CN102157732A - Titanium dioxide/carbon composite nanotube and preparation and application thereof - Google Patents
Titanium dioxide/carbon composite nanotube and preparation and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000002071 nanotube Substances 0.000 title claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 14
- 239000008103 glucose Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000005416 organic matter Substances 0.000 claims description 8
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000010406 cathode material Substances 0.000 abstract 2
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000012496 blank sample Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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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
- 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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Abstract
Description
技术领域technical field
本发明属于化学电源领域，特别是一种二氧化钛/碳复合纳米管及其制备以及作为锂离子电池负极材料的应用。The invention belongs to the field of chemical power sources, in particular to a titanium dioxide/carbon composite nanotube and its preparation and application as a lithium ion battery negative electrode material.
背景技术Background technique
目前，商业上用的锂离子电池负极材料为碳材料，它存在一定的缺点，比如，碳的电位接近金属锂的电位，在充放电过程中容易发生锂枝晶析出，从而引发安全问题。锐钛矿相二氧化钛作为锂离子电池负极材料具有明显的优势：在充放电过程中体积变化很小，循环性能好，在1.7V（vs,Li+/Li）处出现平台，与商品的碳材料相比，二氧化钛具有更好的安全性能。但是二氧化钛的导电性较差，影响了材料的高倍率性能，制约了它的应用。目前，提高二氧化钛的高倍率性能的方法有制备纳米尺寸材料以缩短锂离子扩散距离、体相掺杂、表面包覆导电相等途径。At present, the negative electrode material of commercially used lithium-ion batteries is carbon material, which has certain disadvantages. For example, the potential of carbon is close to that of metal lithium, and lithium dendrites are prone to precipitate during charging and discharging, thus causing safety problems. Anatase phase titanium dioxide has obvious advantages as the anode material of lithium-ion batteries: the volume change is small during charge and discharge, the cycle performance is good, and a platform appears at 1.7V (vs, Li + /Li), which is different from commercial carbon materials. Compared with titanium dioxide, it has better safety performance. However, the poor conductivity of titanium dioxide affects the high-rate performance of the material and restricts its application. At present, the methods to improve the high-rate performance of titanium dioxide include the preparation of nano-sized materials to shorten the diffusion distance of lithium ions, bulk phase doping, and surface coating conductive methods.
钛酸纳米管自1998年报道以来，人们采用了多种方法尝试制备了这种管状结构材料，并对其性能进行了深入的研究。研究发现，钛酸纳米管热稳定性差，当煅烧温度高于300℃时，其晶体结构转变为锐钛矿，同时其管状形貌遭到破坏，变为颗粒或短棒状结构。而若能制备具有管状结构的锐钛矿相二氧化钛，同时在其表面包覆碳，提高其导电性，将有望获得具备良好倍率性能的锂电池负极材料。Since titanate nanotubes were reported in 1998, people have used various methods to try to prepare this tubular structure material, and have conducted in-depth research on its properties. Studies have found that titanate nanotubes have poor thermal stability. When the calcination temperature is higher than 300 ° C, its crystal structure changes to anatase, and its tubular morphology is destroyed, turning into particles or short rod-like structures. However, if anatase titanium dioxide with a tubular structure can be prepared, and carbon can be coated on its surface to improve its conductivity, it is expected to obtain a negative electrode material for lithium batteries with good rate performance.
发明内容Contents of the invention
本发明的目的在于提供一种二氧化钛/碳复合纳米管，以克服作为锂离子电池负极材料时二氧化钛的导电性较差的缺陷。The object of the present invention is to provide a titanium dioxide/carbon composite nanotube to overcome the defect of poor electrical conductivity of titanium dioxide when used as a negative electrode material of a lithium ion battery.
本发明采用的技术方案如下：The technical scheme that the present invention adopts is as follows:
一种二氧化钛/碳复合纳米管，所述的复合纳米管为管状结构，由锐钛矿相二氧化钛与碳构成。A titanium dioxide/carbon composite nanotube, the composite nanotube has a tubular structure and is composed of anatase phase titanium dioxide and carbon.
