CN112864437B - Iron-lead single flow battery and preparation method thereof - Google Patents
Iron-lead single flow battery and preparation method thereof Download PDFInfo
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- CN112864437B CN112864437B CN202110097724.2A CN202110097724A CN112864437B CN 112864437 B CN112864437 B CN 112864437B CN 202110097724 A CN202110097724 A CN 202110097724A CN 112864437 B CN112864437 B CN 112864437B
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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
- 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
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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
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- 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
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Abstract
The invention provides an iron-lead single flow battery and a preparation method thereof, wherein the battery comprises an iron-lead single flow battery structure, and the iron-lead single flow battery structure comprises a negative electrode material layer, an ion selective permeation membrane and a positive electrode material layer which are sequentially arranged; and the negative electrode material layer is filled with negative electrolyte, the positive electrode material layer is filled with positive electrolyte, and the positive electrolyte circularly flows in the positive electrode material layer. According to the invention, the all-solid-state lead negative electrode and the soluble iron salt positive electrode are combined into the single flow battery for the first time, so that the generation of lead crystal branches is effectively avoided, and the battery performance is obviously improved.
Description
Technical Field
The invention relates to the technical field of flow batteries, in particular to an iron-lead single flow battery and a preparation method thereof.
Background
With the increasing prominence of environmental problems and energy problems, the demand of clean renewable energy sources is increasing. Batteries are receiving increasing attention as one of energy storage technologies in new energy utilization. The flow battery is a novel battery technology, has the advantages of long service life, safety, environmental protection, capacity and power independent design, deep charge and discharge and the like compared with the conventional batteries such as lead-acid batteries and lithium batteries, and is particularly suitable for large-scale energy storage. In the existing flow battery technology, the all-vanadium flow battery is taken as a typical representative, and the performance index of the all-vanadium flow battery already meets the application requirement. However, the vanadium element is used as the energy storage active material in the all-vanadium redox flow battery, the positive electrode adopts the solution of tetravalent vanadium ions and pentavalent vanadium ions as the energy storage material, and the negative electrode adopts the solution of trivalent vanadium and divalent vanadium ions as the energy storage material. The vanadium resource reserves are not abundant enough and the cost is high, so that the cost of the all-vanadium redox flow battery is low, and the problem becomes a bottleneck problem in large-scale application. In order to solve the cost problem, scientists and engineers have focused on the use of inexpensive metal elements as energy storage materials, such as all-iron flow batteries and all-lead flow batteries (Journal of the Electrochemical Society,1987,134(12): 3083-9). The cathode of the all-iron flow battery adopts metallic iron and ferrous ion solution as energy storage substances, and the anode adopts ferrous ion and ferric ion solution as energy storage substances. However, The negative electrode of The all-iron flow battery generates a large amount of hydrogen evolution reaction during charging, which causes The problems of irreversible charging and discharging reaction, low energy conversion efficiency, and The like, and always hinders The practical application of The all-iron flow battery (Journal of The Electrochemical Society,2014,161(10): A1662-A71). All-lead flow batteries use lead as an energy storage material, in which a divalent soluble lead salt (such as lead methanesulfonate) undergoes a redox reaction with metallic lead at the negative electrode and is oxidized to lead peroxide at the positive electrode. Although an all-lead flow battery can adopt cheap lead as an energy storage element, the all-lead flow battery currently has two technical problems, so that the all-lead flow battery cannot be practically applied: 1) negative dendrite problems. The reduction reaction of the negative electrode is that soluble divalent lead salt solution is reduced to metallic lead simple substance, and the metallic lead generates dendrite towards the positive electrode in the reduction process, so that the internal battery is short-circuited. 2) The lead peroxide of the positive electrode falls off. Lead peroxide generated in the positive electrode is easily separated from the electrode, and the performance of the battery is seriously influenced (Journal of Energy Storage 15(2018) 69-90). In a traditional lead-acid battery, positive and negative electrodes all use a solid lead-containing substance which is insoluble in an electrolyte as an active substance. The negative electrode is the oxidation-reduction reaction of lead sulfate and lead, and the positive electrode is the oxidation-reduction reaction of lead sulfate and lead peroxide. However, a common problem of lead-acid batteries is that during charging and discharging, the negative electrode generates irreversible lead sulfate crystals to cause obvious capacity reduction, the cycle life is short, and the service life requirement of large-scale energy storage cannot be met. In addition, lead-acid batteries have a low charge-discharge rate, which is generally less than 0.2C for a long time. Only Zhao et al have proposed the concept of an iron-lead flow battery (Journal of Power Sources 346(2017) 97-102): the negative electrode utilizes the oxidation-reduction reaction between soluble divalent lead salt solution and metallic lead, and the positive electrode utilizes soluble divalent ferric salt and trivalent ferric salt as energy storage substances, so that the battery has two problems: 1) because the negative electrode is the metal lead generated by reduction in a soluble lead salt solution, the generation of lead dendrite cannot be avoided in the prior art, and the problem of internal short circuit risk exists; 2) the theoretical voltage of the battery is only 0.9V, and the voltage is lower. Therefore, the value of practical use is lacking.
