CN102394294A - Preparation method of highly graphitized activated carbon-transition metal oxide nanocomposite material - Google Patents
Preparation method of highly graphitized activated carbon-transition metal oxide nanocomposite material Download PDFInfo
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 28
- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 121
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 238000005087 graphitization Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 4
- 239000003049 inorganic solvent Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 11
- 239000010405 anode material Substances 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- 229910003481 amorphous carbon Inorganic materials 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 13
- 229910000428 cobalt oxide Inorganic materials 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000000840 electrochemical analysis Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000004966 Carbon aerogel Substances 0.000 description 3
- -1 activated carbon/transition group metal oxide Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 230000037023 motor activity Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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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
本发明涉及一种高度石墨化活性碳/过渡金属氧化物纳米复合材料的制法，该方法包括以下步骤：按重量份，取1份活性碳，用去离子水清洗并在90℃-120℃烘干，加入1-3份的金属盐溶液中混合均匀，经过超声处理，置于真空烧结炉中加热至600℃-1000℃，保温1-3h进行石墨化处理，即得高度石墨化活性碳/过渡金属氧化物纳米复合材料产品。与现有技术相比，本发明所得到纳米复合材料由于活性碳基体中石墨层良好的导电性、三维联通的多孔结构、均匀分散的纳米金属氧化物颗粒，非晶碳的活性位点以及高的比表面积，作为锂离子电池负极材料具有可观的容量和优异的循环稳定性。
The invention relates to a method for preparing a highly graphitized activated carbon/transition metal oxide nanocomposite material. The method comprises the following steps: take 1 part of activated carbon in parts by weight, wash it with deionized water and heat it at 90°C-120°C Dry, add 1-3 parts of metal salt solution and mix evenly, after ultrasonic treatment, heat to 600°C-1000°C in a vacuum sintering furnace, keep warm for 1-3h for graphitization treatment, and obtain highly graphitized activated carbon / Transition metal oxide nanocomposite products. Compared with the prior art, the nanocomposite material obtained by the present invention is due to the good conductivity of the graphite layer in the activated carbon matrix, the porous structure of the three-dimensional interconnection, the uniformly dispersed nano-metal oxide particles, the active sites of the amorphous carbon and the high The specific surface area, as a lithium-ion battery anode material has considerable capacity and excellent cycle stability.
Description
技术领域 technical field
本发明涉及复合材料技术领域的制备方法，具体涉及一种一步法获得过渡族金属氧化物/高度石墨化活性碳纳米复合材料的制备方法，得到的复合材料具有高可逆容量及循环稳定性，将在锂电池负极材料上得到应用。The invention relates to a preparation method in the technical field of composite materials, in particular to a preparation method for obtaining a transition metal oxide/highly graphitized activated carbon nanocomposite material in one step. The obtained composite material has high reversible capacity and cycle stability. Applied in lithium battery anode materials.
背景技术 Background technique
新能源汽车的关键部件是锂离子电池，降低成本、提高性能是锂离子电池发展的主攻方向，主要依赖于电池中各组分材料的改进开发及电池工艺的革新。据统计，仅手机电池一项的负极材料需求量为4000吨/年，随着电动汽车的迅速发展，作为锂电池负极材料更具光明前景。商用石墨负极材料具有稳定性好、低成本以及低锂嵌电位的优势，但由于其理论容量有限(372mAh g-1)，而限制了它的应用。现在广泛研究的金属负极材料(如Sn，Si)具极高的理论容量，遗憾的是在充放电过程中由于体积的膨胀，而引起容量的大幅下降；另外一种就是金属氧化物负极材料(如CoOx and FeOx)，也具有较高的理论容量，但是在充放电循环中，嵌锂电位太高。由此可见，目前实用化的负极材料还是碳材料。如何提高碳材料的容量是关键。The key components of new energy vehicles are lithium-ion batteries. Reducing costs and improving performance are the main directions for the development of lithium-ion batteries, which mainly rely on the improvement and development of various component materials in batteries and the innovation of battery technology. According to statistics, the demand for anode materials for mobile phone batteries alone is 4,000 tons per year. With the rapid development of electric vehicles, it has a brighter prospect as anode materials for lithium batteries. The commercial graphite anode material has the advantages of good stability, low cost and low lithium intercalation potential, but its application is limited due to its limited theoretical capacity (372mAh g -1 ). The widely studied metal anode materials (such as Sn, Si) have extremely high theoretical capacity, but unfortunately, the volume expansion during charge and discharge causes a large drop in capacity; the other is the metal oxide anode material ( Such as CoO x and FeO x ), also has a high theoretical capacity, but in the charge and discharge cycle, the lithium intercalation potential is too high. It can be seen that the current practical anode material is still carbon material. How to improve the capacity of carbon materials is the key.
