CN102723518A - All-lead liquid flow battery - Google Patents
All-lead liquid flow battery Download PDFInfo
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- CN102723518A CN102723518A CN2011100783116A CN201110078311A CN102723518A CN 102723518 A CN102723518 A CN 102723518A CN 2011100783116 A CN2011100783116 A CN 2011100783116A CN 201110078311 A CN201110078311 A CN 201110078311A CN 102723518 A CN102723518 A CN 102723518A
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Abstract
The invention belongs to the electrochemical engineering and industrial fields, particularly to a lead liquid flow battery. The single battery cell consists of a deposition-type lead dioxide anode, a deposition-type lead dioxide cathode and an electrolyte containing soluble lead salt. A galvanic pile can be formed by a plurality of battery cells being connected serially or in parallel. The electrolyte of the galvanic pile is stored in a storage tank and the electrolyte pushed by a liquid pump keeps flowing between the storage tank and the pile pipes in the process of charging and discharging. The lead in the electrolyte is deposited on current collectors of the positive electrode and the negative electrode to become the lead dioxide and metallic lead when the battery is charged. And the lead dioxide and metallic lead dissolve in the electrolyte to become lead ions when the battery is discharged. The liquid flow battery is characterized by simple manufacture, low cost and long cycle life.
Description
Technical field
The invention belongs to Electrochemical Engineering and commercial plant field, particularly a kind of complete plumbous flow battery of battery production technical field is used for making up simply and easily complete plumbous flow battery.
Background technology
The energy becomes the important foundation of social development now, and fossil energy faces exhaustion.Greatly developing regenerative resources such as wind energy, solar energy is the important channel of realizing China's energy sustainable development.Renewable energy power generation has time difference property and unsteadiness, has limited its utilization of being incorporated into the power networks on a large scale.Electric power storage is effective ways that solve the instability problem of regenerative resource, can realize the regenerative resource large-scale application.
Flow battery (Flow cell, Flow battery) optimum scale energy storage to develop at present in the chemical storage batteries.Flow battery flexible design, life cycle cost are minimum, be the chemical cell of the most suitable scale energy storage now, so competitiveness are very strong, and application prospect is boundless.
Be different from the traditional secondary battery; Flow battery is dissolved in respectively in the solution that is contained in two big fluid reservoirs as the right active material of OR electricity; Respectively make the both sides of flow of solution high selectivity amberplex in liquid stream battery stack, reduction and oxidation reaction take place on its catalysis electrode with a pump.During these, the electric charge of amberplex both sides solution must have a kind of ion (like H in order to reach balance
+) synchronously move to another utmost point solution through amberplex by a utmost point solution.In addition, also developed the flow battery that metal ion (and nonmetallic ion) dissolving/deposition reaction takes place on one or two electrode.Researched and developed multiple flow battery system at present, research comparatively deeply in addition the system that begins to get into commercialization demonstration operation sodium polysulfide/bromine flow battery, zinc bromine flow battery and all-vanadium flow battery are arranged.
2004, (Ahmed Hazza, Derek Pletcher such as Britain Pletcher; Richard Wills.Phys.Chem.Chem.Phys; (6): 1773-1778,2004) propose a kind of novel lead-acid flow energy-storage battery system, this system adopts plumbous (II) solution of acidic methylene sulfonic acid; Divalence lead during charging in the solution is deposited as metallic lead on negative pole, be deposited as brown lead oxide on the positive pole; During discharge just/that negative reaction forms soluble divalence is plumbous.The both positive and negative polarity reactive activity is high, good reversibility.But the overpotential of brown lead oxide nucleation is bigger, is prone to produce oxygen, and causes energy loss (energy efficiency is about 65%), and negative pole has plumbous residue behind the battery discharge, repeatedly causes Pb accumulation after the circulation, needs logical oxygen dissolving.In addition, the deposition of negative electrode lead is prone to form dendrite, and generation comes off.Be the roughness and raising PbO that reduces negative pole Pb deposition
2Kinetics, studied organic and influence inorganic additive, but effect is all undesirable.Chinese patent CN101853956A proposes electrodes use carbon dust and high density polyethylene (HDPE) and is pressed into pressing glass transition carbon-coating behind the substrate; As Britain Pletcher etc., adopt the plumbous pyrovinic acid aqueous solution of pyrovinic acid as electrolyte; Charging and discharging currents efficient increases, and energy efficiency reaches 76%.
