CN104319409A - High-activity asymmetric electrode for all-vanadium redox flow battery and preparation method thereof - Google Patents
High-activity asymmetric electrode for all-vanadium redox flow battery and preparation method thereof Download PDFInfo
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000000694 effects Effects 0.000 title claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002131 composite material Substances 0.000 claims abstract description 46
- 239000007772 electrode material Substances 0.000 claims abstract description 38
- 239000002121 nanofiber Substances 0.000 claims abstract description 31
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 25
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 25
- 239000012528 membrane Substances 0.000 claims abstract description 25
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 17
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000001523 electrospinning Methods 0.000 claims abstract description 17
- 238000003763 carbonization Methods 0.000 claims abstract description 13
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- 238000009987 spinning Methods 0.000 claims description 56
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 150000001621 bismuth Chemical class 0.000 claims description 14
- 239000011888 foil Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002048 multi walled nanotube Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000002109 single walled nanotube Substances 0.000 claims description 6
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims description 5
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical group Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000014759 maintenance of location Effects 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003411 electrode reaction Methods 0.000 description 8
- 238000011056 performance test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
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Abstract
本发明涉及电池制造及能源存储领域，具体为一种全钒液流电池用高活性不对称电极及其制备方法。该高活性不对称电极以碳纳米管/纳米碳纤维复合电极材料作为正极，铋基催化剂/纳米碳纤维复合电极材料作为负极，正极和负极所用的复合电极材料均由静电纺丝技术及后续碳化工艺制备。先通过静电纺丝技术制备出所需要的纳米纤维膜，然后在空气中对纳米纤维膜进行预氧化，在惰性气氛管式气氛炉中碳化，得到所需要的复合电极材料。采用本发明方法制备的不对称电极不仅能同时提高正极和负极的反应活性，也能减小二者之间的反应速率差异。另外，将铋基催化剂/纳米碳纤维复合电极材料用作负极，可以有效地抑制析氢副反应，从而提高电池的容量保持率。The invention relates to the fields of battery manufacturing and energy storage, in particular to a highly active asymmetric electrode for an all-vanadium redox flow battery and a preparation method thereof. The highly active asymmetric electrode uses carbon nanotube/carbon nanofiber composite electrode material as the positive electrode, bismuth-based catalyst/carbon nanofiber composite electrode material as the negative electrode, and the composite electrode materials used in the positive and negative electrodes are prepared by electrospinning technology and subsequent carbonization process . First, the required nanofiber membrane is prepared by electrospinning technology, and then the nanofiber membrane is pre-oxidized in the air, and carbonized in an inert atmosphere tube atmosphere furnace to obtain the required composite electrode material. The asymmetric electrode prepared by the method of the invention can not only improve the reactivity of the positive electrode and the negative electrode simultaneously, but also reduce the difference in reaction rate between the two. In addition, the use of bismuth-based catalyst/carbon nanofiber composite electrode material as the negative electrode can effectively suppress the side reaction of hydrogen evolution, thereby improving the capacity retention rate of the battery.
Description
技术领域technical field
本发明涉及电池制造及能源存储领域，具体为一种全钒液流电池用高活性不对称电极及其制备方法。The invention relates to the fields of battery manufacturing and energy storage, in particular to a highly active asymmetric electrode for an all-vanadium redox flow battery and a preparation method thereof.
背景技术Background technique
全钒液流电池是一种利用钒离子不同价态的化学变化进行储能的新型二次电池，其正负极活性物质均为钒的硫酸溶液，电极反应均发生于液相，极大的降低了电化学极化，其额定功率及额定功率均能单独设计，通过更换电解液能达到瞬时充电，100％深度放电也不会对电池有所损害。基于以上优点，其可以广泛应用于风能、太阳能等储能、电网调峰、不间断电源等方面。The all-vanadium redox flow battery is a new type of secondary battery that utilizes the chemical changes in different valence states of vanadium ions to store energy. The electrochemical polarization is reduced, and its rated power and rated power can be designed separately. Instantaneous charging can be achieved by replacing the electrolyte, and 100% deep discharge will not damage the battery. Based on the above advantages, it can be widely used in wind energy, solar energy and other energy storage, power grid peak regulation, uninterruptible power supply, etc.
目前，全钒液流电池所用的电极结构主要为对称电极结构，即将碳素类的石墨毡或炭毡同时作为正极和负极。然而，既由于全钒液流电池电极反应在炭毡表面的电化学活性较低，也由于电池在炭毡上的负极反应速率慢于正极的，使得电池性能受到很大制约。所以，需要改变这种以炭毡为正负极的对称电极，在改善电极反应活性的同时减小正负极反应速率差异，从而切实有效地提高电池能量效率。At present, the electrode structure used in all-vanadium redox flow batteries is mainly a symmetrical electrode structure, that is, carbon graphite felt or carbon felt is used as the positive electrode and the negative electrode at the same time. However, both due to the low electrochemical activity of the all-vanadium redox flow battery electrode reaction on the surface of carbon felt, and because the reaction rate of the negative electrode on the carbon felt is slower than that of the positive electrode, the battery performance is greatly restricted. Therefore, it is necessary to change the symmetrical electrode with carbon felt as the positive and negative electrodes, and reduce the difference in the reaction rate of the positive and negative electrodes while improving the reaction activity of the electrode, so as to effectively improve the energy efficiency of the battery.