经对现有技术文献的检索发现，《Advanced Functional Materials》(《先进功能材料》)，于2007年，17期，1873页上报道的“Synthesis of Hierarchically PorousCarbon Monoliths with Highly Ordered Microstructure and Their Application inRechargeable Lithium Batteries with High-Rate Capability”(“具有高度规整微观结构的分级多孔碳材料的制备及其在高倍率可充锂离子电池方面的应用)：以多孔二氧化硅为模板制备具有规整结构的多孔碳材料，这种方法制备的多孔碳材料，由于三维联通的多孔道结构以及高的比表面积，为电解质提供了流动的通道，同时非晶碳中较高的碳氢比，给锂离子的嵌入和脱出提供了更多的位点，从而使得材料的循环容量得以突破传统石墨材料的理论容量(800mAh/g)。遗憾的是介孔碳的制备利用组装的介孔碳为模板，不但工艺复杂，而且结构难以控制，难以工业化应用。由此可见，价格低廉的活性炭具有高的比表面以及多孔道结构，有望成为制备负极材料的基体材料。广大科研工作者一直在寻求各种方式对其进行设计，以期在保证循环稳定性的前提下获得更高的容量。包括尝试对其进行石墨化处理，以增强其导电性，和其它负极材料活性物质进行复合等方法，但一般的处理工艺复杂，导致生产周期加长和成本的提高，使得其工业化应用受到限制。进一步的研究发现，《Langmuir》(《兰格缪尔》)，于2000年，16期，4367页上报道的“Catalytic Graphitization ofCarbon Aerogels by Transition Metals”(“碳气凝胶的过渡族金属催化石墨化”)：用铁镍钴等过渡金属作为催化剂对碳气凝胶进行石墨化处理，能够得到高度石墨化的多孔碳材料，但是气凝胶复杂的制备工艺和较高的石墨化处理温度(1000-1800℃)使得处理的成本较高。Through the retrieval of prior art documents, "Advanced Functional Materials" ("Advanced Functional Materials"), in 2007, No. 17, "Synthesis of Hierarchically Porous Carbon Monoliths with Highly Ordered Microstructure and Their Application in Rechargeable Lithium" reported on page 1873 Batteries with High-Rate Capability" ("Preparation of Hierarchical Porous Carbon Materials with Highly Regular Microstructure and Its Application in High-rate Rechargeable Li-ion Batteries): Preparation of Porous Carbon with Regular Structure Using Porous Silica as a Template Material, the porous carbon material prepared by this method, due to the three-dimensional interconnected porous structure and high specific surface area, provides a flow channel for the electrolyte, and at the same time, the high carbon-hydrogen ratio in amorphous carbon provides lithium ion intercalation and The detachment provides more sites, so that the cycle capacity of the material can break through the theoretical capacity (800mAh/g) of traditional graphite materials. Unfortunately, the preparation of mesoporous carbon uses assembled mesoporous carbon as a template, which is not only complicated in process, but also Moreover, the structure is difficult to control and is difficult to apply industrially. It can be seen that the low-cost activated carbon has a high specific surface area and a porous structure, and is expected to become a matrix material for the preparation of negative electrode materials. The majority of scientific researchers have been seeking various ways to design it , in order to obtain a higher capacity under the premise of ensuring cycle stability. Including trying to graphitize it to enhance its conductivity, and compound with other negative electrode material active substances, but the general processing process is complicated, resulting in The lengthening of production cycle and the raising of cost make its industrial application restricted.Further study found that "Langmuir" ("Langmuir"), in 2000, 16 phases, "Catalytic Graphitization of Carbon Aerogels by 4367" reported on page Transition Metals" ("transition metal-catalyzed graphitization of carbon aerogels"): carbon aerogels are graphitized by using transition metals such as iron, nickel and cobalt as catalysts, and highly graphitized porous carbon materials can be obtained, but gas The complex preparation process of the gel and the high graphitization treatment temperature (1000-1800°C) make the treatment cost higher.
