CN108987729B - A kind of lithium-sulfur battery cathode material and preparation method thereof, and lithium-sulfur battery - Google Patents
A kind of lithium-sulfur battery cathode material and preparation method thereof, and lithium-sulfur battery Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000010406 cathode material Substances 0.000 title abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 54
- 239000010941 cobalt Substances 0.000 claims abstract description 54
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 45
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 45
- 239000007774 positive electrode material Substances 0.000 claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 33
- 239000011593 sulfur Substances 0.000 claims abstract description 33
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
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- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 23
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 13
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 11
- 239000011149 active material Substances 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 238000005191 phase separation Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- WQBPQZDFTKFWQZ-UHFFFAOYSA-N C1(C(C=CCC1)(N)N)(N)N Chemical compound C1(C(C=CCC1)(N)N)(N)N WQBPQZDFTKFWQZ-UHFFFAOYSA-N 0.000 claims 1
- IFYLVUHLOOCYBG-UHFFFAOYSA-N eticyclidine Chemical compound C=1C=CC=CC=1C1(NCC)CCCCC1 IFYLVUHLOOCYBG-UHFFFAOYSA-N 0.000 claims 1
- 239000002055 nanoplate Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 18
- 239000002184 metal Substances 0.000 abstract description 18
- 238000007599 discharging Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000004020 conductor Substances 0.000 abstract description 2
- 238000009413 insulation Methods 0.000 abstract description 2
- 239000002071 nanotube Substances 0.000 abstract description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- 229920001021 polysulfide Polymers 0.000 description 9
- 239000005077 polysulfide Substances 0.000 description 9
- 150000008117 polysulfides Polymers 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
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- 239000007788 liquid Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910018091 Li 2 S Inorganic materials 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 239000010410 layer Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
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- 239000012046 mixed solvent Substances 0.000 description 1
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Abstract
本发明公开了一种锂硫电池正极材料及其制备方法与锂硫电池。所述锂硫电池正极材料包括若干氧化钒纳米片、分散在每个氧化钒纳米片上的若干钴颗粒、在若干钴颗粒表面生长的碳纳米管、及分散在碳纳米管里以及同时分散在碳纳米管形成的网络中的硫单质。本发明提供的锂硫电池正极材料以金属钴单质和过渡金属氧化物为模板生长碳纳米管进行载硫，有效的缓解了充放电过程中的体积膨胀问题，并且金属钴单质及碳纳米管都是良好的导电材料，弥补了硫绝缘性的缺点，使得到的锂硫电池的倍率性能和循环稳定性能得到大大提高。并且该制备方法过程简单、操作方便，环境友好，有利于大规模生产，具有实用性。
The invention discloses a positive electrode material for a lithium-sulfur battery, a preparation method thereof, and a lithium-sulfur battery. The lithium-sulfur battery cathode material includes several vanadium oxide nanosheets, several cobalt particles dispersed on each vanadium oxide nanosheet, carbon nanotubes grown on the surface of several cobalt particles, and dispersed in the carbon nanotubes and simultaneously dispersed in the carbon nanotubes. Elemental sulfur in the network formed by nanotubes. The positive electrode material of the lithium-sulfur battery provided by the invention uses metal cobalt and transition metal oxides as templates to grow carbon nanotubes to carry sulfur, which effectively alleviates the problem of volume expansion during charging and discharging, and the metal cobalt and carbon nanotubes are both It is a good conductive material, which makes up for the shortcomings of sulfur insulation, so that the rate performance and cycle stability of the obtained lithium-sulfur battery are greatly improved. In addition, the preparation method has the advantages of simple process, convenient operation, environment-friendly, favorable for large-scale production and practicality.
Description
技术领域technical field
本发明属于锂硫电池正极材料领域，更具体地，涉及一种锂硫电池正极材料及其制备方法与锂硫电池。The invention belongs to the field of positive electrode materials for lithium-sulfur batteries, and more particularly, relates to a positive electrode material for lithium-sulfur batteries, a preparation method thereof, and a lithium-sulfur battery.
背景技术Background technique
随着现代工业的发展，汽车的普及，导致化石能源日渐减少，环境问题日趋严重，形势不容乐观。急需研究清洁的、可再生的能源来代替现有的不可再生的化石能源，与此同时，储能问题的解决就被提上日程。目前，锂离子电池研究、应用较为广泛，因其功率密度、能量密度相对较高、循环寿命长，绿色环保等优点，使其在各类移动电源，大型储能设备及新能源电动汽车上广泛应用。然而，现如今研究的锂离子正负极材料，其容量几乎达到其理论容量，难以满足日渐增长的储能需求。因此，急需研究出具有更高的能量密度的电极材料来推动社会的进一步发展。此时，锂硫电池以其高的比能量及材料的理论比容量逐渐登上储能的舞台。With the development of modern industry and the popularization of automobiles, fossil energy is decreasing day by day, environmental problems are becoming more and more serious, and the situation is not optimistic. There is an urgent need to study clean and renewable energy to replace the existing non-renewable fossil energy. At the same time, the solution of the energy storage problem is put on the agenda. At present, lithium-ion batteries are widely researched and applied. Because of their relatively high power density, energy density, long cycle life, and green environmental protection, they are widely used in various mobile power sources, large-scale energy storage equipment and new energy electric vehicles. application. However, the capacity of lithium-ion cathode and anode materials currently studied almost reaches its theoretical capacity, which is difficult to meet the growing demand for energy storage. Therefore, it is urgent to develop electrode materials with higher energy density to promote the further development of society. At this time, lithium-sulfur batteries have gradually entered the stage of energy storage due to their high specific energy and theoretical specific capacity of materials.
