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    • 专利摘要:
    Carbon electrodes for vanadium redox flow batteries modified by incorporating a salt of a metal, drying and subsequent heat treatment. The impregnation of conductive carbonaceous electrodes is carried out by means of a solution with the necessary amount of chloride, nitrate, sulfate, oxalate, carbonate, etc., of metals group viiib, ib, rhenium (re), manganese (mn), indium (in), titanium (ti), molybdenum (mo), niobium (nb), zirconium (zr), tungsten (w) or mixtures of these compounds, to obtain an electrode with up to 0.1-20% by weight of metal. After the incorporation of the metal solution, the elimination of the water present in the electrode can be carried out following two processes: 1) drying room temperature for 10-24 hours and 2) by freeze-drying process 10-20 hours. After the elimination of the water the electrode is calcined at 300-500ºc in an oven for 10-20 hours. This is how we get electrodes with high conductivity and high resistance to redox and corrosión processes. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2646938A1
    申请号:ES201600506
    申请日:2016-06-15
    公开日:2017-12-18
    发明作者:Javier PORCAR VIVES；Antonio Chica Lara；Javier Francisco DA COSTA SERRA；Rubén BENEITO RUIZ；Asunción CLIMENT ALOS；Rafael ROS PÉREZ
    申请人:Innotecno Dev S L；Innotecno Development SL；
    IPC主号:
    专利说明:

    image 1
    image2
    image3 DESCRIPTION
    Procedure for the modification of carbon electrodes for use in vanadium redox flow batteries. Technical sector
    The patent is addressed to the energy sector and more specifically to the energy storage sector of batteries.
    The present invention relates to a method for obtaining carbon-based electrodes for a vanadium redox flow battery and its manufacturing method. Background of the invention
    Conventional redox flow battery electrodes are mainly composed of a carbon-based conductive material, such as carbon fiber, graphite fiber, graphite felt or the like. In order to improve the electrochemical activity of these electrodes, increasing their energy efficiency and durability, the surface of the electrode can be modified. This modification can be done through different treatments. As it can be an acid, thermal treatment or through an ion exchange process so that the surface of the carbon-based electrode is coated with a metal of the group VIIB, IB, manganese (Mn), indium (In), titanium ( Ti), molybdenum (Mo), niobium (Nb), zirconium (Zr), tungsten (W) or mixtures thereof. In addition, the metal can be used in elemental form or formed part of another compound. For example, hydroxides, oxides, nitrates, carbonates, chlorides, oxalates and acetates have been used.
    Some researchers have improved the catalytic properties and conductivity of carbon felt by depositing metals on the surface of the electrode. Wang et al incorporated Ir into the carbon felt by immersing it in a solution of H21rCI6 containing 10% by weight ethanol [W.H. Wang, X.D. Wang, Electrochim. Minutes 52 (2007) 6755 6762]. This method of incorporation includes a vacuum drying step followed by a calcination at 450 ° C. The immersion, vacuum drying and calcination process must be repeated 8 times, which is a serious inconvenience from the point of view applied. In another work Sun and Skyllas-Kazacos [B.T. Sun, M. Skyllas-Kazacos, Electrochim. Minutes 36 (1 991) 513-517] modified carbon felt electrodes through impregnation with ions such as Pt (IV), Pd (ll), Au (IV), Mn (ll), Te (IV), In (III) and Ir (III). The type of metal precursors used for the incorporation of each metal is not mentioned. The incorporation method used was ion exchange with a 0.1 M solution of the metal for 50 h. The Ir (III) electrode was tuned to improve its performance as a positive electrode in a vanadium redox flow battery. Fabjan et al. [C. Fabjan, J. Garche, B. Harrer, L. Jorissen, C. Kolbeck, F. Philippi, G. Tomazic, F. Wagner, Electrochim. Minutes 47 (2001) 825-831] reported that the Ru (RuO2) oxide incorporated in the positive electrode improved the reaction rate and decreased side reactions such as gas evolution. More recently, an improvement in electrocatalytic activity has also been found with the incorporation of non-precious elements such as bismuth into the positive electrode [Z. González, A. Sánchez, C. Blanco, M. Granda, R. Menéndez, R. Santamaría, Electrochem. Commun. 13 (2011) 1379-1382], manganese in hausmannite (Mn3O4) [K.J. Kim, M.S. Park, J.H. Kim, U. Hwang, N.J. Lee, G.J. Jeong, Y.-J. Kim, Chem. Commun. 48 (2012) 5455-5457]; cerium; [P. Leung, X. Li, C. Ponce de León, L. Berlouis, C.T.J. Low,
