CN106711486A - Lead redox flow battery electrolyte - Google Patents

Lead redox flow battery electrolyte Download PDF

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Publication number
CN106711486A
CN106711486A CN201611144823.7A CN201611144823A CN106711486A CN 106711486 A CN106711486 A CN 106711486A CN 201611144823 A CN201611144823 A CN 201611144823A CN 106711486 A CN106711486 A CN 106711486A
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Prior art keywords
lead
electrolyte
fluid cell
cell electrolyte
powder
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CN201611144823.7A
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CN106711486B (en
Inventor
吴旭
陈渊
纪良鑫
董金鑫
谢梦茹
李金东
杨家宽
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • 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

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention belongs to the field of battery electrolytes and discloses a lead redox flow battery electrolyte. A solvent of the lead redox flow battery electrolyte is deionized water, and solute contains lead methanesulfonate with the mole concentration of 0.1-2 mol/L and methanesulfonic acid with the mole concentration of 0.1-1 mol/L. The lead redox flow battery electrolyte prepared from recovered lead powder has smaller difference in battery performance than an electrolyte prepared from conventional analytically pure chemical reagents, the electrolyte applicable to a lead redox flow battery is prepared from more environment-friendly lead powder instead of analytically pure PbO, the cost is reduced, and scrapped lead-acid batteries can be effectively utilized.