Tetrafluoro boric acid is compared with pyrovinic acid, and its molecular weight is low, and price is 1/2nd of a pyrovinic acid, and solidifying point is lower than solidifying point (10 ℃) temperature of pyrovinic acid, so the cryogenic property of solution is good.Pyrovinic acid also has labile shortcoming under the certain condition.In electroplating industry, lead fluoborate lead plating technology is quite ripe, has the advantages that electrolyte solution is stable, composition is simple, easy to operate, the coating crystallization is closely careful, and current efficiency is high.We test discovery in the fluoborate aqueous solution of lead fluoborate on the suitable collector brown lead oxide deposition/dissolved efficiency higher.Therefore we propose complete plumbous flow battery; Battery cell is anodal by the appositional pattern brown lead oxide, the plumbous negative pole of appositional pattern and the electrolyte that contains soluble lead salt are formed; But become pile by multiple batteries monomer serial or parallel connection; The electrolyte of pile is stored in the storage tank, and electrolyte constantly flows between storage tank and pile through pipeline under liquid pump promotes in charge and discharge process.Lead deposits to the positive and negative electrode collector respectively during charging from electrolyte becomes brown lead oxide and metallic lead, and zinc brown lead oxide and metallic lead are dissolved into and generate lead ion in the electrolyte during discharge.This flow battery has that manufacturing process is simple, cost is low, the cycle life advantages of higher.
Summary of the invention
The objective of the invention is to design a kind of complete plumbous flow battery, problem such as the positive and negative electrode efficiency for charge-discharge that occurs easily when suppress adopting pyrovinic acid solution is inconsistent and improve energy efficiency.
The objective of the invention is to realize through following method: sketch map is seen Fig. 1; A kind of complete plumbous flow battery; Battery cell (1) is made up of positive collector electrode (2), negative collector electrode (3) and electrolyte (4); Electrolyte (4) promotes lower edge pipeline (6) at pump (5) and between storage tank (7) and battery cell (1), flows; Electrolyte (4) flows through the surface of positive collector electrode (2) and negative collector electrode (3) and separates positive collector electrode (2) and negative collector electrode (3) in battery cell (1); Wherein electrolyte (4) is gone up deposition brown lead oxide (8), is gone up plated metal plumbous (9) in negative collector electrode (3) in positive collector electrode (2) during charging for containing the plumbous tetrafluoroborate solution of tetrafluoro boric acid, and brown lead oxide during discharge (8) and metallic lead (9) all dissolve to be got back in the electrolyte (4).
The positive collector electrode of complete plumbous flow battery (2) can be a material with carbon element, can be titanium or the titanium alloy with conductive oxide or nitride film surface, has the tantalum or the tantalum alloy on conductive oxide, nitride or carbide membrane surface.
The negative collector electrode of complete plumbous flow battery (3) can be material with carbon element, iron, stainless steel, copper or copper alloy.
Complete plumbous flow battery can be combined into pile (10) by a plurality of battery cells (1), the shared electrolyte of wherein a plurality of battery cells (1) (4), pump (5), pipeline (6) and storage tank (7).
Do not adorn barrier film between the positive collector electrode (2) of complete plumbous flow battery monomer (1) and the negative collector electrode (3), or install the barrier film that prevents anodal and negative pole short circuit additional.