In summary, the conventional flow batteries, including a full flow battery (the active energy storage material circulates on two electrodes) and a single flow battery (the active energy storage material circulates on one electrode), all have the problems of cost or performance at present, so that there is an urgent need to develop a large-scale energy storage battery with low cost and performance capable of meeting the energy storage requirement, so as to meet the requirement of using clean and renewable energy.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an iron-lead single flow battery and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
the invention provides an iron-lead single flow battery structure, which comprises a negative electrode material layer, an ion selective permeation membrane and a positive electrode material layer which are sequentially arranged; the negative electrode material layer is filled with negative electrolyte, the positive electrode material layer is filled with positive electrolyte, and the positive electrolyte circularly flows in the positive electrode material layer;
the negative electrode material layer comprises two or three components of a lead simple substance, a solid divalent lead salt and a conductive agent;
the negative electrode electrolyte is an inorganic acid aqueous solution;
the positive electrode material layer is a porous carbon electrode layer;
the positive electrolyte comprises a mixed aqueous solution formed by a ferric salt solution, a ferrous salt and an inorganic acid.
Preferably, additives such as bismuth oxide, barium sulfate, humic acid, gallium oxide, indium oxide, and the like, but not limited thereto, may also be added to the negative electrode material layer;
additives such as methanesulfonic acid, magnesium sulfate, sodium fluoride, and the like may also be added to the negative electrode electrolyte, but are not limited thereto.
Additives such as ammonium sulfate, ammonium chloride, potassium sulfate, potassium chloride, and the like may be further added to the positive electrolyte, but not limited thereto.
Preferably, the solid divalent lead salt is one or two of lead sulfate and lead chloride;
the conductive agent is one or a combination of more of conductive carbon black, graphene, carbon powder, carbon nano tubes, carbon fibers and copper.
Preferably, in the negative electrode material layer, the total mass of the lead simple substance and the solid divalent lead salt is 20-100% of the mass of the electrode material layer, more preferably in the range of 50-95%, and most preferably in the range of 65-85%.
More preferably, in the negative electrode material layer, the mass percentage of the conductive agent is 2-35%.
Preferably, the solid divalent lead salt is selected from lead sulfate and lead chloride.
Preferably, the negative electrode material layer further contains a binder.
Preferably, the thickness of the negative electrode material layer is 0.5-20mm, more preferably 1-5mm, and most preferably 1.5-3 mm; the negative electrode material layer is a porous solid electrode, the pores are open pores, electrolyte can enter the inside of the electrode, and the porosity is 10-80%, and more preferably 30-60%.
Preferably, the porous carbon electrode layer is one or a combination of a plurality of carbon felts, carbon papers, carbon cloths and porous carbon plates;
the ferrous salt is one or the combination of two of ferrous sulfate and ferrous chloride, and the ferric salt is one or the combination of two of ferric sulfate and ferric chloride;
the inorganic acid is one or the combination of two of sulfuric acid or hydrochloric acid;
the ion selective membrane is one or a combination of more of an ion exchange resin membrane, a porous polymer membrane and a swelling polymer membrane; the ion permselective membrane is arranged between the anode and the cathode, is used for separating electrolytes of the anode and the cathode to prevent series flow, and has the function of conducting protons to balance ions between the anode and the cathode so that charge-discharge reaction can be continuously carried out.
Preferably, the mass fraction of the inorganic acid aqueous solution is 3-20%.
The charge-discharge reaction of the cathode formed by the cathode material layer and the cathode electrolyte adopted by the invention is the oxidation-reduction reaction of lead simple substance and lead sulfate, and the reaction equation is as follows:
or the charge-discharge reaction of the negative electrode is lead simple substance and lead chlorideThe reaction equation is as follows:
the charge-discharge reaction of the anode formed by the anode material layer and the anode electrolyte is the oxidation-reduction reaction of a ferric iron salt solution and a ferrous iron salt, and the reaction equation is as follows:
the charge-discharge reaction of the iron-lead single flow battery structure is as follows:
the invention also provides an iron-lead single flow battery, which comprises the iron-lead single flow battery structure, and further comprises a positive plate, a positive plate frame, a negative plate frame and an end plate;
the negative plate is arranged on the outer side of the negative material layer, the positive plate is arranged on the outer side of the positive material layer, and end plates are respectively arranged on the outer sides of the negative plate and the positive plate;
a negative plate frame is arranged around the negative material layer, and a positive plate frame is arranged around the positive material layer;
and the anode plate frame is provided with a pipeline, and the other end of the pipeline is communicated with the anode electrolyte storage tank.
Preferably, a circulating pump is arranged on the pipeline;
the positive plate and the negative plate are both prepared from metal or carbon materials;
a channel for supplementing cathode electrolyte and exhausting is arranged on the cathode plate frame;
current collecting plates are arranged between the positive plate and the end plate and between the negative plate and the end plate; the collector plate is made of metal or carbon material.
Preferably, the current collecting plate and the positive plate, and the current collecting plate and the negative plate may be respectively a whole; or the positive plate frame and the positive plate, and the negative plate frame and the negative plate can be respectively integrated; or the current collecting plate, the positive plate frame and the positive plate can be integrated with the current collecting plate, the negative plate frame and the negative plate respectively.
