CN111430735A - Nitrobenzene organic nonaqueous flow battery - Google Patents
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 125
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- -1 nitrobenzene compound Chemical class 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000012982 microporous membrane Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 7
- 150000005181 nitrobenzenes Chemical class 0.000 claims description 7
- 239000003115 supporting electrolyte Substances 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 229910018830 PO3H Inorganic materials 0.000 claims description 4
- 229910006069 SO3H Inorganic materials 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- LQNUZADURLCDLV-IDEBNGHGSA-N nitrobenzene Chemical group [O-][N+](=O)[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 LQNUZADURLCDLV-IDEBNGHGSA-N 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 10
- 239000013543 active substance Substances 0.000 abstract description 5
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 238000010248 power generation Methods 0.000 abstract description 3
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- MBIONSXAVAVHNN-UHFFFAOYSA-N 1,4-ditert-butyl-2-methoxy-5-(2-methoxyethoxy)benzene Chemical compound COCCOC1=CC(C(C)(C)C)=C(OC)C=C1C(C)(C)C MBIONSXAVAVHNN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 238000003860 storage Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 229940021013 electrolyte solution Drugs 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920001342 Bakelite® Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000004637 bakelite Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011263 electroactive material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention belongs to the field of electrochemical energy storage, and relates to a nitrobenzene organic nonaqueous flow battery. The novel organic nonaqueous flow battery is constructed by taking nitrobenzene molecules with high solubility, good electrochemical reversibility and chemical stability as a negative active substance and taking 2,5-di-tert-butyl-1-methoxy-4- [ 2' -methoxy-ethoxy ] benzene (DBMB) or other organic nonaqueous positive active substances. The battery has the advantages of low cost, high energy density, excellent battery performance and the like, and has wide application prospect in the fields of wind energy, photovoltaic and other renewable energy power generation, power grid peak regulation, frequency modulation and the like.
Description
Technical Field
The invention relates to the field of electrochemical energy storage, in particular to a nitrobenzene organic nonaqueous flow battery.
Background
In recent years, in order to solve the problems of energy shortage, environmental pollution, greenhouse effect and the like, renewable clean energy sources such as wind energy, tidal energy, solar energy and the like are vigorously developed in all countries in the world. However, the characteristics of the renewable energy sources such as intermittency, volatility and strong time variation can generate huge impact on the power grid, and further the further development and utilization of the new energy sources are hindered. Therefore, the development of a large-scale electricity storage system with low cost, high efficiency and reliability becomes an effective way to solve the problem. In the existing electricity storage technology, a redox flow battery is regarded as a solution to this problem. The flow battery is used as an energy storage device with low cost, safety and high efficiency, has the advantages of mutually independent capacity and power, good expandability, good safety, long cycle life, short response time and the like, can store wind energy, solar energy and the like at the peak value, and then releases the energy at the valley value, thereby providing possibility for the new energy technologies to be incorporated into an intelligent integrated power grid. A typical flow battery includes several major components: a liquid storage tank, a battery reactor and a peristaltic pump. The active substances of the flow battery are stored in the liquid storage tank, reach the battery stack through the driving of the pump, and generate oxidation-reduction reaction in the battery stack, and electrons flow to an external circuit through the current collector.
Currently, the flow battery systems studied mainly include inorganic aqueous flow systems such as all-vanadium flow batteries, zinc-bromine flow batteries, and iron-chromium flow batteries. However, there are few types of inorganic electroactive materials, and many inorganic elements such as vanadium and bromine are either low in solubility, expensive, or have a great environmental hazard. Compared with inorganic substances, the organic electroactive compounds can be selected from a wide variety, and have designability on the molecular structure, namely important properties such as potential, solubility, kinetic parameters and the like of electroactive substances can be regulated and controlled by adding functional groups. In addition, the main disadvantage of the inorganic aqueous fluid systems studied so far is the low open circuit voltage. The maximum voltage of such cells does not exceed 1.5V, limited by the decomposition voltage of water. Therefore, in recent years, more and more research is focused on developing nonaqueous organic electroactive molecules, wherein benzoquinone, TEMPO, phenazine and ferrocene organic active molecules are reported and show better electrochemical performance. However, the organic molecules reported at present have disadvantages of high synthesis cost and low energy density of the battery. The nitrobenzene electroactive molecules are used as cheap chemical synthesis raw materials, have the advantages of low production cost, proper oxidation-reduction potential, high solubility in organic solvents and the like, and have high potential utilization value. In addition, nitrobenzene electroactive materials are not reported as negative electrodes of organic flow batteries at present.
