CN101677135B - Zinc-manganese flow battery - Google Patents
Zinc-manganese flow battery Download PDFInfo
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- CN101677135B CN101677135B CN2008102112275A CN200810211227A CN101677135B CN 101677135 B CN101677135 B CN 101677135B CN 2008102112275 A CN2008102112275 A CN 2008102112275A CN 200810211227 A CN200810211227 A CN 200810211227A CN 101677135 B CN101677135 B CN 101677135B
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- 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
- Y02E60/10—Energy storage using batteries
Abstract
A zinc-manganese flow battery consists of a galvanic pile, an electrolyte storage tank, a liquid pump and a pipeline, wherein the galvanic pile comprises an anode, a cathode and a packaging shell, wherein the anode is manganese oxide or composite oxide or oxide mixture of manganese, nickel, cobalt, lead, bismuth, silver, tungsten and molybdenum, the cathode is a zinc electrode deposited on a cathode current collector, and the electrolyte is alkaline solution containing soluble zinc salt and is mainly stored in the electrolyte storage tank. In the charging and discharging process, the electrolyte is pushed by the liquid pump to continuously flow between the electrolyte storage tank and the electric pile through the pipeline. Zinc is deposited on the negative current collector from the electrolyte to become a negative active material during charging, and zinc is dissolved in the electrolyte from the negative current collector during discharging. The flow battery has the advantages of simple manufacturing process, low cost, long cycle life and the like.
Description
Technical Field
The invention relates to a combination principle and a preparation method of a novel battery, in particular to a principle and a preparation method of a zinc-manganese flow battery, belongs to the field of chemical engineering, and can be widely applied to the fields of electronic industry, transportation, electric power, mining and metallurgy and the like.
Background
The existing alkaline zinc-manganese battery is a fourth generation product of a zinc-manganese battery series, and the commercialization is realized in the 50 s of the 20 th century. The alkaline zinc-manganese battery adopts electrolytic manganese dioxide as a positive electrode active substance, zinc paste as a negative electrode active substance and potassium hydroxide as an electrolyte solution, and has the advantages of excellent heavy-current discharge performance and continuous discharge performance, high capacity, good low-temperature performance and the like. The alkaline zinc-manganese battery has the advantages of rich raw materials, low cost and wide market. The alkaline zinc-manganese battery is classified into a primary alkaline zinc-manganese battery and a secondary alkaline zinc-manganese battery according to the operational characteristics of the battery.
Primary alkaline zinc-manganese batteries are a pet of the primary battery market and have captured over 50% of the primary battery value. The primary battery can not be reused and is difficult to recycle, which causes resource waste and is an important disadvantage.
The secondary alkaline zinc-manganese battery, also called a renewable alkaline battery, maintains the excellent performance of the primary alkaline zinc-manganese battery, can be repeatedly used for many times, not only saves resources, but also can reduce environmental pollution, and is a requirement of human beings on sustainable development of the battery industry. After years of efforts of researchers at home and abroad, the secondary alkaline zinc-manganese dioxide battery reaches a certain level, and if the discharge depth is 25%, the battery can be safely cycled for 40-50 times.
The reason for the poor cycle life of the secondary alkaline zinc-manganese dioxide battery is mainly MnO 2 Poor rechargeability, and poor zinc electrode life is another important reason. When MnO is protected by limiting capacity of zinc electrode 2 The main reason for the performance degradation of the secondary alkaline zinc-manganese dioxide battery is the degradation of the zinc electrode performance. The reasons for the change in the performance of zinc electrodes are the deformation of the electrode and the production of zinc dendrites.
In concentrated alkali solution, the anode dissolved product of zinc is soluble zincate:
Zn+4OH - ＝Zn(OH) 4 2- +2e -
when the solution is saturated with zincate or OH - The anodic product of zinc is Zn (OH) when the ion concentration decreases 2 Or ZnO:
Zn+2OH - ＝Zn(OH) 2 +2e - or Zn +2OH - ＝ZnO+H 2 O+2e -
It has been found that the two modes can be performed for bulk zinc electrodes only when operated at very low current densities. When the current density is increased, the polarization is intensified, if the current density exceeds a critical value, the electrode potential is suddenly changed to the positive direction, the anode oxidation process of the zinc is greatly retarded, and the battery can not continuously work. This phenomenon is called anodic passivation.
