CN104638256B - Nanocomposite, method for preparing nanocomposite, and lithium ion battery - Google Patents
Nanocomposite, method for preparing nanocomposite, and lithium ion battery Download PDFInfo
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 78
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 9
- 239000000463 material Substances 0.000 claims abstract description 80
- 229920000767 polyaniline Polymers 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 45
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 239000002052 molecular layer Substances 0.000 claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 29
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims 2
- 238000007254 oxidation reaction Methods 0.000 claims 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 56
- 239000002073 nanorod Substances 0.000 abstract description 9
- 231100000252 nontoxic Toxicity 0.000 abstract description 6
- 230000003000 nontoxic effect Effects 0.000 abstract description 6
- 238000010586 diagram Methods 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000001237 Raman spectrum Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000000608 laser ablation Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000003491 array Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004626 scanning electron microscopy Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 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
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
本发明公开了一种纳米复合材料及其制备方法和锂离子电池，该纳米复合材料由上部的聚苯胺纳米层、中间的TiO2/氧化石墨烯复合层以及下部的聚苯胺纳米层构成；其中，所述的聚苯胺纳米层为纳米棒状聚苯胺阵列；所述的TiO2/氧化石墨烯复合层为TiO2纳米颗粒分布在多层氧化石墨烯的网状结构中所形成的复合层。本发明实施例所提供的纳米复合材料不仅具有优良的循环稳定性和高倍率放电性能，而且材料无毒、环境友好、价格便宜；而该纳米复合材料的制备方法操作简单，绿色高效。
The invention discloses a nanocomposite material, a preparation method thereof and a lithium ion battery. The nanocomposite material is composed of an upper polyaniline nanolayer, a middle TiO 2 /graphene oxide composite layer and a lower polyaniline nanolayer; wherein , the polyaniline nano-layer is a nano-rod polyaniline array; the TiO 2 /graphene oxide composite layer is a composite layer formed by TiO 2 nanoparticles distributed in a network structure of multi-layer graphene oxide. The nanocomposite material provided by the embodiment of the present invention not only has excellent cycle stability and high rate discharge performance, but also is non-toxic, environmentally friendly and cheap; and the preparation method of the nanocomposite material is simple to operate, green and efficient.
Description
技术领域technical field
本发明涉及纳米材料领域，尤其涉及一种纳米复合材料及其制备方法和使用该纳米复合材料制得的锂离子电池。The invention relates to the field of nanometer materials, in particular to a nanocomposite material, a preparation method thereof and a lithium ion battery prepared by using the nanocomposite material.
背景技术Background technique
随着科技水平的不断进步，储能设备正朝着高性能、小型化的方向发展。锂离子电池不仅具有自放电率小、循环寿命长、无记忆效应、工作电压高等优点，而且具有优良的高低温放电性能、绿色环保，因此锂离子电池是目前最受人们广泛认可的储能设备。With the continuous advancement of science and technology, energy storage equipment is developing in the direction of high performance and miniaturization. Lithium-ion batteries not only have the advantages of small self-discharge rate, long cycle life, no memory effect, high working voltage, etc., but also have excellent high and low temperature discharge performance, and are environmentally friendly. Therefore, lithium-ion batteries are currently the most widely recognized energy storage devices. .
在现有技术中，锂离子电池的负极材料主要采用碳材料、锡基材料、硅基材料、钛基材料、氮化物和过渡金属氧化物等材料，但这些材料均存在一些难以克服的缺点，例如：①一些材料在形成SEI膜的过程中，容易形成锂枝晶，从而造成短路；②一些材料在锂的脱嵌过程中，会引起较大的体积膨胀，从而造成材料结构的崩塌，进而导致材料的循环稳定性下降；③还有一些Ti基负极材料虽然原料丰富、无毒无害、便宜稳定、安全性好，但比容量不高、电子导电率低，表面无法形成有效的电场。鉴于以上几点，人们开始制备量子点、合金等材料来减小体积膨胀，提高循环稳定性，但是尺寸小且活性高的纳米材料容易聚集，在锂插入合金后，机械稳定性差，容易使材料粉化。In the prior art, the negative electrode materials of lithium-ion batteries mainly use materials such as carbon materials, tin-based materials, silicon-based materials, titanium-based materials, nitrides, and transition metal oxides, but these materials have some insurmountable shortcomings. For example: ① some materials are easy to form lithium dendrites during the formation of SEI film, which will cause a short circuit; ② some materials will cause a large volume expansion during the lithium deintercalation process, resulting in the collapse of the material structure, and then ③ There are still some Ti-based negative electrode materials that are rich in raw materials, non-toxic, harmless, cheap, stable, and safe, but their specific capacity is not high, their electronic conductivity is low, and an effective electric field cannot be formed on the surface. In view of the above points, people began to prepare quantum dots, alloys and other materials to reduce volume expansion and improve cycle stability. However, nanomaterials with small size and high activity are easy to aggregate. After lithium is inserted into the alloy, the mechanical stability is poor, and it is easy to make the material chalking.