发明内容Contents of the invention
本发明的目的在于提供一种全钒液流电池用高活性不对称电极及其制备方法，解决现有技术中存在的全钒液流电池电极反应在电极材料表面活性低、正负极反应速率不匹配、负极的析氢副反应严重等问题。The purpose of the present invention is to provide a high-activity asymmetric electrode for an all-vanadium redox flow battery and a preparation method thereof, so as to solve the problem of low surface activity of the electrode material and the reaction rate of the positive and negative electrodes in the electrode reaction of the all-vanadium redox flow battery in the prior art. Mismatch, serious side reactions of hydrogen evolution at the negative electrode, etc.
本发明的技术方案为：Technical scheme of the present invention is:
一种全钒液流电池用高活性不对称电极，以碳纳米管/纳米碳纤维复合电极材料作为全钒液流电池的正极，铋基催化剂/纳米碳纤维复合电极材料作为全钒液流电池的负极。A highly active asymmetric electrode for an all-vanadium redox flow battery, using carbon nanotube/nano-carbon fiber composite electrode material as the positive electrode of the all-vanadium redox flow battery, and bismuth-based catalyst/nano-carbon fiber composite electrode material as the negative electrode of the all-vanadium redox flow battery .
所述的全钒液流电池用高活性不对称电极的制备方法，包括以下的步骤和工艺方法：The preparation method of the highly active asymmetric electrode for the all-vanadium redox flow battery comprises the following steps and process method:
1)纺丝液的制备：将聚丙烯腈以一定比例加入到二甲基甲酰胺中，水浴条件下搅拌均匀；1) Preparation of spinning solution: adding polyacrylonitrile to dimethylformamide in a certain proportion, stirring evenly under water bath conditions;
其中，聚丙烯腈的平均分子量为50000～200000，聚丙烯腈与二甲基甲酰胺的质量比为5：95到20：80，水浴温度为40～80℃；Among them, the average molecular weight of polyacrylonitrile is 50,000-200,000, the mass ratio of polyacrylonitrile to dimethylformamide is 5:95 to 20:80, and the temperature of the water bath is 40-80°C;
2)将铋盐或碳纳米管按比例加入到1)所述的纺丝液中，通过搅拌或者超声的方式使其分散均匀；2) adding bismuth salt or carbon nanotubes in proportion to the spinning solution described in 1), and dispersing them evenly by means of stirring or ultrasonic;
其中，所加入的铋盐或碳纳米管与溶液中的聚丙烯腈的质量比为1：100到10:1；Wherein, the mass ratio of the added bismuth salt or carbon nanotubes to the polyacrylonitrile in the solution is 1:100 to 10:1;
3)将步骤2)得到的复合纺丝液利用静电纺丝技术得到纳米纤维膜，纳米纤维膜的厚度为0.01～5毫米；3) Using the composite spinning solution obtained in step 2) to obtain a nanofiber membrane by electrospinning technology, the thickness of the nanofiber membrane is 0.01 to 5 mm;
4)将步骤3)得到的纳米纤维膜经过气氛炉进行预氧化及碳化；4) pre-oxidizing and carbonizing the nanofiber membrane obtained in step 3) through an atmosphere furnace;
其中，预氧化温度为200～300℃，时间为0.5～4小时；碳化温度为600～1500℃，时间为0.5～10小时，惰性保护气氛为氮气或者氩气；Among them, the pre-oxidation temperature is 200-300°C, and the time is 0.5-4 hours; the carbonization temperature is 600-1500°C, the time is 0.5-10 hours, and the inert protective atmosphere is nitrogen or argon;
5)将步骤4)得到的碳纳米管/纳米碳纤维复合电极材料装在全钒液流电池正极，铋基催化剂/纳米碳纤维复合电极材料装在其负极。5) Install the carbon nanotube/carbon nanofiber composite electrode material obtained in step 4) on the positive electrode of the all-vanadium redox flow battery, and install the bismuth-based catalyst/carbon nanofiber composite electrode material on the negative electrode thereof.
所述的全钒液流电池用高活性不对称电极的制备方法，步骤1)中，聚丙烯腈在二甲基甲酰胺中的搅拌时间0.5～24小时。In the method for preparing a high-activity asymmetric electrode for an all-vanadium redox flow battery, in step 1), the stirring time of polyacrylonitrile in dimethylformamide is 0.5 to 24 hours.