The invention also provides an iron-lead single flow battery stack which is formed by the iron-lead single flow battery structure in a series connection and/or parallel connection mode.
Preferably, when the iron-lead single flow battery structure is formed in a series connection mode, the iron-lead single flow battery structure further comprises a positive plate, a positive plate frame, a negative plate frame, a bipolar plate and an end plate;
bipolar plates are arranged among the iron-lead single flow battery structures, the negative plate is arranged on the outer side of the negative material layer on the outermost side, the positive plate is arranged on the outer side of the positive material layer on the outermost side, and end plates are respectively arranged on the outer sides of the negative plate and the positive plate; a negative plate frame is arranged on the periphery of the negative material layer, and a positive plate frame is arranged on the periphery of the positive material layer; the anode plate frame is provided with a pipeline, and the other end of the pipeline is communicated with the anode electrolyte storage tank;
when the iron-lead single flow battery structure is formed in a parallel connection mode, every two anodes share one cathode; the specific structural unit comprises a positive electrode material layer, an ion selective permeable membrane, a negative electrode material layer, an ion selective permeable membrane and a positive electrode material layer which are sequentially arranged; the positive plate and the end plate are sequentially arranged outside the positive material layers on the two sides; the negative plate, the channel that is used for replenishing negative pole electrolyte and exhaust are provided with respectively on the negative plate frame, be provided with the pipeline on the positive plate frame, the anodal electrolyte storage pot is communicate to the pipeline other end.
Preferably, when the iron-lead single flow battery structure is formed in a parallel connection mode, a current collecting plate is further arranged between the positive plate and the end plate.
Although the present invention is directed to a battery, the positive and negative reaction principles are not first discovered and applied. However, the invention provides the single flow battery by combining the all-solid-state lead negative electrode and the soluble ferric salt positive electrode for the first time, and the problem of dendritic crystal growth in the reduction process of the soluble lead salt of the negative electrode can be effectively solved; in order to improve the performance of the battery, a great deal of experiments and improvements are carried out on the composition and the structure of the negative electrode, for example, the rate performance and the capacity of the negative electrode are obviously improved through the unique design of the porous 3D electrode and the innovative design and optimization of the composition of the negative electrode material, and the charge and discharge stability is also obviously improved. Meanwhile, the problem of rapid capacity reduction caused by the continuous and obvious formation of irreversible lead sulfate crystals in the oxidation reduction process between the solid divalent lead salt and the metallic lead is solved. The high performance low cost energy storage cells of the present invention cannot be obtained by simple recombination of existing cell technologies. For example, a negative electrode of a commercial lead-acid battery [ a negative electrode, sponge-shaped fiber active substances (solid divalent lead salt and metallic lead) are coated on a lead-antimony-calcium alloy grid ] and a positive electrode (soluble divalent iron salt and trivalent iron salt) of an all-iron flow battery are assembled into a single flow battery according to the battery structure, and test results show that the capacity of the battery is reduced by more than 30% after 10 times of charge and discharge, so that the battery cannot meet the application requirements.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention combines the all-solid-state lead negative electrode and the soluble ferric salt positive electrode into the single flow battery for the first time, thereby effectively avoiding the generation of lead crystal branches.
2) The theoretical voltage of the iron-lead single flow battery prepared by the invention can reach as high as: 1.13V; after 300 cycles of charging and discharging, no obvious dendrite is generated on the negative electrode.
3) The iron-lead single flow battery prepared by the invention has the advantages that the current efficiency can reach more than 99% and the energy efficiency can reach more than 90% under the multiplying power of 0.5C; under the multiplying power of 3C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach 80 percent; the capacity fade may be less than 2% after 100 charge and discharge cycles.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
fig. 1 is an iron-lead single flow battery structure of example 1 of the present invention;
fig. 2 is an iron-lead single flow battery structure of example 2 of the invention;
fig. 3 is an iron-lead single flow battery stack structure of example 3 of the present invention;
fig. 4 is an iron-lead single flow battery stack structure of example 4 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The embodiment provides an iron-lead single flow battery, as shown in fig. 1, which includes an iron-lead single flow battery structure, and further includes a positive plate, a positive plate frame, a negative plate frame, a current collecting plate, and an end plate;
the iron-lead single flow battery structure comprises a negative electrode material layer, an ion selective permeation membrane and a positive electrode material layer which are sequentially arranged; the negative electrode material layer is filled with negative electrode electrolyte, the positive electrode material layer is filled with positive electrode electrolyte, and the positive electrode electrolyte circularly flows in the positive electrode material layer;
the negative electrode material layer consists of 60% of metallic lead, 25% of lead sulfate and 15% of acetylene black in parts by mass;
the negative electrode electrolyte is an aqueous solution of sulfuric acid, and the mass fraction of the sulfuric acid is 10%;
the positive electrode material layer is a porous carbon electrode layer, in particular a graphite felt;
the positive electrolyte is a mixed aqueous solution formed by ferric sulfate, ferrous sulfate and sulfuric acid (the mass ratio is 1:8: 1).