Description

A kind of lead fluid cell electrolyte
Technical field
The invention belongs to lead fluid cell electrolyte field.
Background technology
Lead-acid accumulator has been subjected to the development course in more than 150 years from invention so far, and it is still accounted in secondary battery industry According to leading position.Lead-acid accumulator manufacturing enterprise mostly domestic at present uses lead powder as the active material of lead-acid accumulator, its Composition refers to by free lead (Pb, PbO of 70%~80% PbO and 20%~30%2And Pb3O4) composition mixture.In electricity Pond is reclaimed by wet recycling process after scrapping and can obtain the lead powder containing certain impurity, but the treatment disposal for reclaiming lead powder is asked Topic is also one of problem that urgent needs are solved at present.Under under a kind of combination redox flow batteries concept of flow battery Generation lead-acid battery, its manufacture craft is relatively easy, and its energy storage cost is less than conventional lead storage cells, has in extensive energy storage field Preferable application prospect.
Electrolyte is stored among fluid reservoir as the core of lead flow battery, and being transferred to inside battery by pump enters Row electrochemical reaction.When battery charges in charge/discharge process, positive pole and negative pole consume/release Pb simultaneously respectively2+From Son.Pb2+The flowing of electrolyte can improve electrode solid liquid interface mass transfer, power density be improved, while the energy storage of lead-acid flow battery Capacity depends on being pumped into from external storage tank the Pb of reative cell2+The amount of electrolyte, therefore the property and cost of electrolyte are to determine Determine one of restraining factors of lead flow battery scale.
The preparation of pyrovinic acid lead electrolytic solution in the prior art is by PbCO3Obtained with pyrovinic acid reaction, however it is this The pyrovinic acid lead that method is prepared is relatively costly, is unfavorable for expansion scale.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of lead fluid cell electrolyte, it is Lead flow battery charge and discharge process provides active material, advantageously accounts for the treatment disposal difficulties of waste and old lead acid flow battery.
To achieve the above object, it is proposed, according to the invention, there is provided a kind of lead fluid cell electrolyte, it is characterised in that described The solvent of lead fluid cell electrolyte is deionized water, and solute includes pyrovinic acid lead and pyrovinic acid, wherein lead methanesulfonate Molar concentration is 0.1mol/L-2mol/L, and the molar concentration of pyrovinic acid is 0.1mol/L-1mol/L.
Preferably, the lead methanesulfonate is obtained using the lead powder that hydrometallurgic recovery scrap lead cream is obtained with pyrovinic acid reaction.
Preferably, the lead powder is non-removal of impurities lead powder.
Preferably, the obtaining step of the lead fluid cell electrolyte is as follows：
1) deionized water is added in the non-removal of impurities lead powder for preparing to hydrometallurgic recovery scrap lead cream, then pyrovinic acid is slowly added into In above-mentioned solution and stir, until reacting completely；
2) by step 1) in reaction completely after solution filtering, the clarified filtrate for obtaining as lead flow battery electrolysis Liquid.
Preferably, the battery electrolyte is used in electrolytic cell prepared by 3D printer, and electrolytic cell both sides encapsulate just respectively Battery lead plate and negative electrode plate.
In general, by the contemplated above technical scheme of the present invention compared with prior art, can obtain down and show Beneficial effect：
(1) the lead powder raw material sources stabilization that the present invention is used, is conducive to preparing pyrovinic acid lead electrolytic solution on a large scale.
(2) hydrometallurgic recovery lead powder is processed without removal of impurities, can be directly applied in pyrovinic acid lead flow battery, is conducive to letter Change back technique, shorten recovery process, effectively reduce cost recovery.
(3) of the present invention, lead fluid cell electrolyte preparation process is simple, makes full use of the activity reclaimed in lead powder Material, effectively reduces battery and makes and operating cost.
(4) it is of the present invention to use the lead fluid cell electrolyte and traditional analysis pure chemistry reagent that reclaim lead powder preparation Prepare to electrolyte on battery performance difference it is smaller, replace the pure PbO of analysis to prepare using more environmentally friendly lead powder applicable In the electrolyte of lead flow battery, cost is both reduced, the lead-acid battery that will can be scrapped again is effectively utilized.
Brief description of the drawings
Fig. 1 prepares the Tafel figures of electrolyte for different material；
Fig. 2 (a) is the cyclic voltammetry curve map of electrolyte prepared by the non-removal of impurities lead powder for reclaiming；
Fig. 2 (b) is the cyclic voltammetry curve map of electrolyte prepared by the lead powder after the removal of impurities reclaimed；
Fig. 3 is the changes of contents figure of Ba impurity in battery CV tests.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as additionally, technical characteristic involved in invention described below each implementation method Not constituting conflict each other can just be mutually combined.
1~Fig. 3 of reference picture, a kind of lead fluid cell electrolyte, the solvent of the lead fluid cell electrolyte is deionization Water, solute includes pyrovinic acid lead and pyrovinic acid, and the wherein molar concentration of lead methanesulfonate is 0.1mol/L-2mol/L, methyl The molar concentration of sulfonic acid is 0.1mol/L-1mol/L.
Further, the lead methanesulfonate is obtained using the lead powder that hydrometallurgic recovery scrap lead cream is obtained with pyrovinic acid reaction.