锂硫电池是以硫元素作为电池正极材料，金属锂作为负极材料的一种锂电池。其中，单质硫在地球的储量相当丰富，使其具有价格低廉的优点，并且硫元素对环境无污染，属于清洁的能源材料。其次，硫作为正极材料，其理论比容量可高达1675mA/g，电池的理论比能量高达2600Wh/kg，远远超过现有市场上的钴酸锂电池容量(150mAh/g)，这就使锂硫电池成为非常具有应用前景的储能方式。但是，锂硫电池也存在其特有的问题：(1)硫的导电性非常差，并且反应的最终产物Li2S2和Li2S都是绝缘体，导致电池倍率性能较差；(2)锂硫电池的中间产物多硫化物会溶解到电解液中，使离子导电性降低，并且多硫化物在正负极间的移动，使活性物质损失，从而使循环稳定性降低；(3)在充放电过程中，硫体积会变大，容易损坏电池且带来安全隐患。A lithium-sulfur battery is a kind of lithium battery with sulfur as the positive electrode material of the battery and metal lithium as the negative electrode material. Among them, the reserves of elemental sulfur in the earth are quite abundant, which makes it have the advantage of low price, and the sulfur element does not pollute the environment and belongs to the clean energy material. Secondly, as the positive electrode material, the theoretical specific capacity of sulfur can be as high as 1675mA/g, and the theoretical specific energy of the battery is as high as 2600Wh/kg, far exceeding the capacity of lithium cobalt oxide batteries on the existing market (150mAh/g), which makes lithium Sulfur batteries have become a very promising energy storage method. However, lithium-sulfur batteries also have their own unique problems: (1) the conductivity of sulfur is very poor, and the final products of the reaction, Li 2 S 2 and Li 2 S are both insulators, resulting in poor battery rate performance; (2) lithium The intermediate product polysulfides of sulfur batteries will dissolve into the electrolyte, reducing the ionic conductivity, and the movement of polysulfides between the positive and negative electrodes will cause the loss of active materials, thereby reducing the cycle stability; (3) during charging During the discharge process, the volume of sulfur will become larger, which can easily damage the battery and bring safety hazards.
为解决锂硫电池现存的问题，需对正极材料进行改性来实现。现在大多数研究的技术主要是，将硫与单一的导电基材料或金属氧化物材料进行复合来提高性能。但是，上述方法中对于材料导电性的提高及多硫化物穿梭效应的抑制作用有限，对同时提高锂硫电池的倍率性能和循环性能能力也有限。In order to solve the existing problems of lithium-sulfur batteries, it is necessary to modify the cathode material. Most of the current research techniques focus on combining sulfur with a single conductive base material or metal oxide material to improve performance. However, the above methods have limited effects on improving the conductivity of materials and inhibiting the shuttle effect of polysulfides, and are also limited in the ability to simultaneously improve the rate performance and cycle performance of lithium-sulfur batteries.
发明内容SUMMARY OF THE INVENTION
针对现有技术中存在的技术问题提供一种锂硫电池正极材料及其制备方法与锂硫电池。该锂硫电池正极材料能够提供高的导电性，催化性能及用化学方式抑制多硫化物的穿梭效应，从而提高锂硫电池的倍率性能及循环性能。Aiming at the technical problems existing in the prior art, a lithium-sulfur battery positive electrode material, a preparation method thereof, and a lithium-sulfur battery are provided. The lithium-sulfur battery cathode material can provide high conductivity, catalytic performance and chemically inhibit the shuttle effect of polysulfides, thereby improving the rate performance and cycle performance of the lithium-sulfur battery.
为解决上述技术问题，本发明采用的技术方案是：In order to solve the above-mentioned technical problems, the technical scheme adopted in the present invention is:
一种锂硫电池正极材料，所述锂硫电池正极材料包括若干氧化钒纳米片、分散在每个氧化钒纳米片上的若干钴颗粒、在若干钴颗粒表面生长的碳纳米管、及分散在碳纳米管里以及同时分散在碳纳米管形成的网络中的硫单质。A lithium-sulfur battery positive electrode material, the lithium-sulfur battery positive electrode material comprises several vanadium oxide nanosheets, several cobalt particles dispersed on each vanadium oxide nanosheet, carbon nanotubes grown on the surfaces of several cobalt particles, and carbon nanotubes dispersed on the surface of several cobalt particles. Elemental sulfur in the nanotubes and simultaneously dispersed in the network formed by the carbon nanotubes.
上述方案中，所述氧化钒纳米片为六边形。In the above scheme, the vanadium oxide nanosheets are hexagonal.
上述方案中，所述氧化钒纳米片的边长为2-3μm，厚1-1.5μm。In the above scheme, the vanadium oxide nanosheet has a side length of 2-3 μm and a thickness of 1-1.5 μm.