The ion selective membrane is a perfluorosulfonic acid membrane;
the thickness of the negative electrode material layer is 1.5mm, the negative electrode material layer is a porous solid electrode material layer, holes are open holes, electrolyte can enter the inside of the electrode, and the porosity is 50%.
The negative plate is arranged on the outer side of the negative material layer, the positive plate is arranged on the outer side of the positive material layer, and the collector plate and the end plate are respectively arranged on the outer sides of the negative plate and the positive plate in sequence;
a negative plate frame is arranged on the outer side of the negative material layer, and a positive plate frame is arranged on the outer side of the positive material layer;
and the anode plate frame is provided with a pipeline, and the other end of the pipeline is communicated with the anode electrolyte storage tank.
A circulating pump is arranged on the pipeline;
the collector plate is made of a copper plate, and the positive plate and the negative plate are made of graphite materials;
and a channel for supplementing the negative electrolyte and exhausting is arranged on the negative plate frame.
The theoretical voltage of the cell prepared in this example is: 1.13V; after 300 cycles of charging and discharging, no obvious dendritic crystal is generated at the negative electrode; under the multiplying power of 0.5C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach more than 90 percent; under the multiplying power of 3C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach 80 percent; the capacity fade may be less than 2% after 100 charge and discharge cycles.
Example 2
This example provides an iron-lead single flow battery, as shown in fig. 2, which is different from example 1 only in that the negative plate frame is not provided with channels for replenishing the negative electrolyte and exhausting air, and the negative electrolyte is added to the negative filler layer in advance during assembly.
The performance of the battery prepared in this example was similar to that of example 1.
Example 3
The present embodiment provides an iron-lead single flow battery stack, as shown in fig. 3. By adopting the iron-lead single flow battery structure in embodiment 1, a bipolar plate is arranged between each iron-lead single flow battery structure, the negative plate is arranged outside the negative electrode material layer on the outermost side, the positive plate is arranged outside the positive electrode material layer on the outermost side, and a current collecting plate and an end plate are sequentially arranged outside the negative plate and the positive plate respectively; the upper end and the lower end of the negative electrode material layer are provided with negative electrode plate frames, and the upper end and the lower end of the positive electrode material layer are provided with positive electrode plate frames; the anode plate frame is provided with a pipeline, and the other end of the pipeline is communicated with the anode electrolyte storage tank;
a circulating pump is arranged on the pipeline;
the collector plate is made of a copper plate, and the positive plate and the negative plate are made of graphite;
and a channel for supplementing the negative electrolyte and exhausting is arranged on the negative plate frame.
The theoretical voltage of the battery stack obtained in the embodiment is the sum of theoretical voltages of a plurality of single batteries, and other performances are similar to those of the embodiment 1.
Example 4
The present embodiment provides an iron-lead single flow battery stack, as shown in fig. 4, in which every two positive electrodes share a negative electrode; the specific structural unit comprises a positive electrode material layer, an ion selective permeable membrane, a negative electrode material layer, an ion selective permeable membrane and a positive electrode material layer which are sequentially arranged (the specific materials adopted by each layer are the same as those adopted in the embodiment 1); the positive plate, the current collecting plate and the end plate are sequentially arranged outside the positive material layers on the two sides; a negative plate and a channel for supplementing negative electrolyte and exhausting gas are respectively arranged on the negative plate frame, a pipeline is arranged on the positive plate frame, and the other end of the pipeline is communicated with the positive electrolyte storage tank;
a circulating pump is arranged on the pipeline;
the collector plate is made of a copper plate, and the positive plate and the negative plate are made of graphite;
and a channel for supplementing the negative electrolyte and exhausting is arranged on the negative plate frame.
The theoretical voltage of the cell stack obtained in the embodiment is the same as the theoretical voltage of a single cell, the current is the sum of the currents of a plurality of single cells, and other performances are similar to those of the embodiment 1.
Example 5
The embodiment provides an iron-lead single flow battery, as shown in fig. 1, which includes an iron-lead single flow battery structure, and further includes a positive plate, a positive plate frame, a negative plate frame, a current collecting plate, and an end plate;
the iron-lead single flow battery structure comprises a negative electrode material layer, an ion selective permeation membrane and a positive electrode material layer which are sequentially arranged; the negative electrode material layer is filled with negative electrode electrolyte, the positive electrode material layer is filled with positive electrode electrolyte, and the positive electrode electrolyte circularly flows in the positive electrode material layer;
the negative electrode material layer consists of 60% of metallic lead, 20% of lead sulfate and 20% of graphite powder in percentage by mass;
the negative electrolyte is an aqueous solution of sulfuric acid, and the mass fraction of the sulfuric acid is 5%;
the positive electrode material layer is a porous carbon electrode layer, in particular a graphite felt;
the positive electrolyte is a mixed aqueous solution formed by ferric sulfate, ferrous sulfate and sulfuric acid (the mass ratio is 4:5: 1).
The ion selective membrane is a perfluorosulfonic acid membrane;
the thickness of the negative electrode material layer is 0.5mm, the negative electrode material layer is a porous solid electrode, the pores are open pores, electrolyte can enter the inside of the electrode, and the porosity is 10%.