    F.C.  Walsh, RSC Adv. 2 (2012) 10125-10156; H. Zhou, J. Xi, Z. Li, Z. Zhang, L. Yu, L. Liu,
    X. Qiu and L Chen, RSC Adv. 4 (2014) 61912-61918], niobium [B. Li, M. Gu, Z. Nie, X. Wei,
    C.  Wang, V. Sprenkle and W. Wang, Nano Lett. 14 (2014) 158-165], lead [X. Wu, H. Xu,
    L.  Lu, H. Zhao, J. Fu, Y. Shen, P. Xu, Y. Dong, J. of Power Sources 250 (2014) 274-278] and tungsten [Y. Shen, H. Xu, P. Xu, X. Wu, Y. Dong, L. Lu, Electrochim. Minutes 132 (2014) 37-41]. Although the electrodes thus obtained have superior electrochemical properties and durability, their manufacturing process is very laborious, which is an inconvenient sin for its industrial implementation. In addition, the improvement works referred to in the mentioned works have been carried out on the positive electrode.
    image4
    Accordingly, the present invention has been carried out taking into account the problems encountered in the aforementioned techniques and is intended to provide an electrode (both positive and negative) for the vanadium redox flow battery, in which both the positive electrode As carbon negative it is modified to increase its conductivity and electrochemical characteristics, and improve battery performance, including electrode durability, corrosion resistance, power density, energy efficiency and cycle properties.
    The object of the present invention is the development of an alternative and easily scalable method of incorporating metals into carbon electrodes that allows manufacturing both positive and negative electrodes of high conductivity (> 100 S / cm) and high resistance to redox processes that they take place in the vanadium redox flow battery; The electrodes have to be resistant to corrosion. Explanation of the invention.
    To obtain the modified carbon electrodes for redox vanadium flow batteries, it is based on conventional carbon-based materials, which are subjected to a wet impregnation at pore volume with a metal precursor, drying and subsequent heat treatment.
    The wet impregnation method at pore volume consists in the incorporation into the electrode of an aqueous solution of the precursor of the desired metal. The amount of solution incorporated would be equivalent to the pore volume of the carbonaceous material used as the electrode.
    The solution used for impregnation contains the necessary amount of a metal precursor of group VIIIB, IB, rhenium (Re), manganese (Mn), indium (In), titanium (Ti), molybdenum (Mo), niobium (Nb) , zirconium (Zr), tungsten (W) or mixtures thereof, to finally obtain an electrode with 0.1-20% by weight of metal. After impregnation, two different methods have been used for drying the electrodes:
    one) At room temperature for 10-24h.
    2) By a freezing stage at temperatures between 0 ° C and -100 ° C for 1-5 hours followed by lyophilization at temperatures between -10 ° C and -100 ° C for 10-20 hours.
    After drying, by one of the methods described above, a calcination is carried out at 300-500 ° C in an oven for 10-20 hours. By proceeding in this way, electrodes of high conductivity (> 100 S / cm) and high resistance to redox processes and corrosion that take place in vanadium redox flow batteries are achieved.
    image5 Preferred Embodiment of the Invention
    In the following, some examples will be described that include the different studies that have given rise to the present invention, in order to obtain the modified carbon electrodes for redox vanadium flow batteries, in which reference will be made in tables to the data obtained : Example 1
    The procedure followed for the incorporation of the Mn in two carbon felt electrodes (GFD 4.6 EA) by the wet pore volume impregnation method is described below. Before incorporating the Mn an activation of the felts is carried out at 400 for 15 hours in muffle. The two carbon felts have dimensions 10x14 cm with a weight of 5,026 g each, to which drop is added
    15 dropwise a solution of 0.905 g of MnCI2 • 4H2O in 54.53 ml of MiliQ water until the wet impregnation at pore volume for each felt is completed. Then, the drying of both felts is carried out. In the present example, said drying was carried out at room temperature, in desiccator, for 16 hours. Once the electrode has dried, it is calcined at 400 ° C for 15 hours.