发明内容Contents of the invention
针对现有技术中的上述不足之处，本发明提供了一种纳米复合材料及其制备方法和使用该纳米复合材料制得的锂离子电池；该纳米复合材料不仅具有优良的循环稳定性和高倍率放电性能，而且材料无毒、环境友好、价格便宜；而该纳米复合材料的制备方法操作简单，绿色高效。Aiming at the above-mentioned deficiencies in the prior art, the invention provides a nanocomposite material and its preparation method and a lithium ion battery made using the nanocomposite material; the nanocomposite material not only has excellent cycle stability and high High rate discharge performance, and the material is non-toxic, environmentally friendly, and cheap; and the preparation method of the nanocomposite material is simple to operate, green and efficient.
本发明的目的是通过以下技术方案实现的：The purpose of the present invention is achieved through the following technical solutions:
一种纳米复合材料，由上部的聚苯胺纳米层、中间的TiO2/氧化石墨烯复合层、下部的聚苯胺纳米层构成；A nanocomposite material consisting of an upper polyaniline nanolayer, a middle TiO 2 /graphene oxide composite layer, and a lower polyaniline nanolayer;
其中，所述的聚苯胺纳米层为纳米棒状聚苯胺阵列；所述的TiO2/氧化石墨烯复合层为TiO2纳米颗粒分布在多层氧化石墨烯的网状结构中所形成的复合层。Wherein, the polyaniline nano-layer is a nano-rod polyaniline array; the TiO 2 /graphene oxide composite layer is a composite layer formed by TiO 2 nano-particles distributed in a network structure of multi-layer graphene oxide.
优选地，所述的多层氧化石墨烯为2～9层的氧化石墨烯。Preferably, the multi-layer graphene oxide is graphene oxide with 2-9 layers.
优选地，所述的TiO2/氧化石墨烯复合层为TiO2纳米颗粒均匀分布在多层氧化石墨烯的网状结构中所形成的复合层。Preferably, the TiO 2 /graphene oxide composite layer is a composite layer formed by uniform distribution of TiO 2 nanoparticles in the network structure of multilayer graphene oxide.
优选地，上部的聚苯胺纳米层和下部的聚苯胺纳米层的厚度均为40～60nm。Preferably, the thicknesses of the upper polyaniline nano-layer and the lower polyaniline nano-layer are both 40-60 nm.
一种纳米复合材料的制备方法，包括如下步骤：A method for preparing a nanocomposite material, comprising the steps of:
步骤一，采用Hummers法制备出氧化石墨和盐酸的混合溶液，并在氧化石墨和盐酸的混合溶液中，采用旋转TiO2靶材进行液相激光熔蚀，从而制得非晶TiO2原位生长的高活性TiO2/氧化石墨烯复合材料；Step 1, using the Hummers method to prepare a mixed solution of graphite oxide and hydrochloric acid, and in the mixed solution of graphite oxide and hydrochloric acid, use a rotating TiO2 target for liquid-phase laser ablation to obtain amorphous TiO2 in situ growth Highly active TiO 2 /graphene oxide composites;
步骤二，对步骤一中制得的高活性TiO2/氧化石墨烯复合材料进行冰浴搅拌，在搅拌半小时后加入苯胺单体，并在搅拌均匀后加入过硫酸铵进行氧化聚合，从而得到聚苯胺/TiO2/氧化石墨烯三元纳米复合材料。Step 2: Stir the highly active TiO 2 /graphene oxide composite material prepared in step 1 in an ice bath, add aniline monomer after stirring for half an hour, and add ammonium persulfate after stirring evenly for oxidative polymerization, thereby obtaining Polyaniline/TiO 2 /graphene oxide ternary nanocomposites.
优选地，在步骤一结束后迅速进行步骤二的处理。Preferably, the processing of step 2 is carried out immediately after the completion of step 1.
优选地，在步骤二中，当加入苯胺单体后，需搅拌半个小时以达到搅拌均匀，再加入过硫酸铵进行氧化聚合。Preferably, in step 2, after the aniline monomer is added, stirring is required for half an hour to achieve uniform stirring, and then ammonium persulfate is added for oxidative polymerization.
一种锂离子电池，该锂离子电池的负极采用上述方案中所述的纳米复合材料制成。A lithium ion battery, the negative electrode of the lithium ion battery is made of the nanocomposite material described in the above scheme.