Disclosure of Invention
The invention provides a brand-new nitrobenzene organic non-aqueous liquid flow battery which has the advantages of low cost, high energy density and the like.
In order to achieve the purpose, the invention provides the following technical scheme:
a nitrobenzene organic nonaqueous flow battery is constructed by using electroactive nitrobenzene molecules as a negative active material and 2,5-di-tert-butyl-1-methoxy-4- [ 2' -methoxy-oxy ] bezene (DBMB) or other organic nonaqueous positive active materials, wherein the electrochemical performance of the organic nonaqueous flow battery is good.
The nitrobenzene organic nonaqueous flow battery takes a mixture of a positive active substance, a negative active substance, an organic solvent and a supporting electrolyte as an electrolyte, takes a polymer microporous membrane as a diaphragm, takes a porous carbon material as an electrode and takes a compact carbon material as a bipolar plate.
In the nitrobenzene organic non-aqueous flow battery, the negative active material is nitrobenzene compounds, the molecular structure of the nitrobenzene compounds contains nitrobenzene groups, and the structure is as follows:
wherein R is independently selected from-H, -OH and-CH3、-CHO、-Cl、-Br、-COOH、-SO3H、-PO3H、-COCH3、-NO2One or more than two of them.
According to the nitrobenzene organic non-aqueous flow battery, the nitrobenzene compounds are monocyclic nitrobenzene compounds or polyphenyl ring nitrobenzene compounds.
The organic solvent in the electrolyte of the nitrobenzene organic nonaqueous flow battery is Acetonitrile (AN), ethylene glycol dimethyl ether (DME), Propylene Carbonate (PC), Dichloromethane (DCM), dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (N: (N-methyl pyrrolidone)NMP) one or more than two; the supporting electrolyte is tetraethylammonium Tetrafluoroborate (TEABF)4) Tetrabutylammonium Tetrafluoroborate (TBABF)4) Lithium bistrifluoromethylsulfonyl imide (L iTFSI) and lithium perchlorate (L iClO)4) One or more than two of them.
The nitrobenzene organic nonaqueous flow battery is characterized in that the polymer microporous membrane is one of polypropylene (PP), Polyethylene (PE), Polystyrene (PS) and Polytetrafluoroethylene (PTFE), wherein the pore diameter of the polymer microporous membrane is 5-200 nm.
The nitrobenzene organic nonaqueous flow battery is characterized in that the porous carbon electrode is one of Carbon Felt (CF), Graphite Felt (GF), Carbon Cloth (CC) and Carbon Paper (CP), wherein the fiber diameter of the fiber is 1-20 mu m, and the porosity is 50-98%.
The compact carbon bipolar plate of the nitrobenzene organic non-aqueous flow battery is a graphite plate, a conductive plastic plate or a conductive rubber plate, the conductivity of the compact carbon bipolar plate is 50-800 mS/cm, and the bipolar plate is provided with or without a flow channel.
The design idea of the invention is as follows: although organic electroactive compounds have the advantages of wide selection of types, strong designability of molecular structures, high open-circuit voltage and the like, most organic molecules have higher synthesis cost and lower energy density. Therefore, the invention focuses on nitrobenzene electroactive molecules with low cost and high solubility, optimizes the electrochemical properties by designing the molecular structure of the nitrobenzene electroactive molecules, and further applies the nitrobenzene electroactive molecules to the field of energy storage of organic nonaqueous flow batteries.
The invention has the advantages and beneficial effects that:
the organic flow battery constructed based on the nitrobenzene has high theoretical energy density, long cycle life and high battery energy efficiency because the electroactive nitrobenzene electroactive substances have good electrochemical reversibility and stability and extremely high solubility. In addition, the nitrobenzene substances are used as basic raw materials for chemical synthesis, and have the characteristics of simple synthesis and low cost. The nitrobenzene organic nonaqueous flow battery has the characteristics of low synthesis cost, high energy density and the like, and has wide application prospects in the fields of wind energy, large-scale electricity storage of photovoltaic power generation and peak regulation of a power grid.