上述方案中，所述钴颗粒和碳纳米管的直径均为10-30nm。In the above solution, the diameters of the cobalt particles and the carbon nanotubes are both 10-30 nm.
所述的锂硫电池正极材料的制备方法，包括以下步骤：The preparation method of the lithium-sulfur battery cathode material comprises the following steps:
(1)将环六亚甲基四胺、六水合氯化钴、偏钒酸铵前驱体加入水中混合，得到混合物；(1) cyclohexamethylenetetramine, cobalt chloride hexahydrate, ammonium metavanadate precursor are added in water and mixed to obtain mixture;
(2)将步骤(1)制备的混合物放入水浴锅，搅拌，即得钒酸钴粉末材料；(2) putting the mixture prepared in step (1) into a water bath and stirring to obtain cobalt vanadate powder material;
(3)将步骤(2)所述的钒酸钴材料放在管式炉中，在一氧化碳气氛下，热处理进行相分离与同步生长碳纳米管包覆层。(3) The cobalt vanadate material described in step (2) is placed in a tube furnace, and in a carbon monoxide atmosphere, heat treatment is performed for phase separation and simultaneous growth of a carbon nanotube coating layer.
(4)将步骤(3)所述的复合材料与升华硫混合后进行真空低温热处理，即得到所述的锂硫电池正极材料。(4) The composite material described in step (3) is mixed with sublimated sulfur and then subjected to vacuum low-temperature heat treatment to obtain the lithium-sulfur battery positive electrode material.
上述方案中，步骤(1)中环六亚甲基四胺、六水合氯化钴及偏钒酸铵的质量比为1:4～5:12～13。In the above scheme, the mass ratio of cyclohexamethylenetetramine, cobalt chloride hexahydrate and ammonium metavanadate in step (1) is 1:4～5:12～13.
上述方案中，步骤(2)所述水浴锅温度为80℃，且保温时间为4h.In the above scheme, the temperature of the water bath described in step (2) is 80°C, and the holding time is 4h.
上述方案中，步骤(3)所述热处理温度为580℃-620℃，升温速率为5℃/min-10℃/min，保温时间为1-3h。In the above scheme, the heat treatment temperature in step (3) is 580°C-620°C, the heating rate is 5°C/min-10°C/min, and the holding time is 1-3h.
上述方案中，步骤(4)的热处理温度为150℃-160℃，升温速率为1℃/min-10℃/min，保温时间为10-13h。In the above scheme, the heat treatment temperature in step (4) is 150°C-160°C, the heating rate is 1°C/min-10°C/min, and the holding time is 10-13h.
一种锂硫电池，包括正极、锂负极和电解液，所述正极包括活性物质，所述活性物质为所述的锂硫电池正极材料或按照所述的制备方法制备得到的锂硫电池正极材料。A lithium-sulfur battery includes a positive electrode, a lithium negative electrode and an electrolyte, the positive electrode includes an active material, and the active material is the positive electrode material of the lithium-sulfur battery or the positive electrode material of the lithium-sulfur battery prepared according to the preparation method. .
与现有技术相比，本发明所具有的有益效果是：Compared with the prior art, the present invention has the following beneficial effects:
本发明提供了一种锂硫电池正极材料及其制备方法和锂硫电池。本发明提供的锂硫电池正极材料包括氧化钒片，包附于片表面的碳纳米管网络和金属钴单质及填充于网络中的硫单质。本发明提供的锂硫电池正极材料以金属钴单质和过渡金属氧化物为模板生长碳纳米管进行载硫，有效的缓解了充放电过程中的体积膨胀问题，并且金属钴单质及碳纳米管都是良好的导电材料，弥补了硫绝缘性的缺点；其次，金属钴单质具有催化作用，促进反应的进行；氧化钒对硫和多硫化物具有化学吸附作用，可以有效地抑制多硫化物在反应过程中的穿梭效应；此外，氧化钒片和***的碳纳米管网络加上钴单质，配合适当的硫含量，使此复合结构能够同时促进电子传输，且能使锂离子快速的传输到低导电的硫上，从而来提高锂硫电池的倍率性能和循环稳定性能。本实验结果表明，本发明提供的锂硫电池正极材料制备的锂硫电池在1C下，200次循环后，放电容量仍能保持501mAh/g，300次循环后放电容量可保持451mAh/g，库伦效率仍保持在100％左右；5C高倍率循环下，放电容量仍能保持532mAh/g，再次回到1C时，放电容量仍可保持679mAh/g。The invention provides a lithium-sulfur battery positive electrode material and a preparation method thereof, and a lithium-sulfur battery. The positive electrode material of the lithium-sulfur battery provided by the invention includes a vanadium oxide sheet, a carbon nanotube network and a metal cobalt element attached to the surface of the sheet, and a sulfur element filled in the network. The positive electrode material of the lithium-sulfur battery provided by the invention uses metal cobalt and transition metal oxides as templates to grow carbon nanotubes to carry sulfur, which effectively alleviates the problem of volume expansion during charging and discharging, and the metal cobalt and carbon nanotubes are both It is a good conductive material, which makes up for the shortcomings of sulfur insulation; secondly, the metal cobalt has a catalytic effect and promotes the reaction; vanadium oxide has a chemical adsorption effect on sulfur and polysulfides, which can effectively inhibit the reaction of polysulfides. The shuttle effect during the process; in addition, the vanadium oxide sheet and the surrounding carbon nanotube network plus cobalt element, with the appropriate sulfur content, make this composite structure can promote electron transport at the same time, and can quickly transport lithium ions to low conductivity on the sulfur to improve the rate performance and cycle stability of lithium-sulfur batteries. The experimental results show that the lithium-sulfur battery prepared by the cathode material of the lithium-sulfur battery provided by the present invention can maintain a discharge capacity of 501mAh/g after 200 cycles at 1C, and a discharge capacity of 451mAh/g after 300 cycles. The efficiency is still maintained at about 100%; the discharge capacity can still maintain 532mAh/g at 5C high rate cycle, and when it returns to 1C again, the discharge capacity can still maintain 679mAh/g.
