonate materials, the specific steps are as follows:
步骤1、将碳酸亚铁高容量负极材料，分散于30ml无水乙醇、60ml去离子水、1ml浓盐酸和0.5g Pss、2.5g抗坏血酸构成的混合溶液，得到分散均匀的混合液；其中，金属含氧酸盐与混合溶液的比例：1g:90ml；Step 1. Disperse the ferrous carbonate high-capacity negative electrode material in a mixed solution composed of 30ml absolute ethanol, 60ml deionized water, 1ml concentrated hydrochloric acid, 0.5g Pss, and 2.5g ascorbic acid to obtain a uniformly dispersed mixed solution; wherein, the metal The ratio of oxo acid salt to mixed solution: 1g:90ml;
步骤2、向步骤1得到的混合溶液中加入5.5g七水合硫酸亚铁，80℃条件下反应24h；反应完成后过滤、洗涤和干燥，得到含结晶水表面重构的材料； Step 2. Add 5.5 g of ferrous sulfate heptahydrate to the mixed solution obtained in step 1, and react at 80° C. for 24 hours; after the reaction is completed, filter, wash and dry to obtain a surface-reconstructed material containing crystal water;
步骤3、在惰性氛围下，将步骤3得到的含结晶水表面重构的材料在300℃下烧结4h，得到锰原子表面重构的高容量锂离子电池负极材料。Step 3. In an inert atmosphere, sinter the surface-reconstructed material containing crystal water obtained in step 3 at 300° C. for 4 hours to obtain a high-capacity lithium-ion battery negative electrode material with manganese atom surface-reconstructed.
以上结合附图对本发明的具体实施方式作了详细说明，但是本发明并不限于上述实施方式，在本领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。The specific embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the above embodiments. Variations.

Claims (5)

  1. 一种颗粒表面重构设计高容量电极材料的方法，其特征在于具体步骤如下：步骤1、将金属含氧酸盐高容量负极材料，分散于有机溶剂和去离子水的混合溶液中，得到分散均匀的混合液；其中，金属含氧酸盐与混合溶液的质量体积比为：0.1～1g:50～200ml；步骤2、向步骤1得到的混合溶液中加入可溶性金属盐，0～200℃条件下反应5～72h，反应完成后过滤、洗涤和干燥，得到含结晶水表面重构的材料；步骤3、在真空或惰性氛围下，将步骤3得到的含结晶水表面重构的材料在200℃～350℃下烧结4～10h，得到表面重构的高容量锂离子电池负极材料。A method for designing a high-capacity electrode material by particle surface reconstruction, characterized in that the specific steps are as follows: Step 1, dispersing the metal oxo-salt high-capacity negative electrode material in a mixed solution of an organic solvent and deionized water to obtain a dispersed Uniform mixed solution; wherein, the mass-volume ratio of the metal oxo acid salt to the mixed solution is: 0.1-1g:50-200ml; step 2, adding soluble metal salts to the mixed solution obtained in step 1, at 0-200°C React for 5 to 72 hours. After the reaction is completed, filter, wash and dry to obtain a surface-reconstructed material containing crystal water; step 3. Under vacuum or an inert atmosphere, the material containing crystal water surface restructure obtained in step 3 is heated at 200 and sintering for 4-10 hours at ℃ to 350 ℃ to obtain a negative electrode material of a high-capacity lithium-ion battery with surface reconstruction.
  2. 根据权利要求1所述的一种颗粒表面重构设计高容量电极材料的方法，其特征在于：所述步骤1中的有机溶剂包括无水乙醇、乙二醇、CTAB、NMP、DMA、DMSO、DMF中的一种或多种组合。A method for designing high-capacity electrode materials by particle surface reconstruction according to claim 1, characterized in that: the organic solvent in the step 1 includes absolute ethanol, ethylene glycol, CTAB, NMP, DMA, DMSO, One or more combinations of DMF.
  3. 根据权利要求1所述的一种颗粒表面重构设计高容量电极材料的方法，其特征在于：所述步骤1中的混合溶液还包括PDDA、Pss、硫酸、盐酸中的一种或多种。A method for designing high-capacity electrode materials by particle surface reconstruction according to claim 1, characterized in that: the mixed solution in the step 1 further includes one or more of PDDA, Pss, sulfuric acid, and hydrochloric acid.
  4. 根据权利要求1所述的一种颗粒表面重构设计高容量电极材料的方法，其特征在于：所述步骤2中的可溶性金属盐包括过渡金属硝酸盐、硫酸盐、醋酸盐中的一种或几种。A method for designing high-capacity electrode materials by particle surface reconstruction according to claim 1, characterized in that: the soluble metal salt in the step 2 includes one of transition metal nitrates, sulfates, and acetates or several.
  5. 根据权利要求1所述的一种颗粒表面重构设计高容量电极材料的方法，其特征在于：所述步骤2中的可溶性金属盐与金属含氧酸盐的摩尔比为：0.01～1：1～0.01。A method for designing high-capacity electrode materials by particle surface reconstruction according to claim 1, characterized in that the molar ratio of the soluble metal salt to the metal oxo acid salt in the step 2 is: 0.01-1:1 ~0.01.
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