An organic negative electrode material for hydrogen ion batteries

Abstract

The application discloses an organic negative electrode material for a hydrogen ion battery, which is prepared by the following steps: reacting 2,3-dichloronaphthoquinone with a sulfur source, refluxing the reaction in a solvent for 2-12 hours, filtering, collecting a filter cake and drying to obtain DTT; assembling the hydrogen ion battery by taking the DTT as an anode and taking MnO2 as a cathode in an acidic electrolyte. The application aims to solve the problems of high pollution, high electrode cost and short service life of the existing hydrogen ion battery.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of hydrogen ion batteries, and particularly relates to an organic negative electrode material for a hydrogen ion battery. BACKGROUND

[0002] Lithium ion batteries have occupied most of the power battery and energy storage markets due to the advantages of high energy density, high output power, long service life, light weight, small size, environmental friendliness and the like. However, in recent years, the high cost and safety problems of lithium ion batteries have gradually attracted people's attention. Therefore, developing an electrochemical energy storage device to replace lithium ion batteries has become a research hotspot at present. Aqueous hydronium battery has the advantages of safety and low cost, and is a promising alternative solution for large-scale energy storage technology. Therefore, aqueous batteries are considered to be a very promising alternative. Under the efforts of researchers at home and abroad, in recent years, aqueous batteries have made many breakthroughs, especially aqueous hydrogen ion batteries. For example, Prussian blue analog (CuFe-TBA) with large three-dimensional channels is selected as the anode of the proton battery, and MoO3 and WO3 with large channels are also matched with MnO2 electrodes, which show good reversible storage of protons. However, the specific capacity of these materials is also relatively low, less than 90 mAh g -1 . Relatively speaking, organic molecules have H+ insertion and weak intermolecular van der Waals forces that mask Coulomb repulsion, which can slow down solid-state diffusion, produce high specific capacity, structural diversity and economic friendliness. These characteristics make organic molecules a sustainable alternative to traditional inorganic electrode materials.

[0003] For example, the Houston, USA, Yao Yan research group (DOI: 10.1038 / NMAT4919) proposed a pyrene-4, 5, 9, 10-tetraone (PTO) as a negative electrode, and PbO2 as a positive electrode hydrogen ion battery. The battery can be relatively stably cycled for 1500 cycles. Subsequently, Wang Yonggang et al. (doi.org / 10.1038 / s41467-020-14748-5) of Fudan University proposed matching pyrene-4, 5, 9, 10-tetraone (PTO) with MnO2 electrode, and the battery showed an open-circuit voltage of 0.85V and could be relatively stably cycled for 5000 cycles in an acidic solution. However, overall, for large-scale energy storage systems, the long cycle stability is still slightly insufficient. In addition, the synthesis of PTO is obviously more complex, which is also not conducive to low-cost energy storage. SUMMARY

[0004] The purpose of the present application is to provide an organic negative electrode material for a hydrogen ion battery with low cost and long cycle stability.

[0005] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows: the use of an organic compound as a hydrogen ion battery negative electrode material, which has the following structure:

[0006]

[0007] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0008] (1) This invention uses a low-cost, scalably synthesized, S-coupled dibenzo[b,i]thiathanthracene-5,7,12,14-tetraone (DTT) as the negative electrode and inexpensive and readily available MnO2 as the positive electrode to assemble a hydrogen ion battery. Tests show that this hydrogen ion battery has a high open-circuit voltage and a proton storage capacity of up to 212 mAh g⁻¹. -1 Long-cycle test DTT at 3A g -1 At current densities, it can stably store and convert energy more than 4,000 times.

[0009] (2) A full cell of MnO2 / DTT can be produced at 2Ag -1 It can stably cycle more than 40,000 times at a current density, far exceeding any existing hydrogen-ion battery, demonstrating the potential application value of this battery in the field of large-scale energy conversion. Attached Figure Description

[0010] The accompanying drawings, which form part of this application, are used to provide a further understanding of the application and to make other features, objects, and advantages of the application more apparent. The illustrative embodiments and descriptions of this application are used to explain the application and do not constitute an undue limitation of the application. In the drawings:

[0011] Figure 1 This is the NMR spectrum of DTT.