The negative plate is arranged on the outer side of the negative material layer, the positive plate is arranged on the outer side of the positive material layer, and the collector plate and the end plate are respectively arranged on the outer sides of the negative plate and the positive plate in sequence;
a negative plate frame is arranged on the outer side of the negative material layer, and a positive plate frame is arranged on the outer side of the positive material layer;
and the anode plate frame is provided with a pipeline, and the other end of the pipeline is communicated with the anode electrolyte storage tank.
Preferably, a circulating pump is arranged on the pipeline;
the collector plate is made of a copper plate, and the positive plate and the negative plate are made of graphite materials;
and a channel for supplementing the negative electrolyte and exhausting is arranged on the negative plate frame.
The theoretical voltage of the cell prepared in this example is: 1.13V; after 300 cycles of charging and discharging, no obvious dendritic crystal is generated at the negative electrode; under the multiplying power of 0.5C, the current efficiency can reach more than 97%, and the energy efficiency can reach more than 85%; under the multiplying power of 3C, the current efficiency can reach more than 98%, and the energy efficiency can reach 81%; the capacity fade may be less than 3% after 100 charge and discharge cycles.
Example 6
The embodiment provides an iron-lead single flow battery, as shown in fig. 1, which includes an iron-lead single flow battery structure, and further includes a positive plate, a positive plate frame, a negative plate frame, and an end plate;
the iron-lead single flow battery structure comprises a negative electrode material layer, an ion selective permeation membrane and a positive electrode material layer which are sequentially arranged; the negative electrode material layer is filled with negative electrode electrolyte, the positive electrode material layer is filled with positive electrode electrolyte, and the positive electrode electrolyte circularly flows in the positive electrode material layer;
the negative electrode material layer consists of 70% of metallic lead, 28% of lead sulfate and 2% of carbon nano tubes in percentage by mass;
the negative electrode electrolyte is an aqueous solution of sulfuric acid, and the mass fraction of the sulfuric acid is 3%;
the positive electrode material layer is a porous carbon electrode layer, specifically carbon paper;
the positive electrolyte is a mixed aqueous solution formed by ferric sulfate, ferrous sulfate and sulfuric acid (the mass ratio is 2:7: 1).
The ion selective membrane is a perfluorosulfonic acid membrane;
the thickness of the negative electrode material layer is 20mm, the negative electrode material layer is a porous solid electrode, the holes are open holes, electrolyte can enter the inside of the electrode, and the porosity is 80%.
The negative plate is arranged on the outer side of the negative material layer, the positive plate is arranged on the outer side of the positive material layer, and the collector plate and the end plate are respectively arranged on the outer sides of the negative plate and the positive plate in sequence;
a negative plate frame is arranged on the outer side of the negative material layer, and a positive plate frame is arranged on the outer side of the positive material layer;
and the anode plate frame is provided with a pipeline, and the other end of the pipeline is communicated with the anode electrolyte storage tank.
Preferably, a circulating pump is arranged on the pipeline;
the positive plate and the negative plate are both prepared from graphite materials;
and a channel for supplementing the negative electrolyte and exhausting is arranged on the negative plate frame.
The theoretical voltage of the cell prepared in this example is: 1.13V; after 300 cycles of charging and discharging, no obvious dendritic crystal is generated at the negative electrode; under the multiplying power of 0.5C, the current efficiency can reach more than 97%, and the energy efficiency can reach more than 86%; under the multiplying power of 3C, the current efficiency can reach more than 98 percent, and the energy efficiency can reach 83 percent; the capacity fade may be less than 2.8% after 100 charge and discharge cycles.
Example 7
The embodiment provides an iron-lead single flow battery, as shown in fig. 1, which includes an iron-lead single flow battery structure, and further includes a positive plate, a positive plate frame, a negative plate frame, a current collecting plate, and an end plate;
the iron-lead single flow battery structure comprises a negative electrode material layer, an ion selective permeation membrane and a positive electrode material layer which are sequentially arranged; the negative electrode material layer is filled with negative electrode electrolyte, the positive electrode material layer is filled with positive electrode electrolyte, and the positive electrode electrolyte circularly flows in the positive electrode material layer;
the negative electrode material layer consists of 68% of metallic lead, 27% of lead chloride and 5% of conductive carbon black in mass fraction;
the negative electrode electrolyte is an aqueous solution of hydrochloric acid, and the mass fraction of the hydrochloric acid is 15%;
the positive electrode material layer is a porous carbon electrode layer, in particular carbon cloth;
the positive electrolyte is a mixed aqueous solution formed by ferric chloride, ferrous chloride and hydrochloric acid (the mass ratio is 6:3: 1).
The ion selective membrane is a porous polyvinylidene fluoride membrane;
the thickness of the negative electrode material layer is 10mm, the negative electrode material layer is a porous solid electrode, the holes are open holes, electrolyte can enter the inside of the electrode, and the porosity is 33%.