由上述本发明提供的技术方案可以看出，本发明实施例所提供的纳米复合材料是一个“三明治结构”，在该“三明治结构”中，氧化石墨烯能够防止高活性纳米粒子的聚集，而外层的纳米棒状聚苯胺阵列为离子及电子的传输提供了便捷的通道，并且在一定程度上阻止了内层活性材料因体积膨胀而引起的结构崩塌，充分发挥了内层TiO2/GO复合材料的储锂性能，因此本发明实施例所提供的纳米复合材料呈现出了优良的循环稳定性和高倍率放电性能。而本发明实施例所提供的纳米复合材料的制备方法利用液相激光熔蚀下氧化石墨烯表面原位生长的纳米颗粒具有较多氧空位和缺陷，并且具有高表面反应活性，特殊的物理化学性质等特点，从而使苯胺单体能够在TiO2/GO复合材料的上下两面以纳米棒状阵列的形式聚合生长，并最终制得本发明实施例所提供的PANI/TiO2/GO三元纳米复合材料。由此可见，本发明实施例所提供的纳米复合材料不仅具有优良的循环稳定性和高倍率放电性能，而且材料无毒、环境友好、价格便宜；而该纳米复合材料的制备方法操作简单，绿色高效。It can be seen from the above-mentioned technical solutions provided by the present invention that the nanocomposite material provided by the embodiments of the present invention is a "sandwich structure", in which graphene oxide can prevent the aggregation of highly active nanoparticles, while The nanorod-like polyaniline array on the outer layer provides a convenient channel for the transport of ions and electrons, and to a certain extent prevents the structural collapse of the inner active material due to volume expansion, giving full play to the inner TiO 2 /GO composite. The lithium storage performance of the material, so the nanocomposite material provided by the embodiment of the present invention exhibits excellent cycle stability and high rate discharge performance. However, the preparation method of the nanocomposite material provided by the embodiment of the present invention utilizes the nanoparticle grown in situ on the surface of graphene oxide under liquid phase laser ablation to have more oxygen vacancies and defects, and has high surface reactivity, special physical and chemical Properties and other characteristics, so that the aniline monomer can be polymerized and grown in the form of nanorod arrays on the upper and lower sides of the TiO 2 /GO composite material, and finally the PANI/TiO 2 /GO ternary nanocomposite provided by the embodiment of the present invention is obtained Material. It can be seen that the nanocomposite material provided by the embodiment of the present invention not only has excellent cycle stability and high rate discharge performance, but also is non-toxic, environmentally friendly, and cheap; and the preparation method of the nanocomposite material is simple to operate, green efficient.
附图说明Description of drawings
为了更清楚地说明本发明实施例的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域的普通技术人员来讲，在不付出创造性劳动行的前提下，还可以根据这些附图获得其他附图。In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the accompanying drawings that need to be used in the description of the embodiments. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For Those skilled in the art can also obtain other drawings based on these drawings without making creative efforts.
图1a为本发明实施例所提供的纳米复合材料的结构示意图。Fig. 1a is a schematic structural view of the nanocomposite material provided by the embodiment of the present invention.
图1b为本发明实施例所提供的纳米复合材料作为锂离子电池负极时的原理示意图。Fig. 1b is a schematic diagram of the principle when the nanocomposite material provided by the embodiment of the present invention is used as the negative electrode of the lithium ion battery.
图2a为本发明提供的现有技术中聚苯胺的SEM(即扫描电子显微镜)分析图。Fig. 2a is a SEM (ie scanning electron microscope) analysis diagram of polyaniline in the prior art provided by the present invention.
图2b为本发明实施例所提供的纳米复合材料的SEM分析图一。Fig. 2b is a SEM analysis diagram 1 of the nanocomposite material provided by the embodiment of the present invention.
图2c为本发明实施例所提供的纳米复合材料的SEM分析图二。Fig. 2c is the second SEM analysis diagram of the nanocomposite material provided by the embodiment of the present invention.
图3为本发明实施例所提供的纳米复合材料，TiO2/GO和TiO2的拉曼光谱图。Fig. 3 is a Raman spectrum diagram of TiO 2 /GO and TiO 2 , the nanocomposite material provided by the embodiment of the present invention.
图4a为本发明实施例所提供的TiO2/GO的TEM(即透射电子显微镜)分析图一。Fig. 4a is a TEM (transmission electron microscope) analysis diagram 1 of TiO 2 /GO provided by the embodiment of the present invention.
图4b为本发明实施例所提供的TiO2/GO的TEM分析图二。Fig. 4b is the second TEM analysis diagram of TiO 2 /GO provided by the embodiment of the present invention.
