CN106532003A - Ti4O7-coated modified lithium titanate composite material and preparation method thereof - Google Patents
Ti4O7-coated modified lithium titanate composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 19
- -1 modified lithium titanate Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 229910009848 Ti4O7 Inorganic materials 0.000 title 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 239000011247 coating layer Substances 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 abstract 1
- 150000002641 lithium Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- 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
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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
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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
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
本发明公开了一种亚氧化钛包覆改性钛酸锂复合材料及其制备方法，所述亚氧化钛改性钛酸锂复合材料的化学式Li4Ti5O12/Ti4O7。本发明技术方案采用具有良好导电性和耐腐蚀性的亚氧化钛作为包覆层对钛酸锂进行改性，钛酸锂表面包覆一层亚氧化钛膜，有效提高钛酸锂导电性、抑制电解液对钛酸锂材料的腐蚀，显著改善其倍率性能及循环性能，使其适应动力锂离子电池的需求。而且，本发明技术方法操作工艺简单，适合工业化生产。
The invention discloses a titanium oxide-coated modified lithium titanate composite material and a preparation method thereof. The chemical formula of the titanium oxide-modified lithium titanate composite material is Li 4 Ti 5 O 12 /Ti 4 O 7 . The technical solution of the present invention adopts titanium oxide with good conductivity and corrosion resistance as the coating layer to modify lithium titanate, and the surface of lithium titanate is covered with a layer of titanium oxide film, which effectively improves the conductivity of lithium titanate, Inhibit the corrosion of the lithium titanate material by the electrolyte, significantly improve its rate performance and cycle performance, and make it suitable for the needs of power lithium-ion batteries. Moreover, the technical method of the present invention has simple operation process and is suitable for industrialized production.
Description
技术领域technical field
本发明属于锂离子电池技术领域，尤其涉及一种亚氧化钛包覆改性钛酸锂复合材料及其制备方法。The invention belongs to the technical field of lithium ion batteries, and in particular relates to a titanium oxide-coated modified lithium titanate composite material and a preparation method thereof.
背景技术Background technique
尖晶石型钛酸锂作为一种新型的锂离子动力电池负极材料，以其优异性能成为碳负极材料的替代材料。该材料在充放电过程中，锂离子的嵌入和脱出基本不会引起晶体结构变化，被称为“零应变材料”。并且，钛酸锂具有较高的嵌锂电位，不易形成锂枝晶，具有很好的安全性能。但是，由于钛酸锂导电性能差，其比容量在高倍率充放电时迅速衰减，这是目前制约钛酸锂商品化应用的关键。因此，要实现钛酸锂在动力锂离子电池中的广泛应用，需要改善该材料的导电性能。常规方法多采用增大比表面积、离子掺杂改性及导电相掺杂及包覆改性。其中，包覆改性方法中使用的包覆材料主要采用碳材料。但碳材料耐腐蚀性差，且在锂离子嵌入脱出过程中结构容易发生变化，导致锂离子电池循环性能较差。Spinel-type lithium titanate, as a new type of anode material for lithium-ion power batteries, has become an alternative material for carbon anode materials due to its excellent performance. During the charge and discharge process of this material, the intercalation and extraction of lithium ions will basically not cause changes in the crystal structure, which is called "zero strain material". Moreover, lithium titanate has a high lithium intercalation potential, is not easy to form lithium dendrites, and has good safety performance. However, due to the poor conductivity of lithium titanate, its specific capacity rapidly decays during high-rate charge and discharge, which is the key to restricting the commercial application of lithium titanate. Therefore, in order to realize the wide application of lithium titanate in power lithium-ion batteries, it is necessary to improve the conductivity of the material. Conventional methods mostly use increasing specific surface area, ion doping modification, conductive phase doping and coating modification. Among them, the coating material used in the coating modification method mainly adopts carbon materials. However, the corrosion resistance of carbon materials is poor, and the structure is easy to change during the process of intercalation and extraction of lithium ions, resulting in poor cycle performance of lithium-ion batteries.