Further, the lead powder is non-removal of impurities lead powder, so can on a large scale obtain lead powder.
Further, the obtaining step of the lead fluid cell electrolyte is as follows：
1) deionized water is added in the non-removal of impurities lead powder for preparing to hydrometallurgic recovery scrap lead cream, then pyrovinic acid is slowly added into In above-mentioned solution and stir, until reacting completely；
2) by step 1) in reaction completely after solution filtering, the clarified filtrate for obtaining as lead flow battery electrolysis Liquid.
Preferably, the battery electrolyte is used in electrolytic cell prepared by 3D printer, and electrolytic cell both sides encapsulate just respectively Battery lead plate and negative electrode plate.
Checking example：
The removal of impurities lead that the non-removal of impurities lead powder (R-2) that is obtained with analysis pure zirconia lead, recovery respectively in fume hood, recovery are obtained Powder (R-3), three kinds not raw material prepare pyrovinic acid lead flow battery electrolyte.
The difference of two kinds of lead powder that recovery is obtained is removed in physicochemical property has less gap, and Main Differences are R-2 It is the lead powder of non-removal of impurities, wherein containing the impurity such as 1197.7mg/L Fe and 1579.7mg/L Ba；And R-3 is then the lead after removal of impurities The impurity contents such as powder, Fe therein and Ba are far below the former.Because both oxidizabilities have differences, and pyrovinic acid only and PbO reacts, therefore the calculating wherein content of PbO weighs appropriate lead powder configuration electrolyte, and its specific consumption is as shown in table 1.
Table 1 configures raw material needed for battery electrolyte (1L)
Pyrovinic acid solution only reacts with the PbO in lead powder, by the solution clarified after filtering.Use two kinds of lead powder After being configured as the electrolyte of same composition, electro-chemical test is carried out；To probe into whether it can be influenceed by raw material.In rotating speed Under for 1600rpm, linear scan test (LSV) is carried out；Fig. 1 is electrolyte prepared by three kinds of different lead powder and analytically pure Electrolyte prepared by raw material carries out LSV tests, it can be seen that little using electrolyte difference prepared by different material, this three The equilibrium potential planted is differed within 10mV each other all in -370mV or so, and other parameters display that its difference Property very little.It can therefore be concluded that different raw materials does not produce considerable influence to lead simple substance deposition course of dissolution in electrolyte.
To probe into long time sedimentation course of dissolution, whether different electrolyte can be variant.By working electrode and to electricity Pole connects platinum filament respectively, carries out long-time cyclic voltammetry, is mutually converted between Pb and PbSO4 in traditional lead acid batteries When phenomenon, it may appear that obvious redox peaks.And in methanesulfonic acid solution the deposition dissolving of Pb it is different and the former, work as current potential The deposition course of dissolution of Pb will occur after deviateing equilibrium potential, so its result shows as an oblique line；For convenience of observing, will Electric current is mapped after taking the logarithm, and Fig. 2 is test result.Knowable to cyclic voltammetry result, after 300 CV are circulated, Two kinds of electrolyte properties keep stabilization, equilibrium potential all in -380mV or so, previously in the knot tested in rotating disk electrode (r.d.e) Fruit has different, because there is forced convertion effect in the latter, can influence mass transport process；And with the continuation of circulation, The equilibrium potential of both R-2 and R-3 30mV or so all to forward migration, because part Pb can sink during CV is circulated Product is not dissolved on platinum filament surface, so as to change the electrical conductivity of whole system.It can be inferred that different raw materials is for identical group The process of Pb depositions dissolving does not have an impact in the electrolyte for dividing.
Electrolyte prepared by R-2 and R-3 both lead powder it is maximum be not both both impurity containing different content, and Content difference is very big, therefore is contained using impurity content in the electrolyte of ICP measure preparations and the impurity in CV cyclic processes Amount, to probe into the process for being shifted with the presence or absence of impurity in the process.The two kinds of electrolyte obtained by R-2 and R-3 are followed in CV It is separately sampled during ring, part solution is taken out at 100,200,300 times respectively, carry out ICP test analysis wherein impurity Content, to probe into whether impurity can be transferred to the Pb and PbO of electrode surface generation in Pb deposition course of dissolutions2In.Fig. 3 is allusion quotation The change of type impurity B a contents in CV cyclic processes.It can be seen that in CV cyclic processes various impurity content Substantially it is consistent, does not increase with the increase of cycle-index.Therefore the electrolyte items that can be prepared with inference different material Can almost without difference, the content of wherein impurity is not influenceed on chemical property, and impurity will not also be deposited in Pb and dissolved During be transferred on the Pb and PbO2 of generation.Therefore the pure PbO of analysis can be replaced to prepare using more environmentally friendly lead powder suitable For the electrolyte of lead-acid flow battery.Both cost is reduced, there is the lead-acid battery that will can be scrapped effectively to be utilized.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, it is not used to The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., all should include Within protection scope of the present invention.