所述的复合纳米管管内径为3-10nm。The internal diameter of the composite nanotube is 3-10nm.
所述的复合纳米管中碳的质量含量优选控制为1-10%。产物中的碳含量可通过调节含碳有机化合物的量来调节，在锂离子电池负极材料中进行应用时优选控制在1-10%。如果在其他不同的应用领域使用时，可以相应的进行碳含量的调整。The mass content of carbon in the composite nanotube is preferably controlled to be 1-10%. The carbon content in the product can be adjusted by adjusting the amount of carbon-containing organic compounds, and it is preferably controlled at 1-10% when applied in lithium-ion battery negative electrode materials. If it is used in other different application fields, the carbon content can be adjusted accordingly.
本发明还进一步提供了一种所述的二氧化钛/碳复合纳米管的制备方法：将钛酸纳米管与可溶性有机物的溶液混合充分反应，之后干燥、研磨均匀，于惰性气氛中进行煅烧，即得所述二氧化钛/碳复合纳米管。The present invention further provides a method for preparing the titanium dioxide/carbon composite nanotube: mix the titanate nanotube and the solution of soluble organic matter to fully react, then dry, grind evenly, and calcinate in an inert atmosphere to obtain The titanium dioxide/carbon composite nanotube.
所述的可溶性有机物为葡萄糖、蔗糖、可溶性淀粉、果糖、酒石酸、柠檬酸、苯甲酸或三聚氰胺。即所述的可溶性有机物可选择可溶性含碳有机化合物，也可为含有其他杂原子的含碳有机化合物。可溶性有机物的溶液的溶剂为水或乙醇。The soluble organic matter is glucose, sucrose, soluble starch, fructose, tartaric acid, citric acid, benzoic acid or melamine. That is to say, the soluble organic matter may be a soluble carbon-containing organic compound, or a carbon-containing organic compound containing other heteroatoms. The solvent of the solution of soluble organic matter is water or ethanol.
所用碳源可溶性含碳有机化合物，将其溶于水或乙醇等溶剂中时，要实现含碳有机化合物溶液和钛酸纳米管的混合均匀，一般加溶剂的量是含碳有机化合物溶液和钛酸纳米管混合后成泥浆状为最佳。The carbon source soluble carbon-containing organic compound used, when dissolving it in solvents such as water or ethanol, to realize the uniform mixing of the carbon-containing organic compound solution and titanate nanotubes, the general amount of solubilizer is the carbon-containing organic compound solution and titanium It is best to mix the acid nanotubes into mud.
所述的钛酸纳米管为钛酸钠纳米管在强酸中浸泡后并洗涤至pH为4-9的钛酸纳米管。The titanate nanotubes are sodium titanate nanotubes soaked in strong acid and washed until the pH is 4-9.
干燥温度为室温至200℃，干燥时间不低于30min，一般不超过2d。The drying temperature is from room temperature to 200°C, and the drying time is not less than 30 minutes, generally not more than 2 days.
煅烧温度为300-500℃，时间为1-6h。The calcination temperature is 300-500°C, and the time is 1-6h.
本发明中采用廉价的碳源，将其溶于合适的溶剂中形成均匀溶液，然后将钛酸纳米管置于溶液中，搅拌混合，并干燥混合物，之后于惰性气氛中煅烧，即可得二氧化钛/碳复合纳米管。In the present invention, a cheap carbon source is used, which is dissolved in a suitable solvent to form a uniform solution, then the titanate nanotubes are placed in the solution, stirred and mixed, and the mixture is dried, and then calcined in an inert atmosphere to obtain titanium dioxide / carbon composite nanotubes.
所述复合纳米管具有良好的管形结构，高的比表面积，尺寸均匀，分散性好。The composite nanotube has good tubular structure, high specific surface area, uniform size and good dispersibility.
所述的二氧化钛/碳复合纳米管作为锂离子电池负极材料有很好的应用，具有优异的电化学性能。The titanium dioxide/carbon composite nanotube has good application as the negative electrode material of lithium ion battery, and has excellent electrochemical performance.