The main reason for the passivation of the zinc electrode is that when the anode of the zinc electrode is dissolved, the concentration of zincate in the solution near the surface of the electrode is gradually increased, and ZnO and Zn (OH) begin to be generated on the surface of the electrode after the zincate is saturated 2 The solid deposit reduces the effective area of the electrode, increases the real current density, aggravates polarization and rapidly moves the electrode potential to the positive direction.When the potential for generating the adsorption ZnO is reached, a compact ZnO adsorption layer is generated on the surface of the zinc electrode, so that the activation energy of the anode dissolution process of zinc is greatly improved, and the anode process of zinc is greatly retarded to enter a passive state. For mass transfer on the electrode surface, due to Zn (OH) 4 2- Diffusion coefficient of (2) to OH - The diffusion coefficient of ions is one order of magnitude smaller, so the passivation process is mainly influenced by Zn (OH) 4 2- And controlling ion diffusion. Therefore, all factors that increase the diffusion of zincate in the electrolyte near the electrode surface and reduce its supersaturation will reduce the passivation of the zinc electrode, so the flow rate of the liquid can be increased to eliminate the anode passivation.
A flow battery, also called a flow redox battery, which can be called a flow power storage station or a flow battery for short, is an electrochemical energy storage concept proposed by Thaller, l.h. (NASALewis Research Center, cleveland, US) in 1974. The core of the flow battery is that active substances for carrying out oxidation-reduction reaction and realizing charging and discharging processes exist in electrolyte, and single cell or half cell electrodes are only used as sites for reaction and are not sites for storing the active substances. Because the active substance is stored in the electrolyte, the flow battery has the advantages of power and capacity separation, long service life and the like. The development of the flow battery has been over 30 years, researchers in various countries obtain various available flow battery systems by converting two oxidation/reduction pairs, the liquid phase energy storage electrochemical system has early Cr/Fe and Ti/Fe systems, and in recent years, the liquid phase energy storage electrochemical system has reports of new systems of vanadium, vanadium/cerium, chromium, uranium and the like and a second generation vanadium (vanadium bromide) system. These systems require the use of an ion exchange membrane to separate the positive/negative electrolytes. However, to date, the more mature sodium polysulfide/bromine and all vanadium (vanadium sulfate) systems alone, and especially all vanadium systems, have begun preliminary commercialization in japan, canada, australia. In recent years, with the increase of vanadium cost sections, the cost of the all-vanadium redox flow battery is increasingly higher, and great difficulty is brought to the popularization and application of the all-vanadium redox flow battery.
The new deposition type liquid flow energy-storing system is characterized by that in the course of charging (discharging) at least one pair of charging (discharging) products is deposited on (or originally on) electrode. For example, in older zinc-bromine batteries, zinc was deposited on the surface of the negative electrode while the bromine molecules generated on the positive electrode remained in the liquid phase during charging. The recent pietcher topic group at the university of south ampton, uk proposed a new flow battery system based on the concept of lead acid secondary batteries. The system adopts an acidic lead methylsulfonate (II) solution, divalent lead in the solution is deposited into metallic lead on a negative electrode during charging, lead dioxide is deposited on a positive electrode, and the positive electrode and the negative electrode react to form soluble divalent lead during discharging. Recently, the research group also reported that alkaline zinc-nickel single fluid cells (application No. 200610109424.7) utilize electrodeposition of zinc in alkaline KOH solution to achieve electrical energy storage. Because the positive and negative electrodes of the deposition type flow battery use the same liquid, the cross contamination of the liquid phase energy storage flow battery is avoided, the use of expensive ion exchange membranes is saved, the charging efficiency of the battery is improved, new interest of researchers is increasingly aroused, and the deposition type flow battery has greater practicability.