所述的全钒液流电池用高活性不对称电极的制备方法，步骤2)中，铋盐或碳纳米管在复合纺丝液中的搅拌时间为1～24小时，超声时间为0.5～10小时。In the preparation method of the highly active asymmetric electrode for the all-vanadium redox flow battery, in step 2), the stirring time of the bismuth salt or carbon nanotubes in the composite spinning solution is 1 to 24 hours, and the ultrasonic time is 0.5 to 10 hours. Hour.
所述的全钒液流电池用高活性不对称电极的制备方法，步骤2)中，铋盐为氯化铋、硝酸铋或柠檬酸铋，碳纳米管为单壁碳纳米管或多壁碳纳米管。In the preparation method of the highly active asymmetric electrode for the all-vanadium redox flow battery, in step 2), the bismuth salt is bismuth chloride, bismuth nitrate or bismuth citrate, and the carbon nanotubes are single-walled carbon nanotubes or multi-walled carbon nanotube.
所述的全钒液流电池用高活性不对称电极的制备方法，步骤3)中，静电纺丝工艺参数为：针头孔径为0.3～2.0毫米，注射器容量为5～500毫升，纺丝液流速为0.2～5毫升/小时，转辊的转速为100～1000转/分钟，针头与转辊之间的电压为10～50千伏，针头与转辊上纳米纤维膜收集板之间的距离为10～50厘米，纺丝温度为20～50℃，纺丝湿度为20～70％RH。In the method for preparing a highly active asymmetric electrode for an all-vanadium redox flow battery, in step 3), the parameters of the electrospinning process are: the aperture of the needle is 0.3-2.0 mm, the capacity of the syringe is 5-500 ml, and the flow rate of the spinning solution is 0.2 to 5 ml/hour, the rotating speed of the roller is 100 to 1000 rpm, the voltage between the needle and the roller is 10 to 50 kV, and the distance between the needle and the nanofiber film collecting plate on the roller is 10-50 cm, the spinning temperature is 20-50°C, and the spinning humidity is 20-70% RH.
所述的全钒液流电池用高活性不对称电极的制备方法，转辊上纳米纤维膜的收集板为炭纸、石墨纸、炭布、铝箔、锡箔、氧化铝箔中的一种，炭纸、石墨纸的厚度为30～300微米，炭布的厚度100～1000微米，铝箔、锡箔、氧化铝箔的厚度为10～100微米。In the preparation method of the highly active asymmetric electrode for the all-vanadium redox flow battery, the collecting plate of the nanofiber film on the rotating roller is one of carbon paper, graphite paper, carbon cloth, aluminum foil, tin foil, aluminum oxide foil, and the carbon paper 1. The thickness of graphite paper is 30-300 microns, the thickness of carbon cloth is 100-1000 microns, and the thickness of aluminum foil, tin foil and aluminum oxide foil is 10-100 microns.
所述的全钒液流电池用高活性不对称电极的制备方法，步骤4)中，预氧化处理的升温速度为2～25℃/分钟，碳化处理的升温速度为2～25℃/分钟，惰性保护中的气体流量为20～100毫升/分钟。In the method for preparing a highly active asymmetric electrode for an all-vanadium redox flow battery, in step 4), the heating rate of the pre-oxidation treatment is 2 to 25° C./min, and the heating rate of the carbonization treatment is 2 to 25° C./minute. The gas flow in the inert protection is 20-100 ml/min.
所述的全钒液流电池用高活性不对称电极的制备方法，最终的全钒液流电池用电极是由碳纳米管/纳米碳纤维复合电极材料作正极，铋基催化剂/纳米碳纤维复合电极材料作负极的高活性不对称电极。In the preparation method of the highly active asymmetric electrode for all-vanadium redox flow battery, the final all-vanadium redox flow battery electrode is made of carbon nanotube/nano-carbon fiber composite electrode material as the positive electrode, bismuth-based catalyst/nano-carbon fiber composite electrode material Highly active asymmetric electrode as negative electrode.