Drawings
FIG. 1 is a graph of the results of electrochemical measurements of the solutions prepared in example 1 of the present invention, using silver/silver nitrate as a reference electrode, and the redox potential results obtained at a sweep rate of 100 mV/s.
FIG. 2 is a plot of cyclic voltammetry versus nitrobenzene scan of example 1 after 200 cycles.
FIG. 3 is a cyclic voltammogram at different scan speeds for example 1.
FIG. 4 is a plot of peak current versus square root of scan rate for different scan rates of example 2.
FIG. 5 shows the flow battery of example 3 at different current densities of 20mA/cm2、30mA/cm2、40mA/cm2Current-capacity diagram in charge and discharge.
FIG. 6 shows the flow battery of example 4 at a constant current density of 30mA/cm2And selecting a charging and discharging voltage time chart from 11 th cycle to 17 th cycle in the charging and discharging cycle.
FIG. 7 shows the flow battery of example 4 at a constant current density of 30mA/cm2Charge-discharge cycle capacity retention and coulombic efficiency plots.
Detailed Description
In the specific implementation process, the nitrobenzene organic nonaqueous flow battery takes nitrobenzene electroactive molecules with high solubility, good electrochemical reversibility and chemical stability as a negative electrode electroactive substance, takes 2, 5-di-tert-butyl-1-method-4- [ 2' -methoxy ] bezene (DBMB) or a mixture of other organic nonaqueous positive electrode electroactive substances, an organic solvent and a supporting electrolyte as an electrolyte, takes a polymer microporous membrane as a diaphragm, takes a porous carbon material as an electrode and takes a compact carbon material as a bipolar plate. Therefore, a novel organic nonaqueous flow battery is constructed.
Among them, 2,5-di-tert-butyl-1-methoxy-4- [ 2' -methoxy ] benzene (DBMB) is available from Huang, J.; Cheng, L.; Assay, R.S.; Wang, P.; Xue, Z.; Burrell, A.K.; Curtiss, L. A.; Zhang, L. L, required catalyst Molecules for non-aqueous Redox FlowBatteries, adv.Energy Mater.2015,5,1401782.
The structure of the nitrobenzene electroactive molecule is as follows:
the electric active molecular structure of nitrobenzene contains the structural groups of nitrobenzene, and R is respectively selected from-H, -OH and-CH3、-CHO、-Cl、-Br、-COOH、-SO3H、-PO3H、-COCH3and-NO2One or more than two of; preferably, R is-H.
The nitrobenzene compounds can be monocyclic nitrobenzene compounds or multicyclic nitrobenzene compounds containing nitro groups (such as:
) (ii) a Preferably, the negative electrode is a monocyclic nitrobenzene compound. R is independently selected from-H, -OH and-CH3、-CHO、-Cl、-Br、-COOH、-SO3H、-PO3H、-COCH3and-NO2One or more than two of; preferably, R is-H.
The organic solvent in the electrolyte can be one or more than two of Acetonitrile (AN), ethylene glycol dimethyl ether (DME), Propylene Carbonate (PC), Dichloromethane (DCM), dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP); preferably, the organic solvent is Acetonitrile (AN).
The supporting electrolyte may be tetraethylammonium Tetrafluoroborate (TEABF)4) Tetrabutylammonium Tetrafluoroborate (TBABF)4) Lithium bistrifluoromethylsulfonyl imide (L iTFSI) and lithium perchlorate (L iClO)4) One or more than two of the above; preferably, the supporting electrolyte is tetraethylammonium Tetrafluoroborate (TEABF)4)。
The polymeric microporous membrane comprises: one of polypropylene (PP), Polyethylene (PE), Polystyrene (PS) and Polytetrafluoroethylene (PTFE), wherein the aperture of the polymer microporous membrane is between 5 and 200nm, the porosity of the polymer microporous membrane is between 41 and 57 percent, and the thickness of the polymer microporous membrane is between 25 and 900 microns; preferably, the polymeric microporous membrane is polypropylene (PP) having a pore size of about 64nm, a porosity of 55%, and a thickness of 135 μm.
The porous carbon electrode can be one of Carbon Felt (CF), Graphite Felt (GF), Carbon Cloth (CC) and Carbon Paper (CP), wherein the fiber diameter is about 1-20 mu m, and the porosity is 50-98%; preferably, the porous carbonaceous electrode is a graphite felt wherein the fibers have a filament diameter of about 10 μm and a density of about 1.39g/cm3The porosity was 93%.