However, the positive electrode nickel electrode of the alkaline zinc-nickel uniflow battery is still expensive, and has a certain price pressure for large-scale energy storage. We therefore investigated the feasibility of MnOx materials for alkaline fluid cells with zinc as the negative electrode.
Disclosure of Invention
The invention provides a zinc-manganese flow battery, which integrates the advantages of the zinc-manganese battery and the flow battery, and stores a negative active material zinc in an electrolyte in the form of a zinc salt solution so as to overcome the problems of passivation and elimination of deformation and dendrite of a zinc electrode during heavy current discharge of the zinc electrode, improve a manganese dioxide electrode and prolong the cycle life of the battery.
The purpose of the invention is realized by the following modes:
the battery consists of an electric pile 1, an electrolyte storage tank 2, a liquid pump 3 and a pipeline 4, wherein the electric pile 1 comprises an anode 5, a cathode 6 and a packaging shell, wherein an active substance of the anode 5 is manganese oxide or composite oxide or oxide mixture of manganese and nickel, cobalt, lead, bismuth, silver, tungsten and molybdenum, the cathode 6 is a zinc 8 electrode deposited on a cathode current collector 7, and an electrolyte 9 is an alkaline solution containing soluble zinc salt and is mainly stored in the electrolyte storage tank 2; during the charging and discharging process, the electrolyte 9 is pushed by the liquid pump 3 to continuously flow between the electrolyte storage tank 2 and the electric pile 1 through the pipeline 4.
The chemical formula of the active material of the anode 5 of the cell stack 1 is MnOx, wherein 2 is more than or equal to x is more than or equal to 1; or the active material of the positive electrode 5 has a chemical formula A σ Mn y B 1-y Oz, wherein 0.2>σ≥0，1>y is more than or equal to 0, A is one or more of K, na, li, mg, ca, cu, zn and Bi, and B is one or more of Ni, co, pb, bi, ag, mo and W. The negative current collector 7 of the stack 1 is a carbon material, a metal foil, a metal plate, or a foamed metal.
The electrolyte 9 is an alkaline electrolyte containing soluble zinc salt, and the main components of alkali in the electrolyte are one or more than one of the following components: ba (OH) 2 NaOH, KOH, liOH; the soluble zinc salt contained in the electrolyte 9 may be derived from ZnO or Zn (OH) 2 、K 2 Zn(OH) 4 、Na 2 Zn(OH) 4 Or mixtures thereof; the electrolyte 9 may contain carbonate, soluble silicate, aluminum salt, aluminate, lead salt, plumbate, indium salt, bismuth salt, molybdate, tungstate, tin salt, stannate, boric acid, borate, alkyl quaternary ammonium salt, or a mixture thereof.
When MnO is used 2 When used as a positive electrode, the electrode reaction is as follows:
negative electrode: zn +4OH - ＝Zn(OH) 4 2- +2e -
And (3) positive electrode: 2MnO 2 +2H 2 O+2e - ＝2MnOOH+2OH -
In the charging and discharging process of the zinc-manganese flow battery, the electrolyte is continuously introduced into the battery pile by the liquid pump, and the flowing of the electrolyte increases the speed of substance transfer in the solution of the electrode interface, thereby eliminating concentration polarization and reducing the possibility of generating zinc dendrites during charging. When the discharging is finished, the metal zinc of the negative electrode is completely dissolved, and the current collector of the negative electrode is recovered to the original state of 'fresh', so that the charging can be effectively carried out again. Meanwhile, the electrolyte is always in a uniform flowing state and cannot be layered, so that the problem of electrode deformation is solved. The electrolyte can be unsaturated solution of zinc salt, so that zinc oxide can not be generated on the positive electrode during charging, and the poisoning problem of the positive electrode is eliminated. Because only the active substance of one electrode is in the electrolyte and the zinc salt does not react at the anode, the zinc-manganese flow battery does not use an ion exchange membrane or even a diaphragm, and the positive electrode and the negative electrode are directly separated by the electrolyte.