发明内容 Contents of the invention
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种方法简单，原材料易得的高度石墨化活性碳/过渡金属氧化物纳米复合材料的制法。The purpose of the present invention is to provide a method for the preparation of a highly graphitized activated carbon/transition metal oxide nanocomposite material with simple method and easy-to-obtain raw materials in order to overcome the above-mentioned defects in the prior art.
本发明的目的可以通过以下技术方案来实现：一种高度石墨化活性碳/过渡金属氧化物纳米复合材料的制法，其特征在于，该方法包括以下步骤：按重量份，取1份活性碳，用去离子水清洗并在90℃-120℃烘干，加入1-3份的金属盐溶液中混合均匀，经过超声处理，置于真空烧结炉中加热至600℃-1000℃，保温1-3h进行石墨化处理，即得高度石墨化活性碳/过渡金属氧化物纳米复合材料产品。The object of the present invention can be achieved through the following technical solutions: a method for preparing a highly graphitized activated carbon/transition metal oxide nanocomposite, characterized in that the method comprises the following steps: by weight, take 1 part of activated carbon , wash with deionized water and dry at 90°C-120°C, add 1-3 parts of metal salt solution and mix evenly, after ultrasonic treatment, heat to 600°C-1000°C in a vacuum sintering furnace, keep warm for 1- After 3 hours of graphitization treatment, a highly graphitized activated carbon/transition metal oxide nanocomposite product is obtained.
所述的活性碳用去离子水清洗至清洗液的pH值为6-8后，再进行烘干。The activated carbon is cleaned with deionized water until the pH value of the cleaning solution is 6-8, and then dried.
所述的金属盐溶液的浓度为0.1-3M，所述的金属盐包括金属的氯化盐，硫酸盐或硝酸盐，所述的金属为具有催化和电机活性的过渡金属。The concentration of the metal salt solution is 0.1-3M, the metal salt includes metal chloride, sulfate or nitrate, and the metal is a transition metal with catalytic and motor activity.
所述的金属包括铁，镍或钴。Said metals include iron, nickel or cobalt.
所述的金属盐溶液为金属盐溶于有机或无机溶剂中配制而成，所述的有机或无机溶剂包括水、醇、DMF或酮。The metal salt solution is prepared by dissolving the metal salt in an organic or inorganic solvent, and the organic or inorganic solvent includes water, alcohol, DMF or ketone.
所述的超声处理的条件是：20-100KHz，100-600w，处理时间0.5-6min。The conditions of the ultrasonic treatment are: 20-100KHz, 100-600w, treatment time 0.5-6min.
与现有技术相比，本发明为一步法获得高度石墨化活性碳/过渡族金属氧化物纳米复合材料的原位制备方法。利用简单易行的处理方法对活性炭进行石墨化处理并在其中原位生长具有电化学活性的纳米过渡金属氧化物颗粒，制备得到高度石墨化活性碳/过渡金属氧化物纳米复合材料。Compared with the prior art, the invention is a one-step in-situ preparation method for obtaining highly graphitized activated carbon/transition group metal oxide nanocomposites. A simple and easy treatment method is used to graphitize activated carbon and in-situ grow electrochemically active nano-transition metal oxide particles in it to prepare highly graphitized activated carbon/transition metal oxide nanocomposites.
本发明使用商用活性碳为原料，原料廉价并易于获得，在经过简单的超声及浸渍处理后进行焙烧，通过一步法完成活性炭的催化石墨化和过渡金属氧化物的引入，制备有纳米过渡金属氧化物均匀分散的高度石墨化碳基复合材料。高度石墨化三维互通的结构不仅具有良好的导电性更保证了电解液的顺利流通；纳米分散的过渡族金属氧化物活性物质不仅提供了电极反应中较短的物质交换路径，同时缓解了在充放电过程中可能的体积膨胀，从而获得了较高的电池容量和循环稳定性。The present invention uses commercial activated carbon as raw material, the raw material is cheap and easy to obtain, and is roasted after simple ultrasonic and impregnation treatment, and the catalytic graphitization of activated carbon and the introduction of transition metal oxide are completed by one-step method, and nano-transition metal oxide is prepared. highly graphitized carbon-based composites with uniform dispersion. The highly graphitized three-dimensional interconnected structure not only has good electrical conductivity, but also ensures the smooth circulation of the electrolyte; the nano-dispersed transition metal oxide active material not only provides a shorter material exchange path in the electrode reaction, but also eases the flow of electrolyte during the charging process. The possible volume expansion during discharge leads to higher battery capacity and cycle stability.