本发明的设计思想是：Design idea of the present invention is:
本发明首先配制实验所需的纺丝液，再将铋盐或碳纳米管与纺丝液混合均匀，通过静电纺丝的方法，制备出所需要的纳米纤维膜。然后在空气中对纳米纤维膜进行预氧化(温度200～300℃)，在惰性气氛管式气氛炉中碳化(温度600～1500℃)，分别正负极所用的复合电极材料。最后，将碳纳米管/纳米碳纤维复合电极材料装在全钒液流电池正极，铋基催化剂/纳米碳纤维复合电极材料装在其负极，即构成高活性不对称电极。由于碳纳米管/纳米碳纤维复合电极材料对全钒液流电池正极反应具有优异的电化学活性，而铋基催化剂/纳米碳纤维复合电极材料对负极反应具有优异的电化学活性。故而，采用本发明方法制备的不对称电极不仅能同时提高正极和负极的反应活性，也能减小二者之间的反应速率差异，从而极大的提高电池的能量效率。另外，将铋基催化剂/纳米碳纤维复合电极材料用作负极，可以有效地抑制析氢副反应，从而提高电池的容量保持率。The invention firstly prepares the spinning solution required for the experiment, then mixes the bismuth salt or the carbon nanotube with the spinning solution evenly, and prepares the required nanofiber film through the electrospinning method. Then pre-oxidize the nanofiber membrane in air (temperature 200-300°C), carbonize in an inert atmosphere tube-type atmosphere furnace (temperature 600-1500°C), and separate the composite electrode materials used for positive and negative electrodes. Finally, the carbon nanotube/carbon nanofiber composite electrode material is installed on the positive electrode of the all-vanadium redox flow battery, and the bismuth-based catalyst/carbon nanofiber composite electrode material is installed on the negative electrode, which constitutes a highly active asymmetric electrode. Since the carbon nanotube/carbon nanofiber composite electrode material has excellent electrochemical activity for the positive electrode reaction of the all-vanadium redox flow battery, and the bismuth-based catalyst/carbon nanofiber composite electrode material has excellent electrochemical activity for the negative electrode reaction. Therefore, the asymmetric electrode prepared by the method of the present invention can not only improve the reactivity of the positive electrode and the negative electrode, but also reduce the difference in reaction rate between the two, thereby greatly improving the energy efficiency of the battery. In addition, the use of bismuth-based catalyst/carbon nanofiber composite electrode material as the negative electrode can effectively suppress the side reaction of hydrogen evolution, thereby improving the capacity retention rate of the battery.
本发明的优点和有益效果如下：Advantage of the present invention and beneficial effect are as follows:
1.本发明提出的高活性不对称电极既能同时提高正极和负极的反应活性，也能减小二者之间的反应速率差异，从而极大的提高电池的能量效率。1. The highly active asymmetric electrode proposed by the present invention can not only improve the reactivity of the positive electrode and the negative electrode, but also reduce the difference in reaction rate between the two, thereby greatly improving the energy efficiency of the battery.
2.本发明提出的高活性不对称电极，可以有效地抑制析氢副反应，从而提高电池的容量保持率。2. The highly active asymmetric electrode proposed by the present invention can effectively suppress the side reaction of hydrogen evolution, thereby improving the capacity retention rate of the battery.
3.本发明所用到的静电纺丝设备简单，实验条件易于满足，且方法价格低廉、易于操作。3. The electrospinning equipment used in the present invention is simple, the experimental conditions are easy to meet, and the method is cheap and easy to operate.
4.本发明的全钒液流电池电极反应在电极材料表面活性高，电极材料性能稳定。4. The electrode reaction of the all-vanadium redox flow battery of the present invention has high surface activity in the electrode material, and the performance of the electrode material is stable.
具体实施方式Detailed ways
在本发明的具体实施方式中，全钒液流电池用高活性不对称电极的制备方法，包括以下的步骤和工艺方法：In a specific embodiment of the present invention, the preparation method of a highly active asymmetric electrode for an all-vanadium redox flow battery comprises the following steps and process:
1)纺丝液的制备：将聚丙烯腈以一定的比例加入到二甲基甲酰胺中，水浴条件下搅拌均匀；1) Preparation of spinning solution: adding polyacrylonitrile to dimethylformamide in a certain proportion, and stirring evenly under water bath conditions;
其中，聚丙烯腈的平均分子量为50000～200000，聚丙烯腈与二甲基甲酰胺的质量比为5：95到20：80(优选为10：90到15：85)，水浴温度为40～80℃，聚丙烯腈在二甲基甲酰胺中的搅拌时间为0.5～24小时(优选为3～6小时)。Among them, the average molecular weight of polyacrylonitrile is 50,000 to 200,000, the mass ratio of polyacrylonitrile to dimethylformamide is 5:95 to 20:80 (preferably 10:90 to 15:85), and the temperature of the water bath is 40 to 20:00. At 80°C, the stirring time of polyacrylonitrile in dimethylformamide is 0.5-24 hours (preferably 3-6 hours).
2)将铋盐或碳纳米管按比例加入到步骤1)所述的纺丝液中，通过搅拌或者超声的方式使其分散均匀。铋盐或碳纳米管在纺丝液中的搅拌时间为1～24小时(优选为6～18小时)，超声时间为0.5～10小时(优选为2～6小时)。2) Add bismuth salt or carbon nanotubes to the spinning solution described in step 1) in proportion, and disperse them uniformly by stirring or ultrasonic. The stirring time of the bismuth salt or carbon nanotubes in the spinning solution is 1-24 hours (preferably 6-18 hours), and the ultrasonic time is 0.5-10 hours (preferably 2-6 hours).