图4c为本发明实施例所提供的纳米复合材料的TEM、HRTEM(即高分辨透射电镜)以及SEAD(即选区电子衍射)的分析图。Fig. 4c is an analysis diagram of TEM, HRTEM (ie, high-resolution transmission electron microscope) and SEAD (ie, selected area electron diffraction) of the nanocomposite material provided by the embodiment of the present invention.
图5a为本发明实施例所提供的锂离子电池的性能示意图一。Fig. 5a is a first schematic diagram of the performance of the lithium-ion battery provided by the embodiment of the present invention.
图5b为本发明实施例所提供的锂离子电池的性能示意图二。Fig. 5b is a second schematic diagram of the performance of the lithium-ion battery provided by the embodiment of the present invention.
图5c为本发明实施例所提供的锂离子电池的性能示意图三。FIG. 5c is a third schematic diagram of the performance of the lithium-ion battery provided by the embodiment of the present invention.
具体实施方式detailed description
下面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，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明的保护范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
下面分别对本发明所提供的纳米复合材料及其制备方法和使用该纳米复合材料制得的锂离子电池进行详细描述。The nanocomposite material provided by the present invention, its preparation method and the lithium ion battery prepared by using the nanocomposite material are described in detail below.
(一)一种纳米复合材料(1) A nanocomposite material
一种纳米复合材料，由上部的聚苯胺(即PANI)纳米层、中间的TiO2/氧化石墨烯(即Graphene oxide，GO)复合层、下部的聚苯胺纳米层构成。A nanocomposite material is composed of an upper polyaniline (ie PANI) nano layer, a middle TiO 2 /graphene oxide (ie Graphene oxide, GO) composite layer, and a lower polyaniline nano layer.
其中，所述的聚苯胺纳米层为纳米棒状聚苯胺阵列；所述的TiO2/氧化石墨烯复合层为TiO2纳米颗粒分布在多层氧化石墨烯的网状结构中所形成的复合层。如图1a和图1b所示，该纳米复合材料是由TiO2/氧化石墨烯复合层以及该TiO2/氧化石墨烯复合层的上、下表面生长的纳米棒状聚苯胺阵列所构成，即通常所说的“三明治结构”；上部的聚苯胺纳米层1和下部的聚苯胺纳米层构成3均是由纳米棒状聚苯胺a所构成的阵列；在TiO2/氧化石墨烯复合层2上，TiO2纳米颗粒c分布在多层氧化石墨烯b的网状结构中。Wherein, the polyaniline nano-layer is a nano-rod polyaniline array; the TiO 2 /graphene oxide composite layer is a composite layer formed by TiO 2 nano-particles distributed in a network structure of multi-layer graphene oxide. As shown in Figure 1a and Figure 1b, the nanocomposite material is composed of a TiO 2 /graphene oxide composite layer and nanorod polyaniline arrays grown on the upper and lower surfaces of the TiO 2 /graphene oxide composite layer, that is, usually The so-called "sandwich structure"; the upper polyaniline nanolayer 1 and the lower polyaniline nanolayer 3 are arrays composed of nanorod polyaniline a; on the TiO 2 /graphene oxide composite layer 2, TiO 2 Nanoparticles c are distributed in the network structure of multilayer graphene oxide b.
具体的，该纳米复合材料的各层的具体实施方案包括：Concrete, the concrete embodiment of each layer of this nanocomposite material comprises:
(1)所述的多层氧化石墨烯最好为2～9层的氧化石墨烯；如果氧化石墨烯的层数大于9层，则丧失了氧化石墨烯结构原本的柔韧性，且不利于大量Li+的嵌入和电子的快速传输；如果氧化石墨烯的层数小于2层，则制备过程中的酸环境会使得氧化石墨烯容易分解和破损，不能形成“三明治结构”。(1) The multilayer graphene oxide is preferably graphene oxide of 2 to 9 layers; if the number of layers of graphene oxide is greater than 9 layers, the original flexibility of the graphene oxide structure is lost, and it is not conducive to a large number of The intercalation of Li + and the rapid transport of electrons; if the number of layers of graphene oxide is less than 2 layers, the acid environment in the preparation process will make graphene oxide easy to decompose and break, and cannot form a "sandwich structure".
(2)所述的TiO2/氧化石墨烯复合层最好为TiO2纳米颗粒均匀分布在多层氧化石墨烯的网状结构中所形成的复合层；TiO2纳米颗粒均匀分布在多层氧化石墨烯的网状结构中的好处是最大限度的增加了TiO2纳米颗粒与电解液的接触面积，能够防止TiO2纳米颗粒聚集带来的储锂容量的损失。(2) The TiO2 /graphene oxide composite layer is preferably a composite layer in which TiO2 nanoparticles are uniformly distributed in the network structure of multilayer graphene oxide ; The advantage of the network structure of graphene is that it maximizes the contact area between TiO 2 nanoparticles and the electrolyte, and can prevent the loss of lithium storage capacity caused by the aggregation of TiO 2 nanoparticles.