本发明所得到高度石墨化活性碳/过渡金属氧化物纳米复合材料由于活性碳基体良好的导电性、纳米过渡金属氧化物粒子的均匀分散的独特结构，非晶碳的保留以及制备得到的复合材料较高的比表面积，使得其作为锂离子电池负极材料具有可观的容量和优异的循环稳定性。The highly graphitized activated carbon/transition metal oxide nano-composite material obtained in the present invention is due to the good conductivity of the activated carbon matrix, the unique structure of uniform dispersion of nano-transition metal oxide particles, the retention of amorphous carbon and the prepared composite material The high specific surface area makes it have considerable capacity and excellent cycle stability as an anode material for lithium-ion batteries.
附图说明 Description of drawings
图1为制备方法的工艺流程图。Figure 1 is a process flow diagram of the preparation method.
图中：1-活性碳，2-孔，3-高度石墨化活性碳/过渡金属氧化物纳米复合材料，4-石墨层，5-过渡族金属氧化物颗粒In the figure: 1-activated carbon, 2-holes, 3-highly graphitized activated carbon/transition metal oxide nanocomposite, 4-graphite layer, 5-transition group metal oxide particles
具体实施方式 Detailed ways
下面对本发明的实施例作详细说明：本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。The embodiments of the present invention are described in detail below: the present embodiment is implemented under the premise of the technical solution of the present invention, and detailed implementation and specific operation process are provided, but the protection scope of the present invention is not limited to the following implementation example.
如图1所示，本发明方法是：用去离子水清洗活性碳1，并在90℃-120℃烘干，活性炭1为多孔结构，其孔2如图1所示，将烘干后的活性炭1加入金属盐溶液中混合均匀，浸渍，经过超声处理，然后置于真空烧结炉中加热至600℃-1000℃，保温1-3h煅烧进行石墨化处理，即得高度石墨化活性碳/过渡金属氧化物纳米复合材料3产品，高度石墨化活性碳/过渡金属氧化物纳米复合材料3包括高度石墨化活性碳/过渡金属氧化物纳米复合材料石墨层4和嵌入孔内的过渡族金属氧化物颗粒5。As shown in Figure 1, the method of the present invention is: clean active carbon 1 with deionized water, and dry at 90 ℃-120 ℃, active carbon 1 is a porous structure, and its hole 2 is as shown in Figure 1, after drying Activated carbon 1 is added to the metal salt solution, mixed evenly, impregnated, and subjected to ultrasonic treatment, then placed in a vacuum sintering furnace and heated to 600°C-1000°C, kept for 1-3 hours and calcined for graphitization treatment to obtain highly graphitized activated carbon/transition Metal oxide nanocomposites3 products, highly graphitized activated carbon/transition metal oxide nanocomposites3 include highly graphitized activated carbon/transition metal oxide nanocomposite graphite layers4 and transition metal oxides embedded in pores Particle 5.
实施例1Example 1
取1重量份份活性碳，用去离子水清洗至清洗液pH为6-8并在90℃烘干，将其用0.2M的氯化铁溶液1重量份混合均匀，经过1h超声处理，置于真空烧结炉中加热至600℃，保温1h进行处理。最终得到高度石墨化活性碳/氧化铁纳米复合材料。XRD，TEM分析表明，活性炭中原位生长石墨层结构，α-Fe2O3的平均粒径30纳米，比表面积906m2/g，孔径分布在3-4纳米，电化学分析表明在1000mA/g的电流密度下，进行100个循环的放电容量仍能保持在340mAh/g。Take 1 part by weight of activated carbon, wash it with deionized water until the pH of the cleaning solution is 6-8, and dry it at 90°C, mix it with 1 part by weight of 0.2M ferric chloride solution, and ultrasonically treat it for 1 hour. Heat it to 600°C in a vacuum sintering furnace and keep it warm for 1h. Finally, highly graphitized activated carbon/iron oxide nanocomposites are obtained. XRD and TEM analysis show that the in-situ growth graphite layer structure in activated carbon, the average particle size of α-Fe 2 O 3 is 30 nanometers, the specific surface area is 906m 2 /g, the pore size distribution is 3-4 nanometers, and the electrochemical analysis shows that it is at 1000mA/g Under the current density of 100 cycles, the discharge capacity can still be maintained at 340mAh/g.