发明内容Contents of the invention
针对现有技术问题，本发明公开了一种亚氧化钛包覆改性钛酸锂复合材料及其制备方法，其创新之处在于复合材料的设计及制备方法。本发明提供的亚氧化钛包覆改性钛酸锂复合材料化学式为Li4Ti5O12/Ti4O7。亚氧化钛(Ti4O7)的导电性及耐腐蚀性能均优于碳材料，可有效的降低内阻，改善钛酸锂材料的倍率性能。本发明提供的制备方法，步骤如下：Aiming at the problems of the prior art, the invention discloses a titanium oxide-coated modified lithium titanate composite material and a preparation method thereof, the innovation of which lies in the design and preparation method of the composite material. The chemical formula of the titanium oxide-coated modified lithium titanate composite material provided by the present invention is Li 4 Ti 5 O 12 /Ti 4 O 7 . The conductivity and corrosion resistance of titanium oxide (Ti 4 O 7 ) are superior to carbon materials, which can effectively reduce internal resistance and improve the rate performance of lithium titanate materials. The preparation method provided by the invention has the following steps:
步骤1钛酸锂粉末于30~200℃下干燥2~10h；Step 1: Dry the lithium titanate powder at 30-200°C for 2-10 hours;
步骤2将钛酸丁酯加入到无水乙醇中搅拌后，依次加入乙酸和去离子水，搅拌3~24h后得到溶胶溶液，其中，所述述钛酸丁酯与乙酸的体积比为(2~5.5):1，所述去离子水的用量为钛酸丁酯体积的1/10；In step 2, after adding butyl titanate to absolute ethanol and stirring, add acetic acid and deionized water successively, and stir for 3 to 24 hours to obtain a sol solution, wherein the volume ratio of said butyl titanate to acetic acid is (2 ~5.5): 1, the consumption of described deionized water is 1/10 of the volume of butyl titanate;
步骤3将步骤1所述的钛酸锂加入到步骤2所述的溶胶溶液中，搅拌6~48h后真空抽滤，于30~150℃下干燥2~10h得前驱体粉末，所述钛酸锂与钛酸丁酯的物质的量比为(4.5～11):1；Step 3: Add the lithium titanate described in step 1 into the sol solution described in step 2, stir for 6-48 hours, vacuum filter, and dry at 30-150°C for 2-10 hours to obtain a precursor powder. The titanate The molar ratio of lithium to butyl titanate is (4.5～11):1;
步骤4将步骤3所述的前驱体粉末在氢气气氛下于830～870℃还原3~6h，冷却至100℃下出炉，即得到亚氧化钛包覆改性钛酸锂复合材料。In step 4, the precursor powder described in step 3 is reduced in a hydrogen atmosphere at 830-870° C. for 3-6 hours, cooled to 100° C., and released from the furnace to obtain a titanium oxide-coated modified lithium titanate composite material.
上述方法中，钛酸丁酯和无水乙醇的体积比为1:( 2～4)。In the above method, the volume ratio of butyl titanate to absolute ethanol is 1:(2-4).
本发明具有以下有益效果：The present invention has the following beneficial effects:
本发明采用具有高导电性的亚氧化钛对钛酸锂材料进行包覆改性，在钛酸锂表面形成一层亚氧化钛薄膜，显著改善钛酸锂的导电性。亚氧化钛作为一种高导电性材料，化学稳定性优异，在高电流密度或高酸条件下耐腐蚀且不易发生钝化。因此，亚氧化钛包覆改性钛酸锂复合材料可进一步提高钛酸锂材料的倍率性能及循环稳定性能。而且，本发明技术方案的工艺简便易操作，适合工业化生产。The invention adopts high-conductivity titanium suboxide to coat and modify the lithium titanate material, forms a layer of titanium suboxide film on the surface of the lithium titanate, and significantly improves the conductivity of the lithium titanate. Titanium oxide is a highly conductive material with excellent chemical stability, corrosion resistance and low passivation under high current density or high acid conditions. Therefore, titanium oxide-coated modified lithium titanate composite materials can further improve the rate performance and cycle stability of lithium titanate materials. Moreover, the process of the technical solution of the present invention is simple and easy to operate, and is suitable for industrial production.
附图说明Description of drawings
图1是实施例1制备的亚氧化钛包覆改性钛酸锂复合材料的扫描电镜图片。FIG. 1 is a scanning electron microscope picture of the titanium oxide-coated modified lithium titanate composite material prepared in Example 1.
图2是实施例1制备的亚氧化钛包覆改性钛酸锂复合材料恒流充放电曲线图。FIG. 2 is a constant current charge and discharge curve of the titanium dioxide-coated modified lithium titanate composite material prepared in Example 1. FIG.
具体实施方式detailed description
下面结合实施例，对本发明进行详细描述。The present invention will be described in detail below in conjunction with the embodiments.
实施例1Example 1
（1）将纳米级钛酸锂粉末于200℃下干燥2h；（2）将钛酸丁酯与无水乙醇按体积比1:4采用搅拌器搅拌均匀，搅拌过程中依次逐渐滴加乙酸和去离子水，乙酸与钛酸丁酯的体积比为1:5.5，去离子水与钛酸丁酯的体积比为1:10，搅拌3h得到均匀溶胶溶液；（3）按照钛酸锂与钛酸丁酯的物质的量比4.5:1，将钛酸锂粉体加入到氧化钛溶胶溶液中，搅拌6h后进行真空抽滤，并于30℃真空干燥10h得前驱体粉末；（4）将前驱体粉末于氢气气氛炉中830℃还原6h，冷却至100℃下出炉，即得亚氧化钛包覆改性钛酸锂复合材料。(1) Dry nanoscale lithium titanate powder at 200°C for 2 hours; (2) Mix butyl titanate and absolute ethanol at a volume ratio of 1:4 with a stirrer, and gradually add acetic acid and Deionized water, the volume ratio of acetic acid and butyl titanate is 1:5.5, the volume ratio of deionized water and butyl titanate is 1:10, stir for 3 hours to obtain a uniform sol solution; (3) according to the lithium titanate and titanium The molar ratio of butyl ester is 4.5:1. Add lithium titanate powder into titanium oxide sol solution, stir for 6 hours, vacuum filter, and vacuum dry at 30°C for 10 hours to obtain precursor powder; (4) The precursor powder was reduced in a hydrogen atmosphere furnace at 830°C for 6 hours, cooled to 100°C and released from the furnace to obtain titanium oxide-coated modified lithium titanate composite material.