其中，铋盐为氯化铋、硝酸铋或柠檬酸铋，碳纳米管为单壁碳纳米管或多壁碳纳米管；所加入的铋盐或碳纳米管与溶液中的聚丙烯腈的质量比为1：100到10:1(优选为1：100到1：1)；Wherein, the bismuth salt is bismuth chloride, bismuth nitrate or bismuth citrate, and the carbon nanotubes are single-wall carbon nanotubes or multi-wall carbon nanotubes; the added bismuth salt or carbon nanotubes and the mass of polyacrylonitrile in the solution The ratio is 1:100 to 10:1 (preferably 1:100 to 1:1);
3)将步骤2)得到的复合纺丝液利用静电纺丝技术得到纳米纤维膜，纳米纤维膜的厚度为0.01～5毫米(优选为0.5～5毫米)；3) Using the composite spinning solution obtained in step 2) to obtain a nanofiber membrane by electrospinning technology, the thickness of the nanofiber membrane is 0.01 to 5 mm (preferably 0.5 to 5 mm);
其中，静电纺丝工艺参数为：针头孔径为0.3～2.0毫米，注射器容量为5～500毫升，纺丝液流速为0.2～5毫升/小时，转辊的转速为100～1000转/分钟，针头与转辊之间的电压为10～50千伏，针头与转辊上纳米纤维膜收集板之间的距离为10～50厘米，纺丝温度为20～50℃，纺丝湿度为20～70％RH(RelativeHumidity)。转辊上纳米纤维膜的收集板为炭纸、石墨纸、炭布、铝箔、锡箔、氧化铝箔中的一种，炭纸、石墨纸的厚度为30～300微米，炭布的厚度100～1000微米，铝箔、锡箔、氧化铝箔的厚度为10～100微米。Among them, the parameters of the electrospinning process are: the diameter of the needle head is 0.3-2.0 mm, the volume of the syringe is 5-500 ml, the flow rate of the spinning solution is 0.2-5 ml/hour, the rotation speed of the roller is 100-1000 rpm, the needle head The voltage between the roller and the roller is 10-50 kV, the distance between the needle and the nanofiber film collecting plate on the roller is 10-50 cm, the spinning temperature is 20-50°C, and the spinning humidity is 20-70 %RH (Relative Humidity). The collecting plate of the nanofiber film on the roller is one of carbon paper, graphite paper, carbon cloth, aluminum foil, tin foil and aluminum oxide foil. The thickness of carbon paper and graphite paper is 30-300 microns, and the thickness of carbon cloth is 100-1000 microns Micron, the thickness of aluminum foil, tin foil, aluminum oxide foil is 10-100 microns.
4)将步骤3)得到的纳米纤维膜经过气氛炉进行预氧化及碳化；4) pre-oxidizing and carbonizing the nanofiber membrane obtained in step 3) through an atmosphere furnace;
其中，预氧化温度为200～300℃，升温速度为2～25℃/分钟，时间为0.5～4小时；碳化温度为600～1500℃，升温速度为2～25℃/分钟，时间为0.5～10小时，惰性保护气氛为氮气或者氩气，气体流量为20～100毫升/分钟；Among them, the pre-oxidation temperature is 200-300°C, the heating rate is 2-25°C/min, and the time is 0.5-4 hours; the carbonization temperature is 600-1500°C, the heating rate is 2-25°C/min, and the time is 0.5-4 hours. 10 hours, the inert protective atmosphere is nitrogen or argon, and the gas flow rate is 20-100 ml/min;
5)将步骤4)得到的碳纳米管/纳米碳纤维复合电极材料装在全钒液流电池正极，铋基催化剂/纳米碳纤维复合电极材料装在其负极；5) The carbon nanotube/carbon nanofiber composite electrode material obtained in step 4) is installed on the positive electrode of the all-vanadium redox flow battery, and the bismuth-based catalyst/carbon nanofiber composite electrode material is installed on its negative electrode;
最终的全钒液流电池用电极是由碳纳米管/纳米碳纤维复合电极材料作正极，铋基催化剂/纳米碳纤维复合电极材料作负极的高活性不对称电极。The final all-vanadium redox flow battery electrode is a high-activity asymmetric electrode with a carbon nanotube/carbon nanofiber composite electrode material as the positive electrode and a bismuth-based catalyst/carbon nanofiber composite electrode material as the negative electrode.
本发明所用实验材料(如：聚丙烯腈、铋盐或碳纳米管等)均为市售，无需后续纯化处理，气体均为高纯气体(纯度≥99.999％)。The experimental materials used in the present invention (such as: polyacrylonitrile, bismuth salt or carbon nanotubes, etc.) are all commercially available, without subsequent purification treatment, and the gases are all high-purity gases (purity ≥ 99.999%).
下面通过实施例对本发明进一步详细描述。The present invention will be described in further detail below by way of examples.
实施例1Example 1
1)质量分数为10％的聚丙烯腈在搅拌条件下加入到二甲基甲酰胺中，水浴温度为60℃下搅拌2小时得到纺丝液，聚丙烯腈的平均分子量为150000。1) Add polyacrylonitrile with a mass fraction of 10% into dimethylformamide under stirring conditions, and stir for 2 hours at a water bath temperature of 60° C. to obtain a spinning solution. The average molecular weight of polyacrylonitrile is 150,000.