实施例2Example 2
取1重量份活性碳，用去离子水清洗至清洗液pH为6-8并在90℃烘干，用2M的硝酸镍溶液3重量份和活性碳混合均匀，经过5h超声处理，置于真空烧结炉中加热至900℃，保温1h进行处理。最终得到高度石墨化活性碳/氧化镍纳米复合材料。XRD，TEM分析表明，活性炭中原位生长石墨层结构，氧化镍的平均粒径40纳米，比表面积816m2/g，孔径分布在3-4纳米，电化学分析表明在50mA/g的电流密度下，，进行100个循环的放电容量600mAh/g。Take 1 part by weight of activated carbon, wash it with deionized water until the pH of the cleaning solution is 6-8 and dry it at 90°C, mix it with 3 parts by weight of 2M nickel nitrate solution and activated carbon evenly, after ultrasonic treatment for 5 hours, place in vacuum Heat it to 900°C in a sintering furnace and keep it warm for 1h for treatment. Finally, highly graphitized activated carbon/nickel oxide nanocomposites are obtained. XRD and TEM analysis show that the in-situ growth graphite layer structure in activated carbon, the average particle size of nickel oxide is 40 nanometers, the specific surface area is 816m 2 /g, and the pore size distribution is 3-4 nanometers. Electrochemical analysis shows that at a current density of 50mA/g ,, The discharge capacity of 100 cycles is 600mAh/g.
实施例3Example 3
取1份活性碳，用去离子水清洗并在95℃烘干，将其用2.5M的硝酸钴溶液2重量份混合均匀，经过6h超声处理，置于真空烧结炉中加热至800℃，保温2h进行处理。最终得到高度石墨化活性碳/氧化钴纳米复合材料。XRD，TEM分析表明，活性炭中原位生长石墨层结构，氧化钴的平均粒径40纳米，比表面积864m2/g，孔径分布在3-4纳米，电化学分析表明在100mA/g的电流密度下，进行100个循环的放电容量540mAh/g。Take 1 part of activated carbon, wash it with deionized water and dry it at 95°C, mix it evenly with 2 parts by weight of 2.5M cobalt nitrate solution, and after ultrasonic treatment for 6 hours, place it in a vacuum sintering furnace and heat it to 800°C. 2h for processing. Finally, highly graphitized activated carbon/cobalt oxide nanocomposites are obtained. XRD and TEM analysis show that the in-situ growth graphite layer structure in activated carbon, the average particle size of cobalt oxide is 40 nanometers, the specific surface area is 864m 2 /g, and the pore size distribution is 3-4 nanometers. Electrochemical analysis shows that at a current density of 100mA/g , the discharge capacity of 100 cycles was 540mAh/g.
实施例4Example 4
取1份活性碳，用去离子水清洗并在100℃烘干，将其用3M的硝酸铁溶液1重量份混合均匀，经过30min超声处理，置于真空烧结炉中加热至750℃，保温2h进行处理。最终得到高度石墨化活性碳/氧化钴纳米复合材料。XRD，TEM分析表明，活性炭中原位生长石墨层结构，氧化钴的平均粒径40纳米，比表面积875m2/g，孔径分布在3-4纳米，电化学分析表明在200mA/g的电流密度下，进行100个循环的放电容量420mAh/g。Take 1 part of activated carbon, wash it with deionized water and dry it at 100°C, mix it evenly with 1 part by weight of 3M ferric nitrate solution, after 30 minutes of ultrasonic treatment, put it in a vacuum sintering furnace, heat it to 750°C, and keep it warm for 2 hours to process. Finally, highly graphitized activated carbon/cobalt oxide nanocomposites are obtained. XRD and TEM analysis show that the in-situ growth graphite layer structure in activated carbon, the average particle size of cobalt oxide is 40 nanometers, the specific surface area is 875m 2 /g, and the pore size distribution is 3-4 nanometers. Electrochemical analysis shows that at a current density of 200mA/g , the discharge capacity of 100 cycles is 420mAh/g.