由于所获得的管状结构材料同时由锐钛矿二氧化钛和碳构成，因此材料同时具有二氧化钛和碳的性质，因此也可用于超级电容器、敏化太阳能电池、有机污染物吸附剂等领域。Since the obtained tubular structure material is composed of anatase titanium dioxide and carbon at the same time, the material has the properties of titanium dioxide and carbon at the same time, so it can also be used in supercapacitors, sensitized solar cells, organic pollutant adsorbents and other fields.
本发明相对于现有技术，有以下优点：Compared with the prior art, the present invention has the following advantages:
本发明的复合纳米管产品形貌均匀，具有良好的管形结构，高的比表面积，分散性好。制备方法简单易行，反应温度低，能耗低，原料廉价易得，无污染，产率高，容易实现规模化生产；获得的产品改善了二氧化钛纳米管锂离子电池负极材料的电导率、充放电性能、循环性能、倍率性能。The composite nanotube product of the invention has uniform appearance, good tubular structure, high specific surface area and good dispersibility. The preparation method is simple and easy, the reaction temperature is low, the energy consumption is low, the raw material is cheap and easy to obtain, no pollution, the yield is high, and it is easy to realize large-scale production; Discharge performance, cycle performance, rate performance.
附图说明Description of drawings
图1为实施例1、2、3、4及钛酸纳米管在惰性气氛400℃煅烧4h得到的空白样锐钛矿二氧化钛纳米管的XRD图；Fig. 1 is the XRD figure of the blank sample anatase titania nanotube obtained by calcining 400 ℃ of
图2为实施例2、5、6的XRD图；Fig. 2 is the XRD figure of
图3为实施例2的HRTEM图；Fig. 3 is the HRTEM figure of
图4为实施例5的HRTEM图；Fig. 4 is the HRTEM figure of
图5为实施例6的HRTEM图；Fig. 5 is the HRTEM figure of
图6为实施例1、2、3、4及惰性气氛400oC煅烧4h得到的空白样锐钛矿二氧化钛纳米管在不同倍率下的倍率性能图；Fig. 6 is the rate performance diagram of the blank sample anatase titanium dioxide nanotubes obtained by calcining at 400 o C for 4 hours in Examples 1, 2, 3, 4 and inert atmosphere at different rates;
图7为实施例1、2、3、4及惰性气氛400oC煅烧4h得到的空白样锐钛矿二氧化钛纳米管在5C下的循环性能图；Fig. 7 is the cycle performance diagram of the blank sample anatase titanium dioxide nanotube obtained by calcination at 400 o C of
图8为实施例2、5、6在不同倍率下的倍率性能图；Figure 8 is a rate performance diagram of Examples 2, 5, and 6 at different rates;
图9为惰性气氛400oC煅烧4h得到的空白样锐钛矿二氧化钛纳米管在0.2C下前5次充放电曲线图；Figure 9 is the charge and discharge curves of the blank sample anatase titanium dioxide nanotubes obtained by calcination at 400 o C for 4 hours at 0.2C for the first five times;
图10为实施例2在0.2C下前5次充放电曲线图。Fig. 10 is the first 5 charging and discharging curves of Example 2 at 0.2C.
具体实施方式Detailed ways
以下以具体实施例来说明本发明的技术方案，但本发明的保护范围不限于此：The technical scheme of the present invention is described below with specific examples, but protection scope of the present invention is not limited thereto:
实施例1Example 1
以葡萄糖为碳源，葡萄糖溶解在适量蒸馏水中，按照C∶TiO2=2∶98的质量比例加入一定量的钛酸纳米管混合研磨均匀，成泥浆状，60℃干燥5h，再研磨均匀，混合物于惰性气氛，升温至400℃进行煅烧，反应时间4h。即得二氧化钛/碳复合纳米管。Using glucose as the carbon source, the glucose was dissolved in an appropriate amount of distilled water, and a certain amount of titanic acid nanotubes were added according to the mass ratio of C:TiO 2 =2:98, mixed and ground into a slurry, dried at 60°C for 5 hours, and then ground evenly. The mixture was heated to 400° C. for calcination in an inert atmosphere, and the reaction time was 4 hours. That is, titanium dioxide/carbon composite nanotubes are obtained.