The compact carbon bipolar plate can be a graphite plate, a conductive plastic plate or a conductive rubber plate, and the conductivity of the compact carbon bipolar plate is about 50-800 mS/cm; the bipolar plate can be provided with or without a flow channel; preferably, the compact carbon bipolar plate is a graphite plate engraved with flow channels, and the conductivity of the compact carbon bipolar plate is 320 mS/cm.
The operating principle of the nitrobenzene-based organic flow battery is as follows: during charging, the negative electrode reacts to obtain electrons for nitrobenzene negative electrode active molecules, a radical product with negative electricity in a reduction state is generated, and the positive electrode loses electrons to generate an oxidation state product. During discharging, the negative electrode reacts to a reduction state product and loses electrons to generate a nitrobenzene product, and an oxidation state product of the positive electrode obtains electrons and returns to the original state.
In the following, the technical solutions in the embodiments of the present application will be clearly and completely described with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. Therefore, the scope of the present invention is not limited to these examples.
Example 1
In this example, the preparation method of the nitrobenzene organic nonaqueous flow battery is as follows:
weighing and dissolving 2.56mg of nitrobenzene in 5 ml of 0.5 mol/L tetraethylammonium tetrafluoroborate anhydrous acetonitrile solution, oscillating and stirring to form a uniform solution, wherein the molar concentration of the uniform solution is 2 mmol/L, bubbling nitrogen for 10 minutes for later use, performing cyclic voltammetry on the prepared electrolyte by adopting a three-electrode system, taking silver/silver nitrate as a reference electrode, a platinum column electrode as a counter electrode, a glassy carbon electrode as a working electrode, and continuously scanning for 200 circles, wherein the scanning speed is 100 mV/s.
As can be seen from the cyclic voltammetry curve data in FIG. 1, nitrobenzene active molecules present a group of redox peaks with good reversibility, and the average half-wave potential of nitrobenzene is about-1.5V with silver/silver nitrate as a reference electrode, and has relatively negative potential. Secondly, when the cyclic voltammetry scanning is carried out on the electrolyte in fig. 2 for more than 200 circles, the peak potential of the oxidation-reduction peak is unchanged, and the graph is kept stable, which proves that the nitrobenzene electroactive molecule has good electrochemical stability.
Example 2
In this example, the preparation method of the nitrobenzene organic nonaqueous flow battery is as follows:
weighing and dissolving 2.56mg of nitrobenzene in 5m L0.5.5 mol/L tetraethylammonium tetrafluoroborate anhydrous acetonitrile solution, oscillating and stirring to form a uniform solution, wherein the molar concentration of the uniform solution is 2 mmol/L, and bubbling nitrogen for 10 minutes for later use, carrying out different sweep rate tests on the prepared electrolyte by adopting a three-electrode system, taking silver/silver nitrate as a reference electrode, a platinum column electrode as a counter electrode, a glassy carbon electrode as a working electrode, and the sweep rates are respectively 20mV/s, 50mV/s, 100mV/s, 200mV/s and 500 mV/s.
Fig. 3 and 4 show: linear fitting of the redox peak potential to the square root of the sweep rate at different sweep rates (20mV/s, 50mV/s, 100mV/s, 200mV/s, and 500mV/s) revealed that the data were linearly related, with a constant slope, further demonstrating that nitrobenzene is electrochemically reversible and that its oxidation and reduction reactions at the electrodes are diffusion controlled.
Example 3
In this example, the preparation method of the nitrobenzene organic nonaqueous flow battery is as follows:
123mg of nitrobenzene is weighed and dissolved in 20m L0.5.5 mol/L tetraethylammonium tetrafluoroborate anhydrous acetonitrile solution, the molar concentration of which is 0.05 mol/L, and the mixture is stirred with shaking to form a uniform solution, then 290mg of positive active material 2,5-di-tert-butyl-1-methoxy-4- [ 2' -methoxy ] benzene (DBMB) is weighed and added into the solution, and the solution is stirred with shaking to form a uniform solution for standby, and in the 20m L mixed electrolyte solution, the molar concentrations of the positive electrode and the negative electrode are respectively 0.05 mol/L.