附图说明Description of drawings
图1为本发明实施例1制备的锂硫电池正极材料的结构示意图；1 is a schematic structural diagram of a lithium-sulfur battery cathode material prepared in Example 1 of the present invention;
图2为本发明实施例1制备得到的金属单质与氧化钒纳米片生长碳纳米管材料的扫描电镜图；Fig. 2 is the scanning electron microscope picture of the metal element and vanadium oxide nano-sheet growth carbon nanotube material prepared by the embodiment of the present invention 1;
图3为本发明实施例1制备得到的金属单质与氧化钒纳米片生长碳纳米管材料吸附多硫化物的吸附效果图；Fig. 3 is the adsorption effect diagram of the metal element and the vanadium oxide nano-sheet growth carbon nanotube material prepared by the embodiment of the present invention 1 to adsorb polysulfide;
图4为本发明实施例1制备得到锂硫电池的充放电曲线；4 is a charge-discharge curve of a lithium-sulfur battery prepared in Example 1 of the present invention;
图5为本发明实施例1制备得到锂硫电池的倍率性能图；5 is a rate performance diagram of a lithium-sulfur battery prepared in Example 1 of the present invention;
图6为本发明实施例1制备得到锂硫电池的循环性能图。FIG. 6 is a cycle performance diagram of the lithium-sulfur battery prepared in Example 1 of the present invention.
具体实施方式Detailed ways
使本领域技术人员更好的理解本发明的技术方案，下面结合附图和具体实施例对本发明作详细说明。To make those skilled in the art better understand the technical solutions of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
如图1所示，其为本发明提供的一种锂硫电池正极材料，包括若干氧化钒纳米片、分散在每个氧化钒纳米片上的若干钴颗粒、在若干钴颗粒表面生长的碳纳米管、及分散在碳纳米管里以及同时分散在碳纳米管形成的网络中的硫单质。As shown in FIG. 1, it is a lithium-sulfur battery positive electrode material provided by the present invention, comprising several vanadium oxide nanosheets, several cobalt particles dispersed on each vanadium oxide nanosheet, and carbon nanotubes grown on the surfaces of several cobalt particles , and the sulfur element dispersed in the carbon nanotubes and simultaneously dispersed in the network formed by the carbon nanotubes.
在本发明中，所述氧化钒纳米片为六边形，其边长为2-4μm，厚1-1.5μm。本发明对所述氧化钒片的含量没有特殊限定。在本发明中，所述氧化钒片具有稳定的形状。在本发明中，所述氧化钒片对硫和多硫化物有化学吸附，可以有效抑制多硫化物的穿梭效应。In the present invention, the vanadium oxide nanosheets are hexagonal, with a side length of 2-4 μm and a thickness of 1-1.5 μm. The present invention does not specifically limit the content of the vanadium oxide flakes. In the present invention, the vanadium oxide sheet has a stable shape. In the present invention, the vanadium oxide sheet has chemical adsorption to sulfur and polysulfides, which can effectively inhibit the shuttle effect of polysulfides.
本发明提供的锂硫电池正极材料还包括散布于氮化钒片上的纳米钴颗粒。在本发明中，所述纳米钴颗粒的粒径优选为10-30nm。本发明对所述纳米钴颗粒在氧化钒片外表面的分布密度没有特殊限定，根据氧化钒和钴纳米颗粒的含量分布均匀即可。在本发明中，所述金属单质纳米钴颗粒具有高的导电率，保证硫的高利用率及优异的倍率性能。在本发明中，所述金属单质纳米钴颗粒对电池的充放电反应具有催化作用，促进反应的顺利进行。The positive electrode material of the lithium-sulfur battery provided by the present invention also includes nano-cobalt particles dispersed on the vanadium nitride sheet. In the present invention, the particle size of the cobalt nanoparticles is preferably 10-30 nm. The present invention does not specifically limit the distribution density of the nano-cobalt particles on the outer surface of the vanadium oxide sheet, and the distribution may be uniform according to the content of the vanadium oxide and cobalt nanoparticles. In the present invention, the metal elemental nano-cobalt particles have high electrical conductivity, ensuring high utilization rate of sulfur and excellent rate performance. In the present invention, the metal elemental nano-cobalt particles have a catalytic effect on the charge-discharge reaction of the battery, and promote the smooth progress of the reaction.