实施例2Example 2
用葡萄糖作为碳源，葡萄糖溶解在适量蒸馏水中，按照Cwt%=5% 即（C∶TiO2=5∶95）加入一定量的钛酸纳米管混合研磨均匀，成泥浆状，60℃干燥8h，再研磨均匀，混合物于惰性气氛，升温至400℃进行煅烧，反应时间4h。即得二氧化钛/碳复合纳米管。Use glucose as a carbon source, dissolve glucose in an appropriate amount of distilled water, add a certain amount of titanic acid nanotubes according to Cwt%=5% (C:TiO 2 =5:95), mix and grind evenly, and dry at 60°C for 8 hours , and then ground evenly, the mixture was calcined at 400° C. in an inert atmosphere, and the reaction time was 4 hours. That is, titanium dioxide/carbon composite nanotubes are obtained.
实施例3Example 3
用葡萄糖作为碳源，葡萄糖溶解在适量蒸馏水中，按照Cwt%=7.5% 即（C∶TiO2=7.5∶92.5）加入一定量的钛酸纳米管混合研磨均匀，成泥浆状，60℃干燥10h，再研磨均匀，混合物于惰性气氛，升温至400℃进行煅烧，反应时间4h。即得二氧化钛/碳复合纳米管。Use glucose as a carbon source, dissolve glucose in an appropriate amount of distilled water, add a certain amount of titanic acid nanotubes according to Cwt%=7.5% (C:TiO 2 =7.5:92.5), mix and grind evenly, and dry at 60°C for 10 hours , and then ground evenly, the mixture was calcined at 400° C. in an inert atmosphere, and the reaction time was 4 hours. That is, titanium dioxide/carbon composite nanotubes are obtained.
实施例4Example 4
用葡萄糖作为碳源，葡萄糖溶解在适量蒸馏水中，按照Cwt%=10% 即（C∶TiO2=10∶90）加入一定量的钛酸纳米管混合研磨均匀，成泥浆状，120℃干燥5h，再研磨均匀，混合物于惰性气氛，升温至400℃进行煅烧，反应时间4h。即得二氧化钛/碳复合纳米管。Use glucose as a carbon source, dissolve glucose in an appropriate amount of distilled water, add a certain amount of titanic acid nanotubes according to Cwt%=10% (C:TiO 2 =10:90), mix and grind evenly, and dry at 120°C for 5 hours , and then ground evenly, the mixture was calcined at 400° C. in an inert atmosphere, and the reaction time was 4 hours. That is, titanium dioxide/carbon composite nanotubes are obtained.
实施例5Example 5
用葡萄糖作为碳源，葡萄糖溶解在适量蒸馏水中，按照Cwt%=5% 即（C∶TiO2=5∶95）加入一定量的钛酸纳米管混合研磨均匀，成泥浆状，120℃干燥6h，再研磨均匀，混合物于惰性气氛，升温至300℃进行煅烧，反应时间4h。即得二氧化钛/碳复合纳米管。Use glucose as a carbon source, dissolve glucose in an appropriate amount of distilled water, add a certain amount of titanate nanotubes according to Cwt%=5% (C:TiO 2 =5:95), mix and grind evenly, and dry at 120°C for 6 hours , and then grind evenly, the mixture is heated to 300° C. for calcination in an inert atmosphere, and the reaction time is 4 hours. That is, titanium dioxide/carbon composite nanotubes are obtained.
实施例6Example 6
用葡萄糖作为碳源，葡萄糖溶解在适量蒸馏水中，按照Cwt%=5% 即（C∶TiO2=5∶95）加入一定量的钛酸纳米管混合研磨均匀，成泥浆状，120℃干燥7h，再研磨均匀，混合物于惰性气氛，升温至500℃进行煅烧，反应时间4h。即得二氧化钛/碳复合纳米管。Use glucose as a carbon source, dissolve glucose in an appropriate amount of distilled water, add a certain amount of titanic acid nanotubes according to Cwt%=5% (C:TiO 2 =5:95), mix and grind evenly, and dry at 120°C for 7 hours , and then ground evenly, the mixture was heated to 500° C. for calcination in an inert atmosphere, and the reaction time was 4 hours. That is, titanium dioxide/carbon composite nanotubes are obtained.