The negative plate is arranged on the outer side of the negative material layer, the positive plate is arranged on the outer side of the positive material layer, and the collector plate and the end plate are respectively arranged on the outer sides of the negative plate and the positive plate in sequence;
a negative plate frame is arranged on the outer side of the negative material layer, and a positive plate frame is arranged on the outer side of the positive material layer;
and the anode plate frame is provided with a pipeline, and the other end of the pipeline is communicated with the anode electrolyte storage tank.
Preferably, a circulating pump is arranged on the pipeline;
the collector plate is made of a copper plate, and the positive plate and the negative plate are made of graphite materials;
and a channel for supplementing the negative electrolyte and exhausting is arranged on the negative plate frame.
The theoretical voltage of the cell prepared in this example is: 1.04V; after 300 cycles of charging and discharging, no obvious dendritic crystal is generated at the negative electrode; under the multiplying power of 0.5C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach more than 89 percent; under the multiplying power of 3C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach 86 percent; the capacity fade may be less than 2.5% after 100 charge and discharge cycles.
Example 8
The embodiment provides an iron-lead single flow battery, as shown in fig. 1, which includes an iron-lead single flow battery structure, and further includes a positive plate, a positive plate frame, a negative plate frame, a current collecting plate, and an end plate;
the iron-lead single flow battery structure comprises a negative electrode material layer, an ion selective permeation membrane and a positive electrode material layer which are sequentially arranged; the negative electrode material layer is filled with negative electrode electrolyte, the positive electrode material layer is filled with positive electrode electrolyte, and the positive electrode electrolyte circularly flows in the positive electrode material layer;
the negative electrode material layer consists of 45% of metallic lead, 20% of lead chloride and 35% of copper powder in percentage by mass;
the negative electrode electrolyte is an aqueous solution of hydrochloric acid, and the mass fraction of the hydrochloric acid is 20%;
the positive electrode material layer is a porous carbon electrode layer, in particular a porous carbon plate;
the positive electrolyte is a mixed aqueous solution formed by ferric chloride, ferrous chloride and hydrochloric acid (the mass ratio is 3:6: 1).
The ion selective membrane is a swelling sulfonated polyether sulfone membrane;
the thickness of the negative electrode material layer is 2mm, the negative electrode material layer is a porous solid electrode, the holes are open holes, electrolyte can enter the inside of the electrode, and the porosity is 46%.
The negative plate is arranged on the outer side of the negative material layer, the positive plate is arranged on the outer side of the positive material layer, and the collector plate and the end plate are respectively arranged on the outer sides of the negative plate and the positive plate in sequence;
a negative plate frame is arranged on the outer side of the negative material layer, and a positive plate frame is arranged on the outer side of the positive material layer;
and the anode plate frame is provided with a pipeline, and the other end of the pipeline is communicated with the anode electrolyte storage tank.
Preferably, a circulating pump is arranged on the pipeline;
the collector plate is made of a copper plate, and the positive plate and the negative plate are made of graphite materials;
and a channel for supplementing the negative electrolyte and exhausting air is arranged on the negative plate frame.
The theoretical voltage of the cell prepared in this example is: 1.04V; after 300 cycles of charging and discharging, no obvious dendritic crystal is generated at the negative electrode; under the multiplying power of 0.5C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach more than 85 percent; under the multiplying power of 3C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach 82 percent; the capacity fade may be less than 4% after 100 charge and discharge cycles.
Example 9
This example provides an iron-lead single flow battery, which has a structure substantially the same as that of example 6, except that: the negative electrode material layer consists of 70% of metallic lead and 30% of lead sulfate in percentage by mass.
The battery prepared in this example had the following properties: the theoretical voltage of the cell prepared in this example is: 1.13V; after 300 cycles of charge and discharge, no obvious dendrite is generated on the negative electrode; under the multiplying power of 0.5C, the current efficiency is 95.9 percent, and the energy efficiency is 76 percent; under the multiplying power of 3C, the current efficiency can reach 96.4%, and the energy efficiency can reach 63%; the capacity fade was 50.2% after 100 times of charge and discharge.
Example 10
This example provides an iron-lead single flow battery, which has a structure substantially the same as that of example 8, except that: the negative electrode material layer is composed of 42% of metallic lead, 18% of lead chloride and 40% of copper powder in percentage by mass.
The battery prepared in this example had the following properties: the theoretical voltage of the cell prepared in this example is: 1.04V; after 300 cycles of charging and discharging, no obvious dendritic crystal is generated at the negative electrode; under the multiplying power of 0.5C, the current efficiency can reach more than 99 percent, and the energy efficiency is 72 percent; under the multiplying power of 3C, the current efficiency can reach more than 97%, and the energy efficiency can reach 65%; the capacity fade was 7.2% after 100 times of charge and discharge.
Example 11
This example provides an iron-lead single flow battery, which has a structure substantially the same as that of example 1, except that: the negative electrode material layer consists of 60% of metallic lead, 25% of lead sulfate and 15% of graphite powder in percentage by mass.
The battery prepared in this example had the following properties: the theoretical voltage of the cell prepared in this example is: 1.13V; after 300 cycles of charging and discharging, no obvious dendritic crystal is generated at the negative electrode; under the multiplying power of 0.5C, the current efficiency can reach more than 98 percent, and the energy efficiency is more than 88 percent; under the multiplying power of 3C, the current efficiency can reach more than 99%, and the energy efficiency can reach 79%; the capacity fade was 2.8% after 100 times of charge and discharge.