2)取两份纺丝液各100克，将氯化铋加入到一份纺丝液中，将多壁碳纳米管加入到另一份纺丝液中。所加入氯化铋与其溶液中聚丙烯腈的质量比为1：50，所加入多壁碳纳米管与其溶液中聚丙烯腈的质量比为1：100。搅拌12小时后，再超声6小时，得到两种均匀的复合纺丝液。2) Take 100 grams each of two spinning solutions, add bismuth chloride to one spinning solution, and add multi-walled carbon nanotubes to the other spinning solution. The mass ratio of the added bismuth chloride to the polyacrylonitrile in the solution is 1:50, and the mass ratio of the added multi-walled carbon nanotubes to the polyacrylonitrile in the solution is 1:100. After stirring for 12 hours, it was ultrasonicated for 6 hours to obtain two homogeneous composite spinning solutions.
3)将经过步骤2)得到的两种复合纺丝液分别加入到20ml的注射器中，各自进行静电纺丝得到纳米纤维膜，本实施例纳米纤维膜的厚度为0.5毫米。纺丝参数为：针头孔径为0.3毫米，针头与转辊上纳米纤维膜收集板的距离为12厘米，它们之间的纺丝电压为25kV，收集板为200微米后厚的炭纸，转辊的转速为200转/分钟，纺丝液流速为0.5毫升/小时，纺丝温度为40℃，湿度为50％RH。3) Add the two composite spinning solutions obtained in step 2) into 20ml syringes respectively, and perform electrospinning respectively to obtain nanofiber membranes. The thickness of the nanofiber membranes in this embodiment is 0.5 mm. The spinning parameters are: the aperture of the needle head is 0.3 mm, the distance between the needle head and the nanofiber membrane collecting plate on the rotating roller is 12 cm, the spinning voltage between them is 25 kV, the collecting plate is carbon paper with a thickness of 200 microns, and the rotating roller The spinning speed is 200 rpm, the spinning solution flow rate is 0.5 ml/hour, the spinning temperature is 40° C., and the humidity is 50% RH.
4)将经过步骤3)得到的两种纳米纤维膜放到管式气氛炉中预氧化和碳化，预氧化温度为250℃，升温速度为20℃/分钟，保温时间为2小时，气氛为空气；碳化温度为900℃，升温速度为10℃/分钟，保温时间为2小时，惰性保护气氛为氮气，气体流量为60毫升/分钟。4) Put the two nanofiber membranes obtained in step 3) into a tubular atmosphere furnace for pre-oxidation and carbonization, the pre-oxidation temperature is 250°C, the heating rate is 20°C/min, the holding time is 2 hours, and the atmosphere is air ; The carbonization temperature is 900° C., the heating rate is 10° C./min, the holding time is 2 hours, the inert protective atmosphere is nitrogen, and the gas flow rate is 60 ml/min.
5)将经过步骤4)得到的多壁碳纳米管/纳米碳纤维复合电极材料装在全钒液流电池正极，铋基催化剂/纳米碳纤维复合电极材料装在负极，进行充放电性能测试。5) Install the multi-walled carbon nanotube/carbon nanofiber composite electrode material obtained in step 4) on the positive electrode of the all-vanadium redox flow battery, and the bismuth-based catalyst/carbon nanofiber composite electrode material on the negative electrode, and perform charge and discharge performance tests.
本实施例中，由于利用静电纺丝技术制备出的全钒液流电池用高活性不对称电极既能同时提高正负极反应的电化学活性，也能减小二者之间的反应速率差异，从而极大地提高电池的能量效率。在电流密度为100mA/cm2的恒流充放电测试条件下，使用该不对称电极的电池的能量效率由未使用的78.9％提高到82.5％，容量保持率也由原来的51％提高到59％(经过100个充放电循环)。In this example, the highly active asymmetric electrode for the all-vanadium redox flow battery prepared by electrospinning technology can not only improve the electrochemical activity of positive and negative electrode reactions, but also reduce the difference in reaction rate between the two. , thereby greatly improving the energy efficiency of the battery. Under the constant current charge and discharge test condition with a current density of 100mA/ cm2 , the energy efficiency of the battery using the asymmetric electrode increased from 78.9% to 82.5%, and the capacity retention rate also increased from the original 51% to 59%. % (after 100 charge and discharge cycles).
实施例2Example 2
1)质量分数为11％的聚丙烯腈在搅拌条件下加入到二甲基甲酰胺中，水浴温度为80℃下搅拌2小时得到纺丝液，聚丙烯腈的平均分子量为120000。1) Add polyacrylonitrile with a mass fraction of 11% into dimethylformamide with stirring, and stir for 2 hours at a water bath temperature of 80° C. to obtain a spinning solution. The average molecular weight of polyacrylonitrile is 120,000.