    20 After this heat treatment the electrodes were incorporated into the vanadium redox flow battery and their behavior was studied.
    Table 1 compares the results obtained with the electrodes modified with
    25 Mn by the wet impregnation method at pore volume and unmodified. As can be seen, the modified electrodes provide higher loading and unloading capacities than the unmodified electrodes. Likewise, the losses of loading and unloading capacity with the number of cycles are also lower in the electrodes modified with Mn.
    30
    Table 1: behavior of electrodes modified with Mn and unmodified
    image6
    image7 Example 2
    This example describes the incorporation of Ni (5% by weight) following the same methodology described in example 1.
    Prior to the wet impregnation at pore volume of Ni, carbon felts have undergone an activation heat treatment at 400 ° C in muffle. Four carbon felts of dimensions 10x14 cm with a weight of 10.14 g are available, to which a solution of 2.06 g of NiCI2 • 6H2O in 110.01 ml of MiliQ water is added dropwise to complete wet impregnation at pore volume for each felt. Then, the drying of the four felts is carried out. In the present example two of the felts are dried at room temperature, in desiccator, for 16 hours. The other two felts are frozen at -80 ° C, placing the felts in an ultra-freezer for 3 hours, then placing them in a freeze-drying chamber that works at -55 ° C and under vacuum, for 16 hours to remove water.
    Once the four electrodes are dried, they are calcined at 400 ° C for 15 hours. After this heat treatment the electrodes are ready for incorporation into the battery and subsequent characterization.
    Table 2 compares the results obtained with the electrodes modified with Ni by the wet impregnation method at pore volume and unmodified. As can be seen, the modified electrodes provide higher loading and unloading capacities than the unmodified electrodes.
    Likewise, the losses of loading and unloading capacity with the number of cycles are also lower in the electrodes modified with Ni. It can also be seen that the two drying methods used (drying at room temperature and by lyophilization) allow to prepare modified electrodes with better properties than without modifying.
    Table 2: behavior of electrodes modified with Ni and unmodified.
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    权利要求:
    Claims (5)
    [1]
    image 1
    image2
    image3
    1. A procedure for the modification of carbon electrodes, for use in vanadium redox flow batteries, which consists in the use of a conventional carbon felt that is subjected to the following process:
    - wet impregnation at pore volume with metals of group VIIIB, group IB, Mn, Re, Mo, W, Nb, Zr, Ti and mixtures thereof to obtain between 0.1 and 20% by weight of metal.
    [2]
    2.  A process in which the electrodes prepared according to claim 1 are dried at room temperature in a desiccator for 10-24 hours and calcined between 300 ° C and 500 ° C for 10-20 hours.
    [3]
    3.  A process in which the electrodes prepared according to claim 1 are subjected to a freezing process between 0 ° C and -100 ° C for 1-5 hours, subsequently lyophilized at a temperature between -10 ° C and -100 ° C for 10-20 hours and finally calcined 300 ° C and 500 ° C for 10-20 hours.
    [4]
    Four.  A method for the preparation of electrodes as set forth in claim 1 wherein the carbonaceous material, instead of carbon felt, comprises carbon fiber, graphite fiber, graphite felt, carbon black, graphene or graphite.
    [5]
    5.  A process for the preparation of electrodes as set forth in claim 1 wherein the precursor compounds of said metals comprise hydroxides, oxides, halides, nitrates, sulfates, carbonates, oxalates or acetates.
    7
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    同族专利:
    公开号 | 公开日
    ES2646938B1|2018-09-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN102867967A|2011-07-05|2013-01-09|中国科学院大连化学物理研究所|Electrode material for all vanadium redox energy storage battery and application thereof|
    KR20160009408A|2014-07-16|2016-01-26|서울과학기술대학교 산학협력단|Catalyst for Vanadium Redox Flow Battery and Method for preparing the Same|CN113943158A|2021-12-20|2022-01-18|杭州德海艾科能源科技有限公司|Preparation method of graphite felt for flow battery|
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