Complete plumbous flow battery of the present invention is in charge and discharge process, and electrolyte (4) is constantly fed in the battery cell (1) by pump (5).During charging; Lead in the electrolyte (4) is being deposited as brown lead oxide (8), on negative collector electrode (3), is being deposited as metallic lead (9) and energy storage on the positive collector electrode (2), brown lead oxide during discharge (8) and metallic lead (9) are dissolved into lead and are got into electrolyte (4).When discharge finished, positive collector electrode (2) and negative collector electrode (3) returned to the reset condition of " fresh " basically, thereby can charge again effectively.Simultaneously, electrolyte flow has increased the speed of the material Transfer in the electrode interface solution, has greatly reduced concentration polarization, and electrolyte is in the homogeneous flow regime all the time can layering and eliminated the inhomogeneous problem that causes electrode deformation that deposits.We test discovery in the fluoborate aqueous solution of lead fluoborate on the suitable collector current efficiency of brown lead oxide deposition/dissolved efficiency can reach more than 93%, even reach more than 98%.And in the fluoborate aqueous solution of lead fluoborate on the suitable collector current efficiency of lead deposit/dissolved efficiency generally all more than 95%.
The current efficiency of complete plumbous flow battery positive and negative electrode of the present invention is very approaching, controls negative electrode lead residue easily, forms problem such as dendrite, and energy efficiency is high, advantage such as have the preparation route and technology is simple, cost is low and have extended cycle life.
Description of drawings
A kind of complete plumbous flow battery of Fig. 1
1 battery cell, 2 positive collector electrode, 3 negative collector electrode, 4 electrolyte, 5 pumps, 6 pipelines, 7 storage tanks, 8 brown lead oxide, 9 lead
A kind of complete plumbous flow battery of Fig. 2
1 battery cell, 2 positive collector electrode, 3 negative collector electrode, 4 electrolyte, 5 pumps, 6 pipelines, 7 storage tanks, 8 brown lead oxide, 9 lead, 10 piles
Embodiment
Like Fig. 1; The high solid graphite plate thick with 3mm is fixed in the complete plumbous flow battery monomer of composition in the plastic casing as positive collector electrode and negative collector electrode separation; The aqueous solution with 1.5 moles every liter tetrafluoro boric acid lead, 1.0 moles of every liter of tetrafluoro boric acids is stored in the polyethylene jar as electrolyte;, use magnetic drive pump to promote electrolyte and flow through positive collector electrode and negative collector electrode separation facing surfaces as pipeline with silicone tube.Lead during charging in the electrolyte is being deposited as brown lead oxide, on negative collector electrode, is being deposited as metallic lead on the positive collector electrode, brown lead oxide and metallic lead are dissolved into lead and are got into electrolyte during discharge.With 20mA/cm
2Current density discharge and recharge, current efficiency can reach more than 95%, energy efficiency about 82%.
Like Fig. 1, the tantalum paper tinsel that the carbonization tantalum film is arranged with the thick surface of 0.1mm is as positive collector electrode, and as negative collector electrode, positive collector electrode and negative collector electrode are separated to be fixed in and formed complete plumbous flow battery monomer in the plastic casing with the thick stainless steel foil of 0.1mm.The aqueous solution with 1.0 moles every liter tetrafluoro boric acid lead, 1.0 moles of every liter of tetrafluoro boric acids is stored in the polyethylene jar as electrolyte;, use magnetic drive pump to promote electrolyte and flow through positive collector electrode and negative collector electrode separation facing surfaces as pipeline with rubber hose.With 40mA/cm
2Current density discharge and recharge, current efficiency can reach more than 98%, energy efficiency about 75%.
Like Fig. 1, the titanium foil that titanium nitride film is arranged with the thick surface of 0.1mm is as positive collector electrode, and as negative collector electrode, positive collector electrode and negative collector electrode are separated to be fixed in and formed complete plumbous flow battery monomer in the plastic casing with the thick steel foil of 0.1mm.The aqueous solution with 1.0 moles every liter tetrafluoro boric acid lead, 1.5 moles of every liter of tetrafluoro boric acids is stored in the polyethylene jar as electrolyte;, use magnetic drive pump to promote electrolyte and flow through positive collector electrode and negative collector electrode separation facing surfaces as pipeline with rubber hose.With 10mA/cm
2Current density discharge and recharge, current efficiency can reach more than 98%, energy efficiency about 85%.