(3)上部的聚苯胺纳米层和下部的聚苯胺纳米层的厚度均为40～60nm，最好均在50nm左右，这一厚度的好处是为离子及电子的传输提供了便捷的通道，不仅能够有效防止聚苯胺纳米层过厚所造成的离子不及时输送，而且能够有效防止聚苯胺纳米层过薄所造成的因体积膨胀引起的结构崩塌。(3) The thickness of the upper polyaniline nanolayer and the lower polyaniline nanolayer are both 40-60nm, preferably about 50nm. The advantage of this thickness is that it provides a convenient channel for the transmission of ions and electrons, not only It can effectively prevent the untimely transport of ions caused by too thick polyaniline nano-layers, and can effectively prevent the structural collapse caused by volume expansion caused by too thin polyaniline nano-layers.
进一步地，如图1a和图1b所示，本发明实施例所提供的纳米复合材料是一个“三明治结构”，在该“三明治结构”中，氧化石墨烯b能够防止高活性纳米粒子的聚集，而外层的纳米棒状聚苯胺a阵列为离子及电子的传输提供了便捷的通道，并且在一定程度上阻止了内层活性材料因体积膨胀而引起的结构崩塌，充分发挥了内层TiO2/GO复合材料的储锂性能，因此本发明实施例所提供的纳米复合材料呈现出了优良的循环稳定性和高倍率放电性能。Further, as shown in Figure 1a and Figure 1b, the nanocomposite material provided by the embodiment of the present invention is a "sandwich structure", in which graphene oxide b can prevent the aggregation of highly active nanoparticles, The nanorod polyaniline a array on the outer layer provides a convenient channel for the transport of ions and electrons, and to a certain extent prevents the structural collapse of the inner active material due to volume expansion, giving full play to the inner TiO 2 / The lithium storage performance of the GO composite material, so the nanocomposite material provided by the embodiment of the present invention exhibits excellent cycle stability and high rate discharge performance.
由此可见，本发明实施例利用了氧化石墨烯对纳米颗粒的分散作用和聚苯胺优异的导电性能解决了液相激光熔蚀技术量产低的问题，保留了所获TiO2/GO复合材料的高活性，从而使本发明实施例所提供的纳米复合材料具有优良的循环稳定性和高倍率放电性能；而该纳米复合材料仅涉及聚苯胺、TiO2、氧化石墨烯这三种物质，因此本发明实施例所提供的纳米复合材料材料无毒、环境友好、价格便宜。It can be seen that the embodiment of the present invention utilizes the dispersion effect of graphene oxide on nanoparticles and the excellent electrical conductivity of polyaniline to solve the problem of low mass production of liquid phase laser ablation technology, and retains the obtained TiO 2 /GO composite material high activity, so that the nanocomposite material provided by the embodiment of the present invention has excellent cycle stability and high rate discharge performance; and the nanocomposite material only involves polyaniline, TiO 2 , graphene oxide these three substances, so The nanocomposite materials provided by the embodiments of the present invention are non-toxic, environmentally friendly and cheap.
(二)该纳米复合材料的制备方法(2) The preparation method of the nanocomposite
上述技术方案中所述纳米复合材料的制备方法，包括如下步骤：The preparation method of the nanocomposite material described in the above-mentioned technical scheme, comprises the steps:
步骤一，采用Hummers法制备出氧化石墨和盐酸的混合溶液，并在氧化石墨和盐酸的混合溶液中，采用旋转TiO2靶材进行液相激光熔蚀，从而制得非晶TiO2原位生长的高活性TiO2/GO复合材料。Step 1, using the Hummers method to prepare a mixed solution of graphite oxide and hydrochloric acid, and in the mixed solution of graphite oxide and hydrochloric acid, use a rotating TiO2 target for liquid-phase laser ablation to obtain amorphous TiO2 in situ growth highly active TiO 2 /GO composites.
步骤二，对步骤一中制得的高活性TiO2/GO复合材料进行冰浴搅拌，在搅拌半小时后加入苯胺单体，并在搅拌均匀后(通常需要搅拌半个小时即可达到搅拌均匀状态)加入过硫酸铵进行氧化聚合，从而得到PANI/TiO2/GO三元纳米复合材料。Step 2: Stir the highly active TiO 2 /GO composite material prepared in step 1 in an ice bath, add aniline monomer after stirring for half an hour, and stir evenly (usually it takes half an hour to achieve uniform stirring) state) by adding ammonium persulfate for oxidative polymerization to obtain PANI/TiO 2 /GO ternary nanocomposites.