Example 12
This example provides an iron-lead single flow battery, which has a structure substantially the same as that of example 1, except that: the negative electrode material layer is composed of, by mass, 60% of metallic lead, 25% of lead sulfate, and 15% of carbon fiber.
The battery prepared in this example had the following properties: the theoretical voltage of the cell prepared in this example is: 1.13V; after 300 cycles of charge and discharge, no obvious dendrite is generated on the negative electrode; under the multiplying power of 0.5C, the current efficiency can reach more than 97%, and the energy efficiency can reach more than 83%; under the multiplying power of 3C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach 77 percent; the capacity fade may be less than 3.3% after 100 charge and discharge cycles.
Example 13
This example provides an iron-lead single flow battery, which has a structure substantially the same as that of example 1, except that: the negative electrode material layer consists of 60% of metallic lead, 25% of lead sulfate and 15% of copper powder in percentage by mass.
The battery prepared in this example had the following properties: the theoretical voltage of the cell prepared in this example is: 1.13V; after 300 cycles of charging and discharging, no obvious dendritic crystal is generated at the negative electrode; under the multiplying power of 0.5C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach more than 85 percent; under the multiplying power of 3C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach 76 percent; the capacity fade may be less than 5.6% after 100 charge and discharge cycles.
Example 14
This example provides an iron-lead single flow battery, which has a structure substantially the same as that of example 1, except that: the thickness of the negative electrode material layer is 0.5 mm.
The theoretical voltage of the cell prepared in this example is: 1.13V; after 300 cycles of charging and discharging, no obvious dendritic crystal is generated at the negative electrode; under the multiplying power of 0.5C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach more than 90 percent; under the multiplying power of 3C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach 80 percent; the capacity fade may be less than 2% after 100 charge and discharge cycles. However, the negative electrode discharge capacity was only 48% of that of example 1, as compared with example 1.
Example 15
The present embodiment provides an iron-lead single flow battery, which has a structure substantially the same as that of embodiment 1, and is different from the structure only in that: the thickness of the negative electrode material layer is 1.0 mm.
The theoretical voltage of the cell prepared in this example is: 1.13V; after 300 cycles of charging and discharging, no obvious dendritic crystal is generated at the negative electrode; under the multiplying power of 0.5C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach more than 90 percent; under the multiplying power of 3C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach 80 percent; the capacity fade may be less than 2% after 100 charge and discharge cycles. However, the negative electrode discharge capacity was 78% of that of example 1, as compared with example 1.
Example 16
This example provides an iron-lead single flow battery, which has a structure substantially the same as that of example 1, except that: the thickness of the negative electrode material layer is 4.0 mm.
The theoretical voltage of the cell prepared in this example is: 1.13V; after 300 cycles of charging and discharging, no obvious dendritic crystal is generated at the negative electrode; under the multiplying power of 0.5C, the current efficiency can reach more than 98%, and the energy efficiency can reach more than 86%; under the multiplying power of 3C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach 77 percent; the capacity fade may be less than 2% after 100 charge and discharge cycles. The negative electrode discharge capacity was 1.6 times that of example 1, compared with example 1.
Example 17
This example provides an iron-lead single flow battery, which has a structure substantially the same as that of example 1, except that: the thickness of the negative electrode material layer is 20 mm.
The theoretical voltage of the cell prepared in this example is: 1.13V; after 300 cycles of charging and discharging, no obvious dendritic crystal is generated at the negative electrode; under the multiplying power of 0.5C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach more than 82 percent; under the multiplying power of 3C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach 73 percent; the capacity fade may be less than 2% after 100 charge and discharge cycles. The negative electrode discharge capacity was 3.2 times that of example 1, compared with example 1.
Example 18
This example provides an iron-lead single flow battery, which has a structure substantially the same as that of example 1, except that: the packing porosity of the negative electrode material layer is 20%.
The theoretical voltage of the cell prepared in this example is: 1.13V; after 300 cycles of charging and discharging, no obvious dendritic crystal is generated at the negative electrode; under the multiplying power of 0.5C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach more than 85 percent; under the multiplying power of 3C, the current efficiency can reach more than 99%, and the energy efficiency can reach 76%; the capacity fade may be less than 2% after 100 charge and discharge cycles.
Example 19
This example provides an iron-lead single flow battery, which has a structure substantially the same as that of example 1, except that: the negative electrode material layer has a packing porosity of 80%.
The theoretical voltage of the cell prepared in this example is: 1.13V; after 300 cycles of charging and discharging, no obvious dendritic crystal is generated at the negative electrode; under the multiplying power of 0.5C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach more than 84 percent; under the multiplying power of 3C, the current efficiency can reach more than 99 percent, and the energy efficiency can reach 75 percent; the capacity fade may be less than 2% after 100 charge and discharge cycles.