2)取两份纺丝液各100克，将硝酸铋加入到一份纺丝液中，将多壁碳纳米管加入到另一份纺丝液中。所加入硝酸铋与其溶液中聚丙烯腈的质量比为1：25，所加入多壁碳纳米管与其溶液中聚丙烯腈的质量比为1：75。搅拌18小时后，再超声8小时，得到两种均匀的复合纺丝液。2) Take 100 grams each of two spinning solutions, add bismuth nitrate to one spinning solution, and add multi-walled carbon nanotubes to the other spinning solution. The mass ratio of the added bismuth nitrate to the polyacrylonitrile in the solution is 1:25, and the mass ratio of the added multi-walled carbon nanotubes to the polyacrylonitrile in the solution is 1:75. After stirring for 18 hours, it was ultrasonicated for 8 hours to obtain two homogeneous composite spinning solutions.
3)将经过步骤2)得到的两种复合纺丝液分别加入到20ml的注射器中，各自进行静电纺丝得到纳米纤维膜，本实施例纳米纤维膜的厚度为1.5毫米。纺丝参数为：针头孔径为0.9毫米，针头与转辊上纳米纤维膜收集板的距离为15厘米，它们之间的纺丝电压为30kV，收集板为200微米后厚的炭纸，转辊的转速为500转/分钟，纺丝液流速为1.0毫升/小时，纺丝温度为50℃，湿度为50％RH。3) Add the two composite spinning solutions obtained in step 2) into 20ml syringes respectively, and perform electrospinning respectively to obtain nanofiber membranes. The thickness of the nanofiber membranes in this embodiment is 1.5 mm. The spinning parameters are: the aperture of the needle head is 0.9 mm, the distance between the needle head and the nanofiber film collecting plate on the rotating roller is 15 cm, the spinning voltage between them is 30 kV, the collecting plate is carbon paper with a thickness of 200 microns, and the rotating roller The spinning speed is 500 rpm, the spinning solution flow rate is 1.0 ml/hour, the spinning temperature is 50° C., and the humidity is 50% RH.
4)将经过步骤3)得到的纳米纤维膜放到管式气氛炉中预氧化和碳化，预氧化温度为300℃，升温速度为20℃/分钟，保温时间为3小时，气氛为空气；碳化温度为1000℃，升温速度为10℃/分钟，保温时间为3小时，惰性保护气氛为氮气，气体流量为80毫升/分钟。4) Put the nanofiber membrane obtained in step 3) into a tubular atmosphere furnace for preoxidation and carbonization, the preoxidation temperature is 300°C, the heating rate is 20°C/min, the holding time is 3 hours, and the atmosphere is air; carbonization The temperature is 1000°C, the heating rate is 10°C/min, the holding time is 3 hours, the inert protective atmosphere is nitrogen, and the gas flow rate is 80 ml/min.
5)将经过步骤4)得到的多壁碳纳米管/纳米碳纤维复合电极材料装在全钒液流电池正极，铋基催化剂/纳米碳纤维复合电极材料装在负极，进行充放电性能测试。5) Install the multi-walled carbon nanotube/carbon nanofiber composite electrode material obtained in step 4) on the positive electrode of the all-vanadium redox flow battery, and the bismuth-based catalyst/carbon nanofiber composite electrode material on the negative electrode, and perform charge and discharge performance tests.
本实施例中，本实施例中，由于利用静电纺丝技术制备出的全钒液流电池用高活性不对称电极既能同时提高正负极反应的电化学活性，也能减小二者之间的反应速率差异，从而极大地提高电池的能量效率。在电流密度为100mA/cm2的恒流充放电测试条件下，使用该不对称电极的电池的能量效率由未使用的78.9％提高到83.6％，容量保持率也由原来的51％提高到64％(经过100个充放电循环)。In this embodiment, in this embodiment, since the high-activity asymmetric electrode for all-vanadium redox flow battery prepared by electrospinning technology can not only improve the electrochemical activity of positive and negative electrode reactions at the same time, but also reduce the difference between the two. The reaction rate difference between them can greatly improve the energy efficiency of the battery. Under the constant current charge and discharge test condition with a current density of 100mA/ cm2 , the energy efficiency of the battery using the asymmetric electrode increased from 78.9% to 83.6%, and the capacity retention rate also increased from the original 51% to 64%. % (after 100 charge and discharge cycles).
实施例3Example 3
1)质量分数为12％的聚丙烯腈在搅拌条件下加入到二甲基甲酰胺中，水浴温度为80℃下搅拌4小时得到纺丝液，聚丙烯腈的平均分子量为150000。1) Add polyacrylonitrile with a mass fraction of 12% into dimethylformamide under stirring conditions, and stir for 4 hours at a water bath temperature of 80° C. to obtain a spinning solution. The average molecular weight of polyacrylonitrile is 150,000.