具体地，在步骤一结束后最好迅速进行步骤二的处理，这是由于步骤一中刚刚制得的新鲜的TiO2/GO复合材料具有高活性，表面具有较多氧空位和缺陷；如果不迅速进行步骤二的处理，那么TiO2/GO复合材料会自发的形成稳定的晶体结构，活性流失，从而不能为苯胺单体提供活性位点聚合生长，导致无法形成复合材料。Specifically, it is best to carry out the treatment of step 2 quickly after the end of step 1, because the fresh TiO 2 /GO composite material just prepared in step 1 has high activity and has more oxygen vacancies and defects on the surface; if not If the second step is performed quickly, the TiO 2 /GO composite material will spontaneously form a stable crystal structure, and the activity will be lost, so that the aniline monomer cannot be provided with active sites for polymerization and growth, resulting in the inability to form a composite material.
进一步地，该纳米复合材料的制备方法利用液相激光熔蚀下氧化石墨烯表面原位生长的纳米颗粒具有较多氧空位和缺陷，并且具有高表面反应活性，特殊的物理化学性质等特点，从而使苯胺单体能够在TiO2/GO复合材料的上下两面以纳米棒状阵列的形式聚合生长，并最终制得本发明实施例所提供的PANI/TiO2/GO三元纳米复合材料。Furthermore, the preparation method of the nanocomposite material utilizes the in-situ growth of nanoparticles on the surface of graphene oxide under liquid phase laser ablation to have more oxygen vacancies and defects, and has the characteristics of high surface reactivity and special physical and chemical properties. Thus, the aniline monomer can be polymerized and grown in the form of nanorod arrays on the upper and lower surfaces of the TiO 2 /GO composite material, and finally the PANI/TiO 2 /GO ternary nanocomposite material provided by the embodiment of the present invention is obtained.
由此可见，本发明实施例所提供的该纳米复合材料的制备方法不仅操作简单，而且绿色环保、生产效率高。It can be seen that the preparation method of the nanocomposite material provided by the embodiment of the present invention is not only simple to operate, but also environmentally friendly and high in production efficiency.
(三)一种锂离子电池(3) A lithium-ion battery
一种锂离子电池，其负极采用上述技术方案中所述的纳米复合材料制成。由上述内容可知，本发明实施例所提供的纳米复合材料在作为锂离子电池的负极使用时，展现出了优良的循环稳定性和高倍率放电性能，因此本发明实施例所提供的锂离子电池具有优良的循环稳定性和高倍率放电性能。A lithium ion battery, the negative pole of which is made of the nanocomposite material described in the above technical solution. It can be seen from the above that the nanocomposite materials provided by the embodiments of the present invention exhibit excellent cycle stability and high-rate discharge performance when used as negative electrodes of lithium-ion batteries. Therefore, the lithium-ion batteries provided by the embodiments of the present invention It has excellent cycle stability and high rate discharge performance.
为了更加清晰地展现出本发明所提供的技术方案及所产生的技术效果，下面通过实验并结合附图对本发明实施例所提供的纳米复合材料及其制备方法和锂离子电池进行详细描述。In order to more clearly demonstrate the technical solutions provided by the present invention and the resulting technical effects, the nanocomposite materials and their preparation methods and lithium-ion batteries provided by the embodiments of the present invention will be described in detail below through experiments and in conjunction with the accompanying drawings.
实验1Experiment 1
为了更好地表征本发明实施例所提供的PANI/TiO2/GO三元纳米复合材料的形貌，获取该PANI/TiO2/GO三元纳米复合材料的SEM分析图，如图2b和图2c所示；同时，利用现有技术中的方法制得聚苯胺，并获取聚苯胺的SEM分析图，如图2a所示。由图2a可知，现有技术中的聚苯胺是直径为50nm左右的纳米线，并均匀无杂质；由图2b和图2c可知，在本发明实施例所提供的PANI/TiO2/GO三元纳米复合材料中，聚苯胺以纳米短棒的形式在TiO2/GO复合材料的上下两面聚集生长并形成阵列结构，这个三元结构复合材料的厚度为115nm左右，单个PANI/TiO2/GO三元纳米复合材料形貌为微米级的片。In order to better characterize the morphology of the PANI/TiO 2 /GO ternary nanocomposite provided by the embodiments of the present invention, obtain the SEM analysis diagram of the PANI/TiO 2 /GO ternary nanocomposite, as shown in Figure 2b and Fig. 2c; at the same time, polyaniline is prepared by the method in the prior art, and the SEM analysis diagram of polyaniline is obtained, as shown in Figure 2a. It can be seen from Figure 2a that the polyaniline in the prior art is a nanowire with a diameter of about 50nm, and is uniform and free of impurities; it can be seen from Figure 2b and Figure 2c that the PANI/TiO 2 /GO ternary provided in the embodiment of the present invention In the nanocomposite material, polyaniline aggregates and grows on the upper and lower sides of the TiO 2 /GO composite material in the form of short nanorods and forms an array structure. The thickness of the ternary structure composite material is about 115nm, and a single PANI/TiO 2 /GO triple The morphology of the meta-nanocomposite is a micron-scale sheet.