本发明提供的锂硫电池正极材料还包括包覆于氧化钒外侧的碳纳米管网络。在本发明中，所述碳纳米管网络为单质硫提供更大的储存空间，提高单质硫的载量并且可以缓解硫在充放电过程中的体积变化。在本发明中，所述碳纳米管直径10-30nm。在本发明中，所述碳纳米管长度为1-3μm。在本发明中，所述碳纳米管具有优异的导电性，弥补单质硫和反应产物硫化锂或硫化二锂的绝缘性。The positive electrode material of the lithium-sulfur battery provided by the present invention further comprises a carbon nanotube network coated on the outside of the vanadium oxide. In the present invention, the carbon nanotube network provides a larger storage space for elemental sulfur, increases the loading of elemental sulfur, and can alleviate the volume change of sulfur during charging and discharging. In the present invention, the diameter of the carbon nanotubes is 10-30 nm. In the present invention, the length of the carbon nanotubes is 1-3 μm. In the present invention, the carbon nanotubes have excellent electrical conductivity, which makes up for the insulating properties of elemental sulfur and the reaction product lithium sulfide or dilithium sulfide.
本发明提供的锂硫电池正极材料包括填充于碳纳米管网络内部及碳纳米管内的硫单质。本发明对所述硫单质在碳纳米管网络中的填充度没有特殊限定，可根据硫单质的含量进行调整。本发明中，所述特定含量的硫单质作为正极材料的活性物质，在片状氧化钒、金属单质纳米钴颗粒和碳纳米管网络的共同作用下，使此复合材料能保证电子和离子的快速传输与移动，达到提高锂硫电池的循环性能和倍率性能。The positive electrode material of the lithium-sulfur battery provided by the present invention includes the elemental sulfur filled in the carbon nanotube network and in the carbon nanotube. In the present invention, the filling degree of the sulfur element in the carbon nanotube network is not particularly limited, and can be adjusted according to the content of the sulfur element. In the present invention, the specific content of sulfur is used as the active material of the positive electrode material, and under the joint action of the flake vanadium oxide, the metal nano-cobalt particles and the carbon nanotube network, the composite material can ensure the rapidity of electrons and ions. Transmission and movement to improve the cycle performance and rate performance of lithium-sulfur batteries.
本发明提供了上述技术方案所述锂硫电池正极材料的制备方法，包括以下步骤：The present invention provides a method for preparing a lithium-sulfur battery positive electrode material according to the above technical solution, comprising the following steps:
1)将环六亚甲基四胺、六水合氯化钴、偏钒酸铵前驱体加入纯水中混合，得到混合物；1) adding hexamethylenetetramine, cobalt chloride hexahydrate, and ammonium metavanadate precursor into pure water and mixing to obtain a mixture;
(2)将步骤(1)制备的混合物放入水浴锅，搅拌，即得钒酸钴粉末材料；(2) putting the mixture prepared in step (1) into a water bath and stirring to obtain cobalt vanadate powder material;
(3)将步骤(2)所述的钒酸钴材料放在管式炉中，在一氧化碳气氛下，热处理进行相分离与同步生长碳纳米管包覆层。(3) The cobalt vanadate material described in step (2) is placed in a tube furnace, and in a carbon monoxide atmosphere, heat treatment is performed for phase separation and simultaneous growth of a carbon nanotube coating layer.
(4)将步骤(3)所述的复合材料与升华硫混合后进行真空低温热处理，即得到所述的锂硫电池正极材料。(4) The composite material described in step (3) is mixed with sublimated sulfur and then subjected to vacuum low-temperature heat treatment to obtain the lithium-sulfur battery positive electrode material.
本发明锂硫电池正极材料的制备原理是由前驱物水浴搅拌合成钒酸钴，在一氧化碳气氛中处理之后，钒酸钴分离出氧化钒和金属钴，在金属钴的催化作用下，一氧化碳提供碳源，并在金属钴表面生长了碳纳米管，最后经过热处理，将硫单质填充入碳纳米管网络中，得到锂硫电池正极材料。The preparation principle of the positive electrode material of the lithium-sulfur battery of the present invention is to synthesize cobalt vanadate by stirring the precursor in a water bath, and after treatment in a carbon monoxide atmosphere, the cobalt vanadate separates vanadium oxide and metal cobalt, and under the catalytic action of the metal cobalt, carbon monoxide provides carbon monoxide. source, and carbon nanotubes are grown on the surface of metal cobalt, and finally, after heat treatment, sulfur is filled into the carbon nanotube network to obtain a lithium-sulfur battery cathode material.
本发明将环六亚甲基四胺、六水合氯化钴、偏钒酸铵前驱体加入纯水中混合，得到混合物。在本发明中，所述环六亚甲基四胺、六水合氯化钴、偏钒酸铵的质量比为1:4～5:12～13。在水浴反应中，温度设置为80℃，经过搅拌4h之后，得到钒酸钴产物。随后将其在一氧化碳气氛中，处理温度为580℃-620℃，时间为1-3h，升温速率设置为5℃/min-10℃/min，便可得到金属-氧化物表面生成碳纳米管网络，经过在温度为150℃-160℃，蒸硫处理10-13h后，便可得到作为载硫介质并应用于锂硫电池正极材料。发明中，所述热处理使单质硫填充在碳纳米管网络中，有限缓解了充放电过程中硫体积变化。In the present invention, cyclohexamethylenetetramine, cobalt chloride hexahydrate and ammonium metavanadate precursor are added into pure water and mixed to obtain a mixture. In the present invention, the mass ratio of cyclohexamethylenetetramine, cobalt chloride hexahydrate, and ammonium metavanadate is 1:4-5:12-13. In the water bath reaction, the temperature was set to 80 °C, and after stirring for 4 h, the cobalt vanadate product was obtained. Then, in a carbon monoxide atmosphere, the treatment temperature is 580°C-620°C, the time is 1-3h, and the heating rate is set at 5°C/min-10°C/min, and the carbon nanotube network can be obtained on the surface of the metal-oxide. , after 10-13 hours of sulfur steam treatment at a temperature of 150°C-160°C, it can be used as a sulfur-carrying medium and used as a positive electrode material for lithium-sulfur batteries. In the invention, the heat treatment causes elemental sulfur to be filled in the carbon nanotube network, so that the volume change of sulfur during charging and discharging is alleviated to a limited extent.