实施例5Example 5
取1份活性碳，用去离子水清洗至清洗液pH为6-8并在120℃烘干，将其用3M的硝酸铁的乙醇溶液1重量份混合均匀，经过20KHz，600w超声处理5h，置于真空烧结炉中加热至600℃，保温3h进行处理。最终得到高度石墨化活性碳/氧化钴纳米复合材料。XRD，TEM分析表明，活性炭中原位生长石墨层结构，氧化钴的平均粒径40纳米，比表面积875m2/g，孔径分布在3-4纳米，电化学分析表明在200mA/g的电流密度下，进行100个循环的放电容量420mAh/g。Take 1 part of activated carbon, wash it with deionized water until the pH of the cleaning solution is 6-8, and dry it at 120°C, mix it with 1 part by weight of 3M ethanol solution of ferric nitrate, and process it with 20KHz, 600w ultrasonic treatment for 5h. Place it in a vacuum sintering furnace and heat it to 600°C, and keep it warm for 3 hours for processing. Finally, highly graphitized activated carbon/cobalt oxide nanocomposites are obtained. XRD and TEM analysis show that the in-situ growth graphite layer structure in activated carbon, the average particle size of cobalt oxide is 40 nanometers, the specific surface area is 875m 2 /g, and the pore size distribution is 3-4 nanometers. Electrochemical analysis shows that at a current density of 200mA/g , the discharge capacity of 100 cycles is 420mAh/g.
实施例5Example 5
取1份活性碳，用去离子水清洗至清洗液pH为6-8并在90℃烘干，将其用0.1M的硫酸钴的DMF溶液1重量份混合均匀，经过100KHz，100w超声处理1h，置于真空烧结炉中加热至1000℃，保温1h进行处理。最终得到高度石墨化活性碳/氧化钴纳米复合材料。XRD，TEM分析表明，活性炭中原位生长石墨层结构，氧化钴的平均粒径40纳米，比表面积875m2/g，孔径分布在3-4纳米，电化学分析表明在200mA/g的电流密度下，进行100个循环的放电容量420mAh/g。Take 1 part of activated carbon, wash it with deionized water until the pH of the cleaning solution is 6-8 and dry it at 90°C, mix it with 1 part by weight of 0.1M cobalt sulfate in DMF solution, and process it with 100KHz, 100w ultrasonic treatment for 1h , placed in a vacuum sintering furnace and heated to 1000°C, and kept for 1h for processing. Finally, highly graphitized activated carbon/cobalt oxide nanocomposites are obtained. XRD and TEM analysis show that the in-situ growth graphite layer structure in activated carbon, the average particle size of cobalt oxide is 40 nanometers, the specific surface area is 875m 2 /g, and the pore size distribution is 3-4 nanometers. Electrochemical analysis shows that under the current density of 200mA/g , the discharge capacity of 100 cycles is 420mAh/g.
本实施例使用活性碳和过渡金属盐作为先驱体，通过一步法进行石墨化制备具有高度石墨化活性碳/过渡族金属氧化物纳米复合材料。结果发现经过设计的高度石墨化活性碳/过渡族金属氧化物纳米复合材料作为锂离子电池负极材料具有较高的理论容量和循环稳定性。参见图1所示的工艺流程。In this example, activated carbon and transition metal salts are used as precursors, and a highly graphitized activated carbon/transition metal oxide nanocomposite material is prepared by one-step graphitization. It was found that the designed highly graphitized activated carbon/transition group metal oxide nanocomposites have high theoretical capacity and cycle stability as anode materials for lithium-ion batteries. See the process flow shown in Figure 1.
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| CN102751500B (en) * | 2012-07-17 | 2015-12-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | There is amorphous carbon material and the manufacture method thereof of graphitization characteristic |
| CN102751500A (en) * | 2012-07-17 | 2012-10-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Amorphous carbon material with graphitizing characteristics and preparation method of amorphous carbon material |
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