[0012] Figure 2 This is the mass spectrum of DTT.

[0013] Figure 3 The cyclic voltammograms (a), rate curve (b), and long-cycle performance curve (c) of the DTT and MnO2 full cell are shown.

[0014] Figure 4 The graph shows the long-cycle performance of DTT and MnO2 full cells.

[0015] Figure 5 The graph shows the long-cycle performance of DTT and MnO2 full cells.

[0016] Figure 6 The graph shows the long-cycle performance of DTT and MnO2 full cells.

[0017] Figure 7 This is a schematic diagram of the full battery structure. Detailed Implementation

[0018] In order to make the person skilled in the art better understand the present application, the technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work should fall within the scope of protection of the present application.

[0019] It should be noted that the terms "preparation", "obtained", "matching", "assembly" should be understood broadly. For example, it can be directly obtained, or it can be obtained through multiple steps of intermediate media; it can be matched two by two between electrodes, or it can be matched through other electrochemical devices, or it can be multi-component matching between multiple electrode units; it can be integrally assembled, assembled between multiple unit electrochemical devices, or detachably assembled. For those skilled in the art, the specific meanings of the above terms in the present application can be understood according to the specific circumstances.

[0020] The dibenzo[b,i]thianthrene-5,7,12,14-tetraone involved in the present application is prepared by reacting 2,3-dichloronaphthoquinone with a sulfur source, refluxing in a solvent for 2-12 hours, then filtering, collecting the filter cake, and drying to obtain the dibenzo[b,i]thianthrene-5,7,12,14-tetraone.

[0021] As a preferred mode of the embodiment, the synthesized sulfur source includes one or more of inorganic sulfur sources S8, Na2S, NaHS, Na2S2O3, K2S, KHS, K2S2O3, NH4SCN, P2S5, one or more of organic sulfur sources CH3NS, CH3CSNH2 (TAA), CH4N2S, CH3SH, CH3CH2SH.

[0022] As a preferred mode of the embodiment, the solvent is one or more of commonly used solvents such as DMF, DMSO, H2O, THF, EA, etc.

[0023] DTT is mixed with conductive carbon and water-based binder in a certain proportion, dispersed in a low molecular alcohol, stirred uniformly, and the above nearly dry slurry is coated on the conductive current collector by rolling film method, then dried in an oven at 60°C for 12-24h to obtain a DTT electrode, i.e. a hydrogen ion battery negative electrode. The DTT electrode is assembled with a MnO2 electrode (positive electrode) in the same electrolyte pool, and relevant battery performance tests are carried out.

[0024] As a preferred mode of the embodiment, the mass ratio of DTT to conductive carbon and water-based binder is 8:1:1-6:3:1.

[0025] As a preferred mode of the embodiment, the low molecular alcohol is any one of ethanol, ethylene glycol, propylene glycol, isopropyl alcohol, glycerol, etc.

[0026] DTT used in the following examples was prepared by refluxing 2,3-dichloro-1,4- benzoquinone with Na2S in H2O under nitrogen atmosphere for 8 hours, then filtered with a large amount of water, and the filter cake was dried to obtain DTT. The spectrum of DTT is shown in Figure 1 and Figure 2 .

[0027] The MnO2 electrode used in the following examples was prepared by in-situ electrodeposition using a hydrophilic graphite felt (GF) carbon conductive substrate as the working electrode, a 2M H2SO4+2M MnSO4 solution as the electrolyte, and a graphite rod as the counter electrode. The MnO2@GF electrode was obtained by constant current oxidation of the Mn2+ solution at a current density of 10 mA cm -2 . 2+

[0028] The active MnO2 electrode was used as the positive electrode of the hydronium battery, and the DTT electrode was used as the negative electrode of the hydronium battery. The positive and negative electrodes were assembled in the same electrolyte pool to obtain a full battery structure. The structure is shown in Figure 7 , and the related battery performance tests were carried out.