本发明将三种前驱物混合的操作没有特殊的限定，采用本领域技术人员熟悉的水浴方法即可。在本发明中，所述环六亚甲基四胺、六水合氯化钴、偏钒酸铵混合物的水浴反应温度优选为80℃。在本发明中所述环六亚甲基四胺、六水合氯化钴、偏钒酸铵混合物的水浴反应优选在不停搅拌下进行；所述搅拌优选为磁力搅拌；所述搅拌的速率优选为300-600r/min，更优选为400-500r/min；所述搅拌的时间优选的为3-6h，更优选为4-5h。The operation of mixing the three precursors in the present invention is not particularly limited, and a water bath method familiar to those skilled in the art can be used. In the present invention, the water bath reaction temperature of the mixture of cyclohexamethylenetetramine, cobalt chloride hexahydrate and ammonium metavanadate is preferably 80°C. In the present invention, the water bath reaction of the mixture of cyclohexamethylenetetramine, cobalt chloride hexahydrate and ammonium metavanadate is preferably carried out under constant stirring; the stirring is preferably magnetic stirring; the stirring rate is preferably is 300-600r/min, more preferably 400-500r/min; the stirring time is preferably 3-6h, more preferably 4-5h.
本发明对所述的钒酸钴的制备的操作没有特殊限定，采用本领域技术人员熟知的水浴反应的技术方案即可。所述钒酸钴的制备优选包括以下步骤：将环六亚甲基四胺、六水合氯化钴、偏钒酸铵和纯水混合，得到混合溶剂。The present invention does not specifically limit the preparation operation of the cobalt vanadate, and the technical solution of the water bath reaction well known to those skilled in the art can be used. The preparation of the cobalt vanadate preferably includes the following steps: mixing cyclohexamethylenetetramine, cobalt chloride hexahydrate, ammonium metavanadate and pure water to obtain a mixed solvent.
水浴反应后，本发明优选的将上述水浴反应的产物进行固液分离，然后将分离得到的固体干燥，得到钒酸钴材料。本发明对所述固液分离和干燥的操作没有特殊限定，采用本领域技术人员熟知的固液分离和干燥的技术方案即可。在本发明中，所述固液分离优选为抽滤，所述抽滤次数优选为2次。After the water bath reaction, the present invention preferably performs solid-liquid separation on the product of the above water bath reaction, and then the separated solid is dried to obtain a cobalt vanadate material. The present invention does not specifically limit the operations of the solid-liquid separation and drying, and the technical solutions of solid-liquid separation and drying well known to those skilled in the art can be adopted. In the present invention, the solid-liquid separation is preferably suction filtration, and the number of times of the suction filtration is preferably 2 times.
得到钒酸钴材料后，本发明将所述钒酸钴材料进行热处理，得到金属单质钴颗粒和片状氧化钒包覆碳纳米管网络。在本发明中，所述热处理温度优选为580℃-620℃，优选为590℃-610℃；所述热处理温度为1-3h，优选为2.5h-1.5h。在本发明中，所述热处理优选在一氧化碳气氛下进行。本发明所述热处理升温速率优选为5℃/min-10℃/min。After the cobalt vanadate material is obtained, the present invention heats the cobalt vanadate material to obtain metal elemental cobalt particles and a flaky vanadium oxide-coated carbon nanotube network. In the present invention, the heat treatment temperature is preferably 580°C-620°C, preferably 590°C-610°C; the heat treatment temperature is 1-3h, preferably 2.5h-1.5h. In the present invention, the heat treatment is preferably performed in a carbon monoxide atmosphere. The heating rate of the heat treatment in the present invention is preferably 5°C/min-10°C/min.
得到片状氧化钒上分布有金属单质钴颗粒及***包覆有碳纳米管网络的材料后，本发明将上述复合材料与硫单质混合后进行热处理，得到锂硫电池正极材料。After obtaining the material with metal elemental cobalt particles distributed on the flaky vanadium oxide and surrounded by carbon nanotube network, the present invention mixes the composite material with sulfur element and heat treatment to obtain the lithium-sulfur battery positive electrode material.