It should be noted that the iron-lead single flow battery of the present invention is not limited to the preparation of the above-mentioned embodiment, for example, a binder may be further added to the negative electrode material layer, and additives, such as bismuth oxide, barium sulfate, humic acid, gallium oxide, indium oxide, etc., may be further added to the negative electrode material layer, but not limited thereto; additives such as methanesulfonic acid, magnesium sulfate, sodium fluoride, and the like may also be added to the negative electrode electrolyte, but not limited thereto; additives such as ammonium sulfate, ammonium chloride, potassium sulfate, potassium chloride, and the like may be further added to the positive electrolyte, but not limited thereto. The iron-lead single flow battery prepared in this way can also achieve the effects of the present invention.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The structure of the iron-lead single flow battery is characterized by comprising a negative electrode material layer, an ion selective permeation membrane and a positive electrode material layer which are sequentially arranged; the negative electrode material layer is filled with negative electrode electrolyte, the positive electrode material layer is filled with positive electrode electrolyte, and the positive electrode electrolyte circularly flows in the positive electrode material layer;
the negative electrode material layer comprises two or three components of a lead simple substance, a solid divalent lead salt and a conductive agent;
the negative electrode electrolyte is a mixed aqueous solution formed by inorganic acid and an additive;
the positive electrode material layer is a porous carbon electrode layer;
the positive electrolyte comprises a mixed aqueous solution formed by a ferric salt solution, a ferrous salt and an inorganic acid.
2. An iron-lead single flow battery structure as claimed in claim 1, wherein said solid divalent lead salt is one or a combination of lead sulfate and lead chloride;
the conductive agent is one or a combination of more of conductive carbon black, graphene, carbon powder, carbon nano tubes, carbon fibers and copper.
3. The structure of the iron-lead single flow battery according to claim 1, wherein the total mass of the elemental lead and the solid divalent lead salt in the negative electrode material layer is 20 to 100% of the mass of the electrode material layer.
4. The structure of claim 1, wherein the negative electrode material layer further comprises a binder.
5. The structure of the iron-lead single flow battery as claimed in claim 1, wherein the thickness of the negative electrode material layer is 0.5-20mm, the negative electrode material layer is a porous solid electrode, the pores are open pores, and the porosity is 10-80%.
6. The structure of the iron-lead single flow battery according to claim 1, wherein the porous carbon electrode layer is one or a combination of carbon felt, carbon paper, carbon cloth and a porous carbon plate;
the ferrous salt is one or the combination of two of ferrous sulfate and ferrous chloride, and the ferric salt is one or the combination of two of ferric sulfate and ferric chloride;
the inorganic acid is one or the combination of two of sulfuric acid or hydrochloric acid;
the ion selective membrane is one or more of ion exchange resin membrane, porous polymer membrane and swelling polymer membrane.
7. An iron-lead single flow battery, comprising the iron-lead single flow battery structure of any one of claims 1 to 6, further comprising a positive plate, a positive plate frame, a negative plate frame, and an end plate;
the negative plate is arranged on the outer side of the negative material layer, the positive plate is arranged on the outer side of the positive material layer, and end plates are respectively arranged on the outer sides of the negative plate and the positive plate;
a negative plate frame is arranged around the negative material layer, and a positive plate frame is arranged around the positive material layer;
and the anode plate frame is provided with a pipeline, and the other end of the pipeline is communicated with the anode electrolyte storage tank.
8. The iron-lead single flow battery as claimed in claim 7, wherein a circulation pump is provided on the pipe;
the positive plate and the negative plate are both prepared from metal or carbon materials;
a channel for supplementing cathode electrolyte and exhausting is arranged on the cathode plate frame;
current collecting plates are arranged between the positive plate and the end plate and between the negative plate and the end plate; the collector plate is made of metal or carbon material.
9. An iron-lead single flow battery stack, characterized in that it is composed of the iron-lead single flow battery structure of any one of claims 1 to 6 in series and/or parallel.
10. The iron-lead single flow battery stack of claim 9, wherein the iron-lead single flow battery structure, when formed in series, further comprises a positive plate, a positive plate frame, a negative plate frame, a bipolar plate, and an end plate;
bipolar plates are arranged among the iron-lead single flow battery structures, the negative plate is arranged on the outer side of the negative material layer on the outermost side, the positive plate is arranged on the outer side of the positive material layer on the outermost side, and end plates are respectively arranged on the outer sides of the negative plate and the positive plate; a negative plate frame is arranged around the negative material layer, and a positive plate frame is arranged around the positive material layer; the anode plate frame is provided with a pipeline, and the other end of the pipeline is communicated with the anode electrolyte storage tank;
when the iron-lead single flow battery structure is formed in a parallel connection mode, every two anodes share one cathode; the specific structural unit comprises a positive electrode material layer, an ion selective permeable membrane, a negative electrode material layer, an ion selective permeable membrane and a positive electrode material layer which are sequentially arranged; the positive plate and the end plate are sequentially arranged outside the positive material layers on the two sides; the negative plate, the channel that is used for replenishing negative pole electrolyte and exhaust are provided with respectively on the negative plate frame, be provided with the pipeline on the positive plate frame, the anodal electrolyte storage pot is communicate to the pipeline other end.
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