[0029] Example 1

[0030] DTT was mixed with conductive carbon (ketjen black) and water-based binder (PTFE Hefei Kexing) at a mass ratio of 7:2:1, dispersed in ethanol, stirred uniformly, and then the nearly dry slurry was coated on the conductive current collector by rolling film to obtain the DTT electrode. Subsequently, the three-electrode measurement method was used, and the DTT electrode (negative electrode) and the MnO2 positive electrode were used as the working electrode, and the graphite was used as the counter electrode, and the Ag / AgCl was used as the reference electrode. The cyclic voltammogram of the working electrode was measured in 1M H2SO4 electrolyte at a scan rate of 0.5 mV s -1 . Figure 3

[0031] The MnO2 electrode and the DTT were immersed in 1M MnSO4+2M H2SO4 electrolyte, and the glass fiber membrane (Whatman, 110um) was used as the separator. Subsequently, the positive and negative electrode materials were connected by an external circuit and battery measurement was carried out. The rate performance diagram is shown in Figure 3 b.Subsequently, the constant current long cycle test was carried out at a current density of 2 Ag -1 .The measured results are shown in Figure 3 c.

[0032] Example 2

[0033] DTT was mixed with conductive carbon (Ketjen black), aqueous binder (PTFE Hefei crystal) in a mass ratio of 7:2:1, dispersed in ethanol, stirred uniformly, and then coated on the conductive current collector using a rolling film method to obtain a DTT electrode. The Mn02 electrode and the DTT were soaked in 2M MnS04+ 2M H2S04electrolyte, and a glass fiber membrane (Whatman, 110 um) was used as a separator. Subsequently, a constant current long cycle test was performed at a current density of 2 Ag -1 -1 Figure 4 .

[0034] Example 3

[0035] DTT was mixed with conductive carbon (Ketjen black), aqueous binder (PTFE Hefei crystal) in a mass ratio of 7:2:1, dispersed in ethanol, stirred uniformly, and then coated on the conductive current collector using a rolling film method to obtain a DTT electrode. The Mn02 electrode and the DTT were soaked in 1M Mn(Ac)2+ 1M HAc electrolyte, and a glass fiber membrane (Whatman, 110 um) was used as a separator. Subsequently, a constant current long cycle test was performed at a current density of 2 Ag -1 -1 Figure 5 .

[0036] Example 4

[0037] DTT was mixed with conductive carbon (Ketjen black), aqueous binder (PTFE Hefei crystal) in a mass ratio of 7:2:1, dispersed in ethanol, stirred uniformly, and then coated on the conductive current collector using a rolling film method to obtain a DTT electrode. The Mn02 electrode and the DTT were soaked in 1M MnS04+ 2M H2S04electrolyte, and a Nafion 212 membrane (DuPont) was used as a separator. Subsequently, a constant current long cycle test was performed at a current density of 2 Ag -1 -1 Figure 6 .

[0038] In summary, the present application proposes a hydronium battery based on an organic quinone dinaptho[b,i]thianthrene-5,7,12,14-tetraone (DTT) as an anode and Mn02 as a cathode in an acidic electrolyte. Its operation involves Mn02 / Mn 2+ conversion reactions in the cathode and quinone / hydroquinone redox reactions in the anode. The DTT anode can match the open-circuit voltage of Mn02 up to 0.9 V, and has unprecedented cycle stability at 2 Ag -1 -1

[0039] The above descriptions are only the preferred embodiments of the present application, and are not intended to limit the present application. The present application can have various modifications and changes for those skilled in the art. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A hydrogen-ion battery, characterized by, A hydrogen ion battery negative electrode is used as an anode, and a MnO2 electrode is used as a cathode in an acidic electrolyte, the hydrogen ion battery negative electrode is prepared by mixing an organic compound with conductive carbon and a water-based binder in a certain proportion, dispersing in a low molecular alcohol, stirring uniformly, using a rolling film method, coating the above nearly dry slurry on a conductive current collector, and then drying in an oven at 60°C for 12-24h, wherein the organic compound has the following structure:

2. The hydrogen ion battery of claim 1, wherein, The organic compound is mixed with conductive carbon and a water-based binder in a mass ratio of 8:1:1-6:3:

1.

3. The hydrogen ion battery of claim 1, wherein, The low molecular alcohol is any one of ethanol, ethylene glycol, propylene glycol, isopropyl alcohol, and glycerol.

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