本发明对上述复合材料与单质硫混合的操作没有特殊规定，采用本领域技术人员熟知的粉末混合的技术方案即可。在本发明中，上述复合材料与单质硫混合优选为研磨混合，所述研磨混合时间优选为0.5-3h，优选为1-2h。混合后进行热处理的温度优选为150℃-165℃，最优选为155℃-160℃；所述热处理时间优选为10-13h，最优选为11-12h。本发明中，所述热处理使单质硫填充在碳纳米管网络中，有限缓解了充放电过程中硫体积变化。The present invention has no special provisions on the operation of mixing the above-mentioned composite material with elemental sulfur, and the technical solution of powder mixing well known to those skilled in the art can be adopted. In the present invention, the above-mentioned composite material is preferably mixed with elemental sulfur by grinding and mixing, and the grinding and mixing time is preferably 0.5-3h, preferably 1-2h. The temperature for heat treatment after mixing is preferably 150°C-165°C, most preferably 155°C-160°C; the heat treatment time is preferably 10-13h, most preferably 11-12h. In the present invention, the heat treatment causes elemental sulfur to be filled in the carbon nanotube network, and the change in the volume of sulfur during charging and discharging is limited.
本发明还提供了一种锂硫电池，包括正极、锂负极和电解液，所述正极包括活性物质，所述活性物质为上述技术方案所述锂硫电池正极材料或按照上述技术方案所述制备方法制备的锂硫电池正极材料。The present invention also provides a lithium-sulfur battery, comprising a positive electrode, a lithium negative electrode and an electrolyte, the positive electrode includes an active material, and the active material is the positive electrode material of the lithium-sulfur battery described in the above technical solution or prepared according to the above technical solution The lithium-sulfur battery cathode material prepared by the method.
下面以几个具体实施例来说明。Several specific embodiments are described below.
实施例1Example 1
本实施例提供该锂硫电池正极材料的制备方法，包括以下步骤：This embodiment provides a method for preparing the positive electrode material of the lithium-sulfur battery, comprising the following steps:
(1)将环六亚甲基四胺、六水合氯化钴、偏钒酸铵前驱体按1:5:12.5混合，得到混合物；(1) cyclohexamethylenetetramine, cobalt chloride hexahydrate, and ammonium metavanadate precursor are mixed at 1:5:12.5 to obtain a mixture;
(2)将装有反应物的容器放入80℃水浴锅，不停搅拌4h，即得钒酸钴材料；(2) put the container containing the reactant into a water bath at 80°C, and keep stirring for 4h to obtain the cobalt vanadate material;
(3)将反应所得的钒酸钴抽滤2遍，除去未反应完全的前驱物；(3) the cobalt vanadate of reaction gained is suction filtered 2 times to remove the unreacted precursor;
(4)将最终所得的钒酸钴材料放在管式炉中，在一氧化碳气氛下热处理，以5℃/min的升温速度加热到600℃，保温时间为2h进行相分离与同步生长碳纳米管网络包覆层，待产物随炉冷却至室温后取出。(4) The final cobalt vanadate material is placed in a tube furnace, heat-treated in a carbon monoxide atmosphere, heated to 600°C at a heating rate of 5°C/min, and the holding time is 2h for phase separation and simultaneous growth of carbon nanotubes The network coating layer is taken out after the product is cooled to room temperature with the furnace.
(5)将上述的复合材料与升华硫混合后充分混合后进行155℃低温热处理12h，即得到所述的锂硫电池正极材料。(5) Mixing the above-mentioned composite material with sublimated sulfur thoroughly, and then performing a low-temperature heat treatment at 155° C. for 12 hours to obtain the lithium-sulfur battery cathode material.
图1中为本发明实施例1制备的流程图；由图2(包括图2A、图2B)的扫描电镜图可知，本实施例制备得到的最终产物为氧化钒片及外层由金属单质钴催化生长的碳纳米管网络结构。由此可知，所得产物为具有高的导电性、催化性、吸附性及较大的载硫空隙。图3为所锂硫电池的充放电曲线，图4为锂硫电池的倍率性能图，图5为锂硫电池的循环性能图，在1C下，200次循环后，放电容量仍能保持501mAh/g，300次循环后放电容量可保持451mAh/g，库伦效率仍保持在98％左右；5C高倍率循环下，放电容量仍能保持532mAh/g，再次回到1C时，放电容量仍可保持679mAh/g。1 is a flow chart of the preparation of Example 1 of the present invention; from the scanning electron microscope images of FIG. 2 (including FIG. 2A and FIG. 2B ), it can be seen that the final product prepared in this example is a vanadium oxide sheet and the outer layer is composed of metal elemental cobalt Catalytically grown carbon nanotube network structure. It can be seen that the obtained product has high conductivity, catalysis, adsorption and large sulfur-carrying voids. Figure 3 is the charge-discharge curve of the lithium-sulfur battery, Figure 4 is the rate performance diagram of the lithium-sulfur battery, and Figure 5 is the cycle performance diagram of the lithium-sulfur battery. At 1C, after 200 cycles, the discharge capacity can still maintain 501mAh/ g, the discharge capacity can be maintained at 451mAh/g after 300 cycles, and the Coulombic efficiency is still maintained at about 98%; under 5C high-rate cycle, the discharge capacity can still maintain 532mAh/g, and when it returns to 1C again, the discharge capacity can still maintain 679mAh /g.