以锂片为负极，在充满氩气的手套箱内，制作扣式电池，在1~3V电压范围内做恒流充放电测试，在0.2C、0.5C、1C、2C、5C、10C倍率下，容量分别为166.2mAh/g、162.1mAh/g、160.2 mAh/g、156.6 mAh/g、147.5 mAh/g、137.1 mAh/g。Using a lithium sheet as the negative electrode, make a button battery in a glove box filled with argon, and do a constant current charge and discharge test in the voltage range of 1~3V, at 0.2C, 0.5C, 1C, 2C, 5C, 10C rate , the capacities are 166.2mAh/g, 162.1mAh/g, 160.2 mAh/g, 156.6 mAh/g, 147.5 mAh/g, 137.1 mAh/g respectively.
实施例2Example 2
（1）将微米级钛酸锂粉末于30℃下干燥10h；（2）将钛酸丁酯与无水乙醇按体积比1:2采用磁力搅拌均匀，搅拌过程中依次逐渐滴加乙酸和去离子水，乙酸与钛酸丁酯的体积比为1:2，去离子水与钛酸丁酯的体积比为1:10，搅拌24h得到均匀溶胶溶液；（3）按照钛酸锂与钛酸丁酯的物质的量比11:1，将钛酸锂粉体加入到氧化钛溶胶溶液中，搅拌48h后进行真空抽滤，并于150℃真空干燥2h得前驱体粉末；（4）将前驱体粉末于氢气气氛炉中870℃还原3h，冷却至100℃下出炉，即得亚氧化钛包覆的钛酸锂复合材料。(1) Dry micron-sized lithium titanate powder at 30°C for 10 hours; (2) Mix butyl titanate and absolute ethanol at a volume ratio of 1:2 using magnetic stirring, and gradually add acetic acid and remove Ionized water, the volume ratio of acetic acid and butyl titanate is 1:2, the volume ratio of deionized water and butyl titanate is 1:10, stir for 24 hours to obtain a uniform sol solution; (3) according to the lithium titanate and titanate The substance ratio of butyl ester is 11:1. Add lithium titanate powder into titanium oxide sol solution, stir for 48 hours, vacuum filter, and vacuum dry at 150°C for 2 hours to obtain precursor powder; (4) Precursor The bulk powder was reduced in a hydrogen atmosphere furnace at 870°C for 3 hours, cooled to 100°C and released from the furnace to obtain a titanium oxide-coated lithium titanate composite material.
以锂片为负极，在充满氩气的手套箱内，制作扣式电池，在1~3V电压范围内做恒流充放电测试，在0.2C、0.5C、1C、2C、5C、10C倍率下，容量分别为168.3mAh/g、165.2mAh/g、162.2 mAh/g、159.5 mAh/g、149.5 mAh/g、138.1 mAh/g。Using a lithium sheet as the negative electrode, make a button battery in a glove box filled with argon, and do a constant current charge and discharge test in the voltage range of 1~3V, at 0.2C, 0.5C, 1C, 2C, 5C, 10C rate , the capacities are 168.3mAh/g, 165.2mAh/g, 162.2 mAh/g, 159.5 mAh/g, 149.5 mAh/g, 138.1 mAh/g respectively.
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Cited By (2)
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| CN109449408A (en) * | 2018-10-30 | 2019-03-08 | 中科廊坊过程工程研究院 | A kind of ferric flouride-Asia titanium oxide composite positive pole and its preparation method and application |
| CN112607769A (en) * | 2020-12-18 | 2021-04-06 | 北方奥钛纳米技术有限公司 | Lithium titanate battery material, preparation method and application thereof |
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| CN102496704A (en) * | 2011-12-08 | 2012-06-13 | 中信国安盟固利电源技术有限公司 | Lithium titanate/titanium black anode material and preparation method thereof |
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| CN109449408A (en) * | 2018-10-30 | 2019-03-08 | 中科廊坊过程工程研究院 | A kind of ferric flouride-Asia titanium oxide composite positive pole and its preparation method and application |
| CN109449408B (en) * | 2018-10-30 | 2021-08-17 | 中科廊坊过程工程研究院 | A kind of iron fluoride-titanium oxide composite cathode material and preparation method and application thereof |
| CN112607769A (en) * | 2020-12-18 | 2021-04-06 | 北方奥钛纳米技术有限公司 | Lithium titanate battery material, preparation method and application thereof |
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