2)取两份纺丝液各100克，将柠檬酸铋加入到一份纺丝液中，将单壁碳纳米管加入到另一份纺丝液中。所加入柠檬酸铋与其溶液中聚丙烯腈的质量比为1：15，所加入单壁碳纳米管与其溶液中聚丙烯腈的质量比为1：50。搅拌24小时后，再超声8小时，得到两种均匀的复合纺丝液。2) Take 100 grams each of two spinning solutions, add bismuth citrate to one spinning solution, and add single-walled carbon nanotubes to the other spinning solution. The mass ratio of the added bismuth citrate to the polyacrylonitrile in the solution is 1:15, and the mass ratio of the added single-walled carbon nanotubes to the polyacrylonitrile in the solution is 1:50. After stirring for 24 hours, it was ultrasonicated for 8 hours to obtain two homogeneous composite spinning solutions.
3)将经过步骤2)得到的两种复合纺丝液分别加入到20ml的注射器中，各自进行静电纺丝得到纳米纤维膜，本实施例纳米纤维膜的厚度为3毫米。纺丝参数为：针头孔径为0.9毫米，针头与转辊上纳米纤维膜收集板的距离为16厘米，它们之间的纺丝电压为30kV，收集板为200微米后厚的炭布，转辊的转速为800转/分钟，纺丝液流速为1.2毫升/小时，纺丝温度为40℃，湿度为50％RH。3) Add the two composite spinning solutions obtained in step 2) into 20ml syringes respectively, and perform electrospinning respectively to obtain nanofiber membranes. The thickness of the nanofiber membranes in this embodiment is 3 mm. The spinning parameters are: the aperture of the needle head is 0.9 mm, the distance between the needle head and the nanofiber membrane collecting plate on the rotating roller is 16 cm, the spinning voltage between them is 30 kV, the collecting plate is carbon cloth with a thickness of 200 microns, and the rotating roller The spinning speed is 800 rpm, the spinning solution flow rate is 1.2 ml/hour, the spinning temperature is 40° C., and the humidity is 50% RH.
4)将经过步骤3)得到的纳米纤维膜放到管式气氛炉中预氧化和碳化，预氧化温度为270℃，升温速度为20℃/分钟，保温时间为4小时，气氛为空气；碳化温度为1100℃，升温速度为10℃/分钟，保温时间为4小时，惰性保护气氛为氮气，气体流量为80毫升/分钟。4) Put the nanofiber membrane obtained in step 3) into a tubular atmosphere furnace for preoxidation and carbonization, the preoxidation temperature is 270°C, the heating rate is 20°C/min, the holding time is 4 hours, and the atmosphere is air; carbonization The temperature is 1100° C., the heating rate is 10° C./min, the holding time is 4 hours, the inert protective atmosphere is nitrogen, and the gas flow rate is 80 ml/min.
5)将经过步骤4)得到的单壁碳纳米管/纳米碳纤维复合电极材料装在全钒液流电池正极，铋基催化剂/纳米碳纤维复合电极材料装在负极，进行充放电性能测试。5) Install the single-walled carbon nanotube/carbon nanofiber composite electrode material obtained in step 4) on the positive electrode of the all-vanadium redox flow battery, and the bismuth-based catalyst/carbon nanofiber composite electrode material on the negative electrode, and perform charge and discharge performance tests.
本实施例中，由于利用静电纺丝技术制备出的全钒液流电池用高活性不对称电极既能同时提高正负极反应的电化学活性，也能减小二者之间的反应速率差异，从而极大地提高电池的能量效率。在电流密度为100mA/cm2的恒流充放电测试条件下，使用该不对称电极的电池的能量效率由未使用的78.9％提高到84.1％，容量保持率也由原来的51％提高到71％(经过100个充放电循环)。In this example, the highly active asymmetric electrode for the all-vanadium redox flow battery prepared by electrospinning technology can not only improve the electrochemical activity of positive and negative electrode reactions, but also reduce the difference in reaction rate between the two. , thereby greatly improving the energy efficiency of the battery. Under the constant current charge and discharge test condition with a current density of 100mA/ cm2 , the energy efficiency of the battery using the asymmetric electrode increased from 78.9% to 84.1%, and the capacity retention rate also increased from the original 51% to 71%. % (after 100 charge and discharge cycles).
实施例结果表明，本发明正极和负极所用的复合电极材料均由静电纺丝技术及后续碳化工艺制备，采用本发明方法制备的不对称电极不仅能同时提高正极和负极的反应活性，也能减小二者之间的反应速率差异，从而极大的提高电池的能量效率。另外，将铋基催化剂/纳米碳纤维复合电极材料用作负极，可以有效地抑制析氢副反应，从而提高电池的容量保持率。The results of the examples show that the composite electrode materials used in the positive and negative electrodes of the present invention are all prepared by electrospinning technology and subsequent carbonization process, and the asymmetric electrodes prepared by the method of the present invention can not only improve the reactivity of the positive and negative electrodes simultaneously, but also reduce the The difference in reaction rate between the two is small, thereby greatly improving the energy efficiency of the battery. In addition, the use of bismuth-based catalyst/carbon nanofiber composite electrode material as the negative electrode can effectively suppress the side reaction of hydrogen evolution, thereby improving the capacity retention rate of the battery.
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