实施例2Example 2
本实施例提供该锂硫电池正极材料的制备方法，包括以下步骤：This embodiment provides a method for preparing the positive electrode material of the lithium-sulfur battery, comprising the following steps:
(1)将环六亚甲基四胺、六水合氯化钴、偏钒酸铵前驱体按1:5:12.5混合，得到混合物；(1) cyclohexamethylenetetramine, cobalt chloride hexahydrate, and ammonium metavanadate precursor are mixed at 1:5:12.5 to obtain a mixture;
(2)将装有反应物的容器放入80℃水浴锅，不停搅拌4h，即得钒酸钴材料；(2) put the container containing the reactant into a water bath at 80°C, and keep stirring for 4h to obtain the cobalt vanadate material;
(3)将反应所得的钒酸钴抽滤2遍，除去未反应完全的前驱物；(3) the cobalt vanadate of reaction gained is suction filtered 2 times to remove the unreacted precursor;
(4)将最终所得的钒酸钴材料放在管式炉中，在一氧化碳气氛下热处理，以5℃/min的升温速度加热到580℃，保温时间为3h进行相分离与同步生长碳纳米管包覆层，待产物随炉冷却至室温后取出。(4) The final cobalt vanadate material is placed in a tube furnace, heat-treated in a carbon monoxide atmosphere, heated to 580°C at a heating rate of 5°C/min, and the holding time is 3h for phase separation and simultaneous growth of carbon nanotubes The coating layer is taken out after the product is cooled to room temperature with the furnace.
(5)将上述的复合材料与升华硫混合后充分混合后进行160℃低温热处理，即得到所述的锂硫电池正极材料。在1C下，200次循环后，放电容量仍能保持497mAh/g，300次循环后放电容量可保持445mAh/g，库伦效率仍保持在98％以上；5C高倍率循环下，放电容量仍能保持526mAh/g，再次回到1C时，放电容量仍可保持661mAh/g。(5) Mixing the above-mentioned composite material with sublimated sulfur and then fully mixing it, and then performing a low temperature heat treatment at 160° C. to obtain the lithium-sulfur battery positive electrode material. At 1C, after 200 cycles, the discharge capacity can still maintain 497mAh/g, after 300 cycles, the discharge capacity can maintain 445mAh/g, and the coulombic efficiency still remains above 98%; under 5C high-rate cycling, the discharge capacity can still maintain 526mAh/g, and when it returns to 1C again, the discharge capacity can still maintain 661mAh/g.
实施例3Example 3
本实施例提供该锂硫电池正极材料的制备方法，包括以下步骤：This embodiment provides a method for preparing the positive electrode material of the lithium-sulfur battery, comprising the following steps:
(1)将环六亚甲基四胺、六水合氯化钴、偏钒酸铵前驱体按1:5:12.5混合，得到混合物；(1) cyclohexamethylenetetramine, cobalt chloride hexahydrate, and ammonium metavanadate precursor are mixed at 1:5:12.5 to obtain a mixture;
(2)将装有反应物的容器放入80℃水浴锅，不停搅拌4h，即得钒酸钴材料；(2) put the container containing the reactant into a water bath at 80°C, and keep stirring for 4h to obtain the cobalt vanadate material;
(3)将反应所得的钒酸钴抽滤2遍，除去未反应完全的前驱物；(3) the cobalt vanadate of reaction gained is suction filtered 2 times to remove the unreacted precursor;
(3)将最终所得的钒酸钴材料放在管式炉中，在一氧化碳气氛下热处理，以5℃/min的升温速度加热到620℃，保温时间为2h进行相分离与同步生长碳纳米管包覆层，待产物随炉冷却至室温后取出。(3) The final cobalt vanadate material is placed in a tube furnace, heat-treated in a carbon monoxide atmosphere, heated to 620°C at a heating rate of 5°C/min, and the holding time is 2h for phase separation and simultaneous growth of carbon nanotubes The coating layer is taken out after the product is cooled to room temperature with the furnace.
(4)将上述的复合材料与升华硫混合后充分混合后进行155℃低温热处理，即得到所述的锂硫电池正极材料。在1C下，200次循环后，放电容量仍能保持491mAh/g，300次循环后放电容量可保持442mAh/g，库伦效率仍保持在98％以上；5C高倍率循环下，放电容量仍能保持528mAh/g，再次回到1C时，放电容量仍可保持670mAh/g。(4) Mixing the above-mentioned composite material with sublimated sulfur thoroughly, and then performing a low temperature heat treatment at 155° C. to obtain the lithium-sulfur battery positive electrode material. At 1C, after 200 cycles, the discharge capacity can still maintain 491mAh/g, after 300 cycles, the discharge capacity can maintain 442mAh/g, and the Coulomb efficiency still remains above 98%; under 5C high-rate cycling, the discharge capacity can still maintain 528mAh/g, and when it returns to 1C again, the discharge capacity can still maintain 670mAh/g.
以上实施例仅为本发明的示例性实施例，不用于限制本发明，本发明的保护范围由权利要求书限定。本领域技术人员可以在本发明的实质和保护范围内，对本发明做出各种修改或等同替换，这种修改或等同替换也应视为落在本发明的保护范围内。The above embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and the protection scope of the present invention is defined by the claims. Those skilled in the art can make various modifications or equivalent replacements to the present invention within the spirit and protection scope of the present invention, and such modifications or equivalent replacements should also be regarded as falling within the protection scope of the present invention.
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