Claims (5)

1. a kind of lead fluid cell electrolyte, it is characterised in that the solvent of the lead fluid cell electrolyte is deionized water, molten Matter includes pyrovinic acid lead and pyrovinic acid, and the wherein molar concentration of lead methanesulfonate is 0.1mol/L-2mol/L, pyrovinic acid Molar concentration is 0.1mol/L-1mol/L.
2. a kind of lead fluid cell electrolyte according to claim 1, it is characterised in that the lead methanesulfonate uses wet method The lead powder that recovery scrap lead cream is obtained is obtained with pyrovinic acid reaction.
3. a kind of lead fluid cell electrolyte according to claim 1, it is characterised in that the lead powder is non-removal of impurities lead Powder.
4. a kind of lead fluid cell electrolyte according to claim 1, it is characterised in that the lead fluid cell electrolyte Obtaining step it is as follows：
1) deionized water is added in the non-removal of impurities lead powder for preparing to hydrometallurgic recovery scrap lead cream, then pyrovinic acid is slowly added into above-mentioned In solution and stir, until reacting completely；
2) by step 1) in reaction completely after solution filtering, the clarified filtrate for obtaining as lead fluid cell electrolyte.
5. a kind of lead fluid cell electrolyte according to claim 1, it is characterised in that the battery electrolyte is used for 3D In electrolytic cell prepared by printer, electrolytic cell both sides encapsulate positive electrode plate and negative electrode plate respectively.
CN201611144823.7A 2016-12-13 2016-12-13 Lead flow battery electrolyte Active CN106711486B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109638329A (en) * 2018-12-19 2019-04-16 中国科学技术大学 A kind of water system flow battery
CN113277550A (en) * 2021-05-24 2021-08-20 湖北华德莱节能减排科技有限公司 Lead-containing solid waste treatment method, and preparation method and application of lead dioxide powder

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110092860A (en) * 2010-02-10 2011-08-18 한국과학기술연구원 Sn or ce ion-added electrolytes for soluble lead acid redox flow battery and batteries comprising the same
CN102618884A (en) * 2012-03-16 2012-08-01 北京化工大学 Lead regeneration method for recovering lead paste from waste lead acid storage battery by wet method
CN102723519A (en) * 2011-03-30 2012-10-10 中国人民解放军63971部队 Lead liquid flow battery electrolyte
CN102723518A (en) * 2011-03-30 2012-10-10 中国人民解放军63971部队 All-lead liquid flow battery
CN103715447A (en) * 2013-11-20 2014-04-09 浩源科技有限公司 Efficient soluble lead-acid flow battery
CN104078695A (en) * 2014-07-22 2014-10-01 沈阳工程学院 Full-sedimentary type lead acid liquid current battery energy storing device
CN105914388A (en) * 2016-04-20 2016-08-31 浩发环保科技（深圳）有限公司 Lead methanesulfonate flow battery electrolyte

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110092860A (en) * 2010-02-10 2011-08-18 한국과학기술연구원 Sn or ce ion-added electrolytes for soluble lead acid redox flow battery and batteries comprising the same
CN102723519A (en) * 2011-03-30 2012-10-10 中国人民解放军63971部队 Lead liquid flow battery electrolyte
CN102723518A (en) * 2011-03-30 2012-10-10 中国人民解放军63971部队 All-lead liquid flow battery
CN102618884A (en) * 2012-03-16 2012-08-01 北京化工大学 Lead regeneration method for recovering lead paste from waste lead acid storage battery by wet method
CN103715447A (en) * 2013-11-20 2014-04-09 浩源科技有限公司 Efficient soluble lead-acid flow battery
CN104078695A (en) * 2014-07-22 2014-10-01 沈阳工程学院 Full-sedimentary type lead acid liquid current battery energy storing device
CN105914388A (en) * 2016-04-20 2016-08-31 浩发环保科技（深圳）有限公司 Lead methanesulfonate flow battery electrolyte

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109638329A (en) * 2018-12-19 2019-04-16 中国科学技术大学 A kind of water system flow battery
CN113277550A (en) * 2021-05-24 2021-08-20 湖北华德莱节能减排科技有限公司 Lead-containing solid waste treatment method, and preparation method and application of lead dioxide powder

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