Then assembling the battery according to a conventional method, namely stacking a first bakelite plate, a first aluminum end plate, a first gold-plated copper current collecting plate, a first graphite plate, a first electrode, a first polytetrafluoroethylene gasket, a first polymer microporous membrane diaphragm, a second polytetrafluoroethylene gasket, a second electrode, a second graphite plate, a second gold-plated copper current collecting plate, a second aluminum end plate and a second bakelite plate in sequence, fastening and assembling to construct a sandwich-shaped flow battery structure, dividing the prepared 20m L mixed electrolyte solution into 2 parts (each 10m L) with equal amount, respectively injecting the two parts into two closed storage tanks, then connecting the inlet and the outlet of each storage tank with a liquid flow pump and the inlet and the outlet of the anode and cathode flow fields of the battery, driving the electrolyte solutions to respectively flow circularly by using a peristaltic pump, controlling the flow at 40m L/min, and then testing the charging and discharging performance of the battery by adopting the current density of 20mA/cm2、30mA/cm2、40mA/cm2And performing charge and discharge tests on the sample.
FIG. 5 shows that: under different current densities, the nitrobenzene negative active molecule respectively presents a charging platform near 2.2V and a discharging platform near 2.1V, and the nitrobenzene-based flow battery has good rate performance: at a current density of 40mA/cm2Still reach 50% active molecule utilization ratio under the condition of (1); FIG. 6 shows that: the charge and discharge curves of the battery exhibited good reproducibility over 5 cycles. The good charge-discharge stability of the nitrobenzene negative electrode molecule is proved.
Example 4
In this example, the preparation method of the nitrobenzene organic nonaqueous flow battery is as follows:
123mg of nitrobenzene is weighed and dissolved in 20m L0.5.5 mol/L tetraethylammonium tetrafluoroborate anhydrous acetonitrile solution with the molar concentration of 0.05 mol/L in a glove box, and the mixture is stirred with shaking to form a uniform solution, then 290mg of positive active material 2,5-di-tert-butyl-1-methoxy-4- [ 2' -methoxy ] benzene (DBMB) is weighed and added into the solution, and the solution is stirred with shaking to form a uniform solution, and in the 20m L mixed electrolyte solution, the molar concentrations of the positive electrode and the negative electrode are respectively 0.05 mol/L.
Then, assembling the battery according to a conventional method, namely, stacking a first bakelite plate, a first aluminum end plate, a first gold-plated copper current collecting plate, a first graphite plate, a first electrode, a first polytetrafluoroethylene gasket, a first polymer microporous membrane diaphragm, a second polytetrafluoroethylene gasket, a second electrode, a second graphite plate, a second gold-plated copper current collecting plate, a second aluminum end plate and a second bakelite plate in sequence, fastening and assembling to construct a sandwich-shaped flow battery structure, dividing the prepared 20m L mixed electrolyte solution into 2 parts (10 m L respectively) with equal quantity, respectively injecting the two parts into two closed storage tanks, then connecting the inlet and the outlet of each storage tank with a liquid flow pump and the inlet and the outlet of a positive and negative flow field of the battery, driving the electrolyte solution to respectively flow circularly by using a peristaltic pump, controlling the flow at 40m L/min, and then adopting a constant current density of 30mA/cm2And performing charge and discharge tests on the sample.
FIG. 7 shows that: at a constant current density of 30mA/cm2The coulombic efficiency of the battery is more than 90 percent under the condition of charging and discharging for 40 circles, and the average capacity retention rate of each charging and discharging cycle is 99 percent, which shows that the battery has good electrochemical cycle performance.
Example 5
In the embodiment, when the nitrobenzene electroactive molecule with good electrochemical reversibility and chemical stability is used as the cathode electroactive substance, the application of the nitrobenzene electroactive molecule is not limited to the flow battery, and the nitrobenzene electroactive molecule can also be used in the field of electric fuels (E-fuel); in the application of the electric fuel field, a polymer microporous membrane with thicker thickness and smaller porosity is adopted for charging, and low-current charging is carried out, so that the coulomb efficiency is improved; during discharging, the polymer microporous membrane with smaller thickness and larger porosity is used for large-current charging, so that the energy efficiency of the battery is improved. Therefore, the total coulombic and energy efficiency can be respectively improved by 2-3%, wherein the coulombic efficiency can reach 96-97%, and the energy efficiency can reach 75-78%.