实验2Experiment 2
分别获取TiO2胶体、本发明实施例步骤一所制得的TiO2/GO复合材料、以及本发明实施例最终制得的PANI/TiO2/GO三元纳米复合材料的拉曼光谱图，具体结果可以如图3所示。在图3中，曲线a为本发明实施例最终制得的PANI/TiO2/GO三元纳米复合材料的拉曼光谱曲线，曲线b为本发明实施例步骤一所制得的TiO2/GO复合材料的拉曼光谱曲线，曲线c为TiO2胶体的拉曼光谱曲线；经对比可知：曲线a不仅具有氧化石墨存在的D峰和G峰，而且增加了1175.8cm-1和1465.3cm-1这两个特征峰，这样的特征峰属于醌基和苯基的C-H振动，这就证明了本发明实施例最终制得的纳米复合材料中存在聚苯胺的生成。Obtain the Raman spectra of the TiO2 colloid, the TiO2 /GO composite material prepared in Step 1 of the embodiment of the present invention, and the PANI/ TiO2 /GO ternary nanocomposite material finally prepared in the embodiment of the present invention, specifically The result can be shown in Figure 3. In Fig. 3, curve a is the Raman spectrum curve of the PANI/TiO 2 /GO ternary nanocomposite material finally prepared in the embodiment of the present invention, and curve b is the TiO 2 /GO prepared in step 1 of the embodiment of the present invention The Raman spectrum curve of the composite material, curve c is the Raman spectrum curve of TiO 2 colloid; by comparison, it can be seen that: curve a not only has the D peak and G peak of graphite oxide, but also increases 1175.8cm-1 and 1465.3cm-1 These two characteristic peaks, such characteristic peaks belong to the CH vibration of the quinone group and the phenyl group, which proves the formation of polyaniline in the nanocomposite material finally prepared in the embodiment of the present invention.
实验3Experiment 3
为了进一步确定本发明实施例最终制得的纳米复合材料的组成和结构，分别对本发明实施例步骤一所制得的TiO2/GO复合材料，以及本发明实施例最终制得的纳米复合材料进行TEM分析。图4a和图4b为本发明实施例步骤一所制得的TiO2/GO复合材料的TEM分析图；图4c为本发明实施例最终制得的纳米复合材料的TEM、HRTEM和SEAD分析图；由图4a、图4b和4c可以看出：无论是TiO2/GO复合材料上的纳米颗粒，还是本发明实施例最终制得的纳米复合材料里包裹的纳米颗粒都呈现出无序的非晶态，并且直径小于等于50nm，而它们的SEAD图也呈现为非晶环。取图4c中的方框1做mapping元素分析，发现Cl元素分布的非常均匀，说明盐酸掺杂好，这也相应的暗示了本发明实施例最终制得的纳米复合材料中聚苯胺优越的导电性。观察Ti元素和O元素的分布，可以肯定纳米颗粒由Ti和O组成。结合SEM图和Raman分析可知，本发明实施例最终制得的纳米复合材料为三明治结构的PANI/非晶TiO2/GO三元纳米复合材料。In order to further determine the composition and structure of the nanocomposite material finally prepared in the embodiment of the present invention, the TiO 2 /GO composite material obtained in step 1 of the embodiment of the present invention and the nanocomposite material finally obtained in the embodiment of the present invention were respectively carried out TEM analysis. Figure 4a and Figure 4b are the TEM analysis diagrams of the TiO 2 /GO composite material prepared in Step 1 of the embodiment of the present invention; Figure 4c is the TEM, HRTEM and SEAD analysis diagram of the nanocomposite material finally prepared in the embodiment of the present invention; It can be seen from Figure 4a, Figure 4b and 4c that both the nanoparticles on the TiO 2 /GO composite material and the nanoparticles encapsulated in the nanocomposite material finally prepared in the embodiment of the present invention present disordered amorphous state, and the diameter is less than or equal to 50nm, and their SEAD diagrams also appear as amorphous rings. Taking box 1 in Figure 4c for mapping element analysis, it was found that the distribution of Cl elements was very uniform, indicating that hydrochloric acid was well doped, which also correspondingly suggested that the polyaniline in the nanocomposite material finally prepared in the embodiment of the present invention has excellent electrical conductivity sex. Observing the distribution of Ti and O elements, it can be confirmed that the nanoparticles are composed of Ti and O. Combining the SEM image and Raman analysis, it can be seen that the nanocomposite material finally prepared in the embodiment of the present invention is a sandwich structure PANI/amorphous TiO 2 /GO ternary nanocomposite material.