对所制备的材料进行电化学性能——恒流充放电测试：The electrochemical performance of the prepared material - constant current charge and discharge test:
进行电化学测试的测试电池电极膜片的组成：正极膜片是锐钛矿二氧化钛纳米管或二氧化钛/碳复合纳米管作为活性物质（在实验室测试时，是组装成半电池），活性物质∶导电剂乙炔黑∶粘结剂聚偏氟乙烯（PVDF）的质量比=80∶10∶10 。研磨半小时后，加适量N-甲基吡咯烷酮（NMP）成泥浆状，密闭容器中磁力搅拌12h后，涂在铜箔上，然后120℃烘大概6h，制出直径15mm的圆片。The composition of the test battery electrode diaphragm for electrochemical testing: the positive diaphragm is anatase titanium dioxide nanotube or titanium dioxide/carbon composite nanotube as the active material (in the laboratory test, it is assembled into a half-cell), the active material: Conductive agent acetylene black: binder polyvinylidene fluoride (PVDF) mass ratio = 80:10:10. After grinding for half an hour, add an appropriate amount of N-methylpyrrolidone (NMP) to make a slurry, stir it magnetically in a closed container for 12 hours, then apply it on a copper foil, and then bake it at 120°C for about 6 hours to produce a disc with a diameter of 15mm.
组装测试的模拟电池过程：封装电池在氩气氛手套箱中进行，金属锂作负极，电解液采用1mol/L LiPF6的EC∶DMC(1:1)混合液，隔膜采用Celgard 2400。从图6可以看出在0.2C、0.5C、1C、2C、5C不同倍率下的放电比容量，通过比较可看出，二氧化钛/碳复合纳米管比空白样TiO2纳米管的性能都好，在400℃时的二氧化钛/碳复合纳米管（5%）的性能最好。空白样TiO2纳米管，随倍率的增加，比容量衰减严重，0.2C充放电5次后，放电比容量为178.2mAh/g,5C充放电5次后，放电比容量为58.1mAh/g；二氧化钛/碳复合纳米管（5%），0.2C充放电5次后，放电比容量为220.3mAh/g，5C充放电5次后，放电比容量为144.3mAh/g。从图7可以看出在5C下，在400℃时的二氧化钛/碳复合纳米管（5%）的循环性也很好。5C下二氧化钛/碳复合纳米管（5%），50次循环后比容量仍保持在146.6mAh/g，而空白样TiO2纳米管，比容量则在60mAh/g。The simulated battery process of the assembly test: the packaged battery was carried out in an argon atmosphere glove box, metal lithium was used as the negative electrode, the electrolyte was a mixture of 1mol/L LiPF 6 EC:DMC (1:1), and the separator was Celgard 2400. It can be seen from Figure 6 that the discharge specific capacity at different rates of 0.2C, 0.5C, 1C, 2C, and 5C can be seen through comparison. The performance of titanium dioxide/carbon composite nanotubes is better than that of the blank sample TiO2 nanotubes. The TiO2/carbon composite nanotubes (5%) performed best at 400°C. Blank sample TiO 2 nanotubes, with the increase of the magnification, the specific capacity decays seriously. After 5 times of 0.2C charge and discharge, the discharge specific capacity is 178.2mAh/g, and after 5C charge and discharge for 5 times, the discharge specific capacity is 58.1mAh/g; Titanium dioxide/carbon composite nanotubes (5%), after 5 times of charging and discharging at 0.2C, the discharge specific capacity is 220.3mAh/g, and after 5 times of charging and discharging at 5C, the discharge specific capacity is 144.3mAh/g. It can be seen from Fig. 7 that at 5C, the cycleability of TiO2/C composite nanotubes (5%) at 400°C is also very good. At 5C, the specific capacity of titanium dioxide/carbon composite nanotubes (5%) remained at 146.6mAh/g after 50 cycles, while the specific capacity of the blank TiO 2 nanotubes was 60mAh/g.
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