The embodiment result shows that the flow battery has the advantages of low cost, high energy density, excellent battery performance and the like, and has wide application prospects in the fields of wind energy, photovoltaic and other renewable energy power generation, power grid peak regulation, frequency modulation and the like as an energy storage battery.
Claims (8)
1. A nitrobenzene organic nonaqueous flow battery is characterized in that an organic nonaqueous flow battery with good electrochemical performance is constructed by taking electroactive nitrobenzene molecules as a negative electrode active material and 2,5-di-tert-butyl-1-methoxy-4- [ 2' -methoxy-oxy ] benzene (DBMB) or other organic nonaqueous positive electrode active materials.
2. The nitrobenzene organic nonaqueous flow battery according to claim 1, wherein a mixture of a positive electrode active material, a negative electrode active material, an organic solvent and a supporting electrolyte is used as an electrolyte solution, a polymer microporous membrane is used as a separator, a porous carbon material is used as an electrode, and a dense carbon material is used as a bipolar plate.
3. The nitrobenzene organic nonaqueous flow battery according to claim 1, wherein the negative electrode active material is a nitrobenzene compound, and each of the nitrobenzene compounds has a molecular structure comprising nitrobenzene groups, and the structure is as follows:
wherein R is independently selected from-H, -OH and-CH3、-CHO、-Cl、-Br、-COOH、-SO3H、-PO3H、-COCH3、-NO2One or more than two of them.
4. The nitrobenzene organic nonaqueous flow battery according to claim 3, wherein the nitrobenzene compound is a monocyclic nitrobenzene compound or a polyphenyl nitrobenzene compound.
5. The nitrobenzene organic nonaqueous flow battery according to claim 2, wherein the organic solvent in the electrolyte is Acetonitrile (AN) or acetonitrile (B)One or more of dimethyl ether glycol (DME), Propylene Carbonate (PC), Dichloromethane (DCM), dimethyl sulfoxide (DMSO) and N-methylpyrrolidone (NMP); the supporting electrolyte is tetraethylammonium Tetrafluoroborate (TEABF)4) Tetrabutylammonium Tetrafluoroborate (TBABF)4) Lithium bistrifluoromethylsulfonyl imide (L iTFSI) and lithium perchlorate (L iClO)4) One or more than two of them.
6. The nitrobenzene organic nonaqueous flow battery according to claim 2, wherein the polymer microporous membrane is one of polypropylene (PP), Polyethylene (PE), Polystyrene (PS) and Polytetrafluoroethylene (PTFE), wherein the pore diameter of the polymer microporous membrane is between 5 and 200 nm.
7. The nitrobenzene organic nonaqueous liquid flow battery according to claim 2, wherein the porous carbon-based electrode is one of a Carbon Felt (CF), a Graphite Felt (GF), a Carbon Cloth (CC) and a Carbon Paper (CP), wherein the fiber has a filament diameter of 1 to 20 μm and a porosity of 50 to 98%.
8. The nitrobenzene organic nonaqueous flow battery according to claim 2, wherein the dense carbon bipolar plate is a graphite plate, a conductive plastic plate or a conductive rubber plate, the conductivity of the dense carbon bipolar plate is 50-800 mS/cm, and the bipolar plate is provided with or without a flow channel.
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| US20160208030A1 (en) * | 2015-01-16 | 2016-07-21 | The Board Of Trustees Of The University Of Illinois | Redox active polymers and colloidal particles for flow batteries |
| CN106532094A (en) * | 2015-09-11 | 2017-03-22 | 中科派思储能技术有限公司 | Lithium-sulfur flow battery |
| CN110265694A (en) * | 2019-05-29 | 2019-09-20 | 西安交通大学 | One kind is talked endlessly pyridine class water system organic oxidation reducing solution galvanic battery |
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| US20160208030A1 (en) * | 2015-01-16 | 2016-07-21 | The Board Of Trustees Of The University Of Illinois | Redox active polymers and colloidal particles for flow batteries |
| CN106532094A (en) * | 2015-09-11 | 2017-03-22 | 中科派思储能技术有限公司 | Lithium-sulfur flow battery |
| CN110265694A (en) * | 2019-05-29 | 2019-09-20 | 西安交通大学 | One kind is talked endlessly pyridine class water system organic oxidation reducing solution galvanic battery |
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Application publication date: 20200717 |