The zinc-manganese flow battery has the advantages of simple manufacturing process, low cost, long cycle life and the like, has higher energy density and power density and high energy utilization efficiency, and can be widely applied to industries such as electric power, traffic, electronics and the like.
Drawings
FIG. 1 Zinc manganese flow cell
1. A zinc-manganese flow battery pile comprises a zinc-manganese flow battery pile, an electrolyte storage tank, a liquid pump, a pipeline, a positive electrode, a negative electrode, a current collector, a zinc deposition layer and an electrolyte layer, wherein the electrolyte storage tank is 2, the liquid pump is 3, the pipeline is 4, the positive electrode is 5, the negative electrode is 6, the negative electrode is 7, the current collector is 8, the zinc deposition layer is 9, and the electrolyte layer is 9
Detailed Description
Example 1
Preparation of positive electrode
Using conductive agent carbonyl nickel powder, adhesive PTFE (polytetrafluoroethylene), electrolytic MnO 2 And Bi 2 O 3 According to the mass ratio of 10:3:80:7, mixing the mixture according to the proportion, mixing the mixture with polyalcohol and water to form slurry, uniformly coating the slurry on a foamed nickel current collector by a wet slurry coating method, drying, rolling and cutting to obtain the anode used for the zinc-manganese flow battery.
Example 2
Preparation of negative electrode
The steel strip is rolled to about 50 mu m, and proper holes are formed on the steel strip by a puncher to obtain the punched steel strip, wherein the general hole rate is required to be 10-50%. The punched steel strip can be used as a negative current collector for a zinc-manganese flow battery after being cut properly and can also be used after being plated with nickel.
Example 3
Electrolyte preparation
450g KOH, 40g NaOH and 20g LiOH are weighed and dissolved in a proper amount of water, and 80g ZnO and 5g ZnCO are added before the solution is cooled 3 And fully dissolved. Dissolving 16g NaAlO in appropriate amount of water 2 、1g Pb(OH) 2 And 2g tetrabutylammonium hydroxide. The two mixed solutions are uniform, and the volume is 1L. Preparing a proper amount of electrolyte, and placing the electrolyte in an electrolyte storage tank.
Example 4
Zinc-manganese flow battery assembly
Arranging positive and negative electrodes in a proper container in a positive and negative opposite mode, reserving a certain gap between the electrodes, arranging an electrolyte circulation channel at the gap, sealing the electrolyte circulation channel into a battery pile, and connecting an electrolyte pipeline, a pump and an electrolyte storage tank. While the electrolyte flows, charging (zinc deposition by the negative electrode) and discharging (re-dissolution of zinc of the negative electrode into the electrolyte) can be performed. The specific energy and specific power of the zinc-manganese flow battery prepared in the way can reach the level of an all-vanadium flow battery.
Claims (4)
1. A zinc-manganese flow battery is characterized by comprising a galvanic pile (1), an electrolyte storage tank (2), a liquid pump (3) and a pipeline (4), wherein the galvanic pile (1) comprises an anode (5), a cathode (6) and a packaging shell, wherein the active substance of the anode (5) is manganese oxide or a composite oxide of manganese and nickel, cobalt, lead, bismuth, silver, tungsten and molybdenum or an oxide mixture of manganese and nickel, cobalt, lead, bismuth, silver, tungsten and molybdenum, the cathode (6) is a zinc (8) electrode deposited on a cathode current collector (7), and the electrolyte (9) is an alkaline solution containing soluble zinc salt and is mainly stored in the electrolyte storage tank (2); in the charging and discharging process, the electrolyte (9) is pushed by the liquid pump (3) to continuously flow between the electrolyte storage tank (2) and the electric pile (1) through the pipeline (4).
2. The zinc-manganese flow battery according to claim 1, characterized in that the active material of the positive electrode of the stack (1) has the chemical formula MnOx, where 2 ≧ x ≧ 1; or the active material of the positive electrode has a chemical formula of A σ Mn y B 1-y Oz, wherein 0.2 & gtsigma & gt, is not less than 0,1 & gty & gt, 0, A is one or more of K, na, li, mg, ca, cu, zn and Bi, and B is one or more of Ni, co, pb, bi, ag, mo and W.