实验4Experiment 4
对发明实施例最终制得的PANI/TiO2/GO三元纳米复合材料进行离心分离烘干，并按照现有技术组装成以该PANI/TiO2/GO三元纳米复合材料为负极的锂离子纽扣电池，再对该锂离子纽扣电池的性能进行测试，其结果如图5a、图5b和图5c所示。图5a为该锂离子纽扣电池的不同循环充放电对比图；图5b为该锂离子纽扣电池的循环性能图；图5c为该锂离子纽扣电池的倍率性能图。由图5a可以看出，在电流密度为100mA/g的情况下，该锂离子纽扣电池首次放电就达到了591.3mAhg-1，即使进行了250个充放电循环后，该锂离子纽扣电池依然保留了443.6mAhg-1的放电。由图5b可以看出，与现有技术中以PANI/GO为负极的纽扣电池相比，以本发明实施例所提供的PANI/TiO2/GO三元纳米复合材料为负极的锂离子纽扣电池呈现了更优越的比容量。由图5c可以看出，在不同的倍率下进行充放电，以本发明实施例所提供的PANI/TiO2/GO三元纳米复合材料为负极的锂离子纽扣电池呈现了一个非常稳定的状态；当进行120个循环后，在10A/g的高电流密度下，以本发明实施例所提供的PANI/TiO2/GO三元纳米复合材料为负极的锂离子纽扣电池依然保有140.9mAhg-1的比容量。由于本发明实施例所提供的PANI/TiO2/GO三元纳米复合材料中三个物质具有不同的嵌锂速率，从而导致了在初始的50个循环内有个容量上升的过程，但是这并不影响本发明实施例所提供的PANI/TiO2/GO三元纳米复合材料具有优良的循环稳定性和倍率性能。The PANI/TiO 2 /GO ternary nanocomposite material finally prepared in the embodiment of the invention is centrifugally separated and dried, and assembled into a lithium-ion lithium ion composite material with the PANI/TiO 2 /GO ternary nanocomposite material as the negative electrode according to the prior art. Button battery, and then test the performance of the lithium-ion button battery, the results are shown in Figure 5a, Figure 5b and Figure 5c. Fig. 5a is a comparison diagram of charging and discharging in different cycles of the lithium ion button battery; Fig. 5b is a cycle performance diagram of the lithium ion button battery; Fig. 5c is a rate performance diagram of the lithium ion button battery. It can be seen from Figure 5a that at a current density of 100mA/g, the lithium-ion button battery reaches 591.3mAhg -1 for the first discharge, even after 250 charge-discharge cycles, the lithium-ion button battery still retains A discharge of 443.6mAhg -1 was achieved. As can be seen from Figure 5b, compared with the button battery with PANI/GO as the negative electrode in the prior art, the lithium-ion button battery with the PANI/TiO 2 /GO ternary nanocomposite material provided by the embodiment of the present invention as the negative electrode Presented a more superior specific capacity. It can be seen from Figure 5c that the lithium-ion button battery with the PANI/TiO 2 /GO ternary nanocomposite material provided by the embodiment of the present invention as the negative electrode presents a very stable state when charging and discharging at different rates; After 120 cycles, under the high current density of 10A/g, the lithium ion button battery with PANI/TiO 2 /GO ternary nanocomposite material provided by the embodiments of the present invention still retains a power of 140.9mAhg -1 Specific capacity. Since the three substances in the PANI/TiO 2 /GO ternary nanocomposites provided by the embodiments of the present invention have different lithium intercalation rates, there is a process of capacity increase in the initial 50 cycles, but this does not Does not affect the PANI/TiO 2 /GO ternary nanocomposite material provided by the embodiment of the present invention has excellent cycle stability and rate performance.
综上可见，本发明实施例所提供的纳米复合材料不仅具有优良的循环稳定性和高倍率放电性能，而且材料无毒、环境友好、价格便宜；而该纳米复合材料的制备方法操作简单，绿色高效。In summary, the nanocomposite material provided by the embodiment of the present invention not only has excellent cycle stability and high rate discharge performance, but also is non-toxic, environmentally friendly, and cheap; and the preparation method of the nanocomposite material is simple to operate, green efficient.
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求书的保护范围为准。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed in the present invention can easily think of changes or Replacement should be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the protection scope of the claims.
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