3. The zinc-manganese flow battery according to claim 1, characterized in that the electrolyte (9) is an alkaline electrolyte containing soluble zinc salts, and the main component of the alkali in the electrolyte is one or more than one of the following: ba (OH) 2 NaOH, KOH, liOH; the soluble zinc salt can be from ZnO, zn (OH) 2 、K 2 Zn(OH) 4 、Na 2 Zn(OH) 4 Or mixtures thereof; the electrolyte (9) may contain carbonate, soluble silicate, aluminum salt, aluminate, lead salt, plumbate, indium salt, bismuth salt, molybdate, tungstate, tin salt, stannate, boric acid, borate, alkyl quaternary ammonium salt, or a mixture thereof.
4. The zinc-manganese flow battery according to claim 1, characterized in that the negative current collector (7) of the stack (1) is a carbon material, a metal foil, a metal plate or a foamed metal.
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| CN2008102112275A CN101677135B (en) | 2008-09-18 | 2008-09-18 | Zinc-manganese flow battery |
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| CN2008102112275A CN101677135B (en) | 2008-09-18 | 2008-09-18 | Zinc-manganese flow battery |
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| CN101677135B true CN101677135B (en) | 2012-10-31 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014074830A1 (en) * | 2012-11-09 | 2014-05-15 | Research Foundation Of The City University Of New York | Secondary zinc-manganese dioxide batteries for high power applications |
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| CN105280964B (en) * | 2014-07-24 | 2018-07-31 | 中国科学院大连化学物理研究所 | A kind of zinc-manganese flow battery |
| CN105280943B (en) * | 2014-07-24 | 2018-04-06 | 中国科学院大连化学物理研究所 | A kind of full manganese flow battery |
| CN105336971B (en) * | 2015-09-25 | 2018-08-17 | 中国人民解放军63971部队 | Water-system zinc-manganese single flow battery |
| CN106129443B (en) * | 2016-07-08 | 2018-11-30 | 北京航空航天大学 | A kind of novel keggin type cobalt wolframic acid flow battery |
| JP2019067632A (en) * | 2017-09-29 | 2019-04-25 | 京セラ株式会社 | Flow battery |
| JP2019067636A (en) * | 2017-09-29 | 2019-04-25 | 京セラ株式会社 | Flow battery |
| JP2019067637A (en) * | 2017-09-29 | 2019-04-25 | 京セラ株式会社 | Flow battery |
| CN110165308B (en) * | 2018-02-13 | 2021-06-29 | 中国科学院大连化学物理研究所 | Application of porous ion conducting membrane with negative charges in alkaline zinc-based battery |
| KR20210019503A (en) * | 2018-06-14 | 2021-02-22 | 리서치 파운데이션 오브 더 시티 유니버시티 오브 뉴욕 | High voltage ion mediated flow/flow auxiliary manganese dioxide-zinc battery |
| CN108808053B (en) * | 2018-06-22 | 2021-10-15 | 浙江裕源储能科技有限公司 | Zinc-nickel liquid flow energy storage battery |
| JP2020021565A (en) * | 2018-07-30 | 2020-02-06 | 京セラ株式会社 | Flow battery |
| CN113437340B (en) * | 2021-05-10 | 2022-10-11 | 中国科学院金属研究所 | Positive electrode electrolyte for zinc-manganese flow battery |
| CN114068995B (en) * | 2021-11-22 | 2022-05-20 | 张明刚 | All-iron oxidation flow battery system |
| CN115312732A (en) * | 2022-08-31 | 2022-11-08 | 河南超力新能源有限公司 | Low-cost alkaline secondary battery positive electrode material and preparation method and application thereof |
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| WO2014074830A1 (en) * | 2012-11-09 | 2014-05-15 | Research Foundation Of The City University Of New York | Secondary zinc-manganese dioxide batteries for high power applications |
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