Like Fig. 1; The titanium plate that titanium, ruthenium and tin mixed oxide film is arranged with the thick surface of 1mm is as positive collector electrode; As negative collector electrode, positive collector electrode and negative collector electrode separation are fixed in and are formed complete plumbous flow battery monomer in the plastic casing with the thick Pot metal paper tinsel of 0.1mm.The aqueous solution with 1.0 moles every liter tetrafluoro boric acid lead, 1.5 moles of every liter of tetrafluoro boric acids is stored in the polyethylene jar as electrolyte;, use magnetic drive pump to promote electrolyte and flow through positive collector electrode and negative collector electrode separation facing surfaces as pipeline with rubber hose.With 50mA/cm
2Current density discharge and recharge, current efficiency can reach more than 96%, energy efficiency about 73%.
Like Fig. 2; The tantalum paper tinsel that the carbonization tantalum film is arranged with the thick surface of 0.1mm is as positive collector electrode; With the thick stainless steel foil of 0.1mm as negative collector electrode; Positive collector electrode and negative collector electrode separation are fixed in and are formed complete plumbous flow battery monomer in the plastic casing, and anodal linking to each other of a plurality of monomers drawn Positive Poles, the continuous negative pole pole of drawing of negative pole.The aqueous solution with 1.0 moles every liter tetrafluoro boric acid lead, 1.0 moles of every liter of tetrafluoro boric acids is stored in the polyethylene jar as electrolyte;, use magnetic drive pump to promote electrolyte and flow through positive collector electrode and negative collector electrode separation facing surfaces as pipeline with rubber hose.With 20mA/cm
2Current density discharge and recharge, current efficiency can reach more than 98%, energy efficiency about 82%.
Claims (4)
1. complete plumbous flow battery; It is characterized in that battery cell (1) is made up of positive collector electrode (2), negative collector electrode (3) and electrolyte (4); Electrolyte (4) promotes lower edge pipeline (6) at pump (5) and between storage tank (7) and battery cell (1), flows; Electrolyte (4) flows through the surface of positive collector electrode (2) and negative collector electrode (3) and separates positive collector electrode (2) and negative collector electrode (3) in battery cell (1); Wherein electrolyte (4) is for containing the plumbous tetrafluoroborate solution of tetrafluoro boric acid; Go up deposition brown lead oxide (8), go up plated metal plumbous (9) in negative collector electrode (3) in positive collector electrode (2) during charging, brown lead oxide during discharge (8) and metallic lead (9) all dissolve to be got back in the electrolyte (4).
2. complete plumbous flow battery according to claim 1 is characterized in that positive collector electrode (2) is material with carbon element, has the surperficial titanium or titanium alloy of conductive oxide film, has the surperficial titanium or titanium alloy of conductive nitride film, has conductive oxide film surperficial tantalum and tantalum alloy, has the tantalum and the tantalum alloy on conductive nitride film surface or have conductive carbide film surperficial tantalum and tantalum alloy.
3. complete plumbous flow battery according to claim 1 is characterized in that negative collector electrode (2) is material with carbon element, iron, stainless steel, copper or copper alloy.
4. complete plumbous flow battery according to claim 1, its characteristic a plurality of battery cells (1) can shared electrolyte (4), pump (5), pipeline (6) and storage tank (7) and be combined into pile (10).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100783116A CN102723518A (en) | 2011-03-30 | 2011-03-30 | All-lead liquid flow battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011100783116A CN102723518A (en) | 2011-03-30 | 2011-03-30 | All-lead liquid flow battery |
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| CN102723518A true CN102723518A (en) | 2012-10-10 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103715447A (en) * | 2013-11-20 | 2014-04-09 | 浩源科技有限公司 | Efficient soluble lead-acid flow battery |
| CN104716373A (en) * | 2013-12-13 | 2015-06-17 | 中国人民解放军63971部队 | Flow battery with negative electrode of titanium pair |
| CN105845960A (en) * | 2016-05-06 | 2016-08-10 | 华中科技大学 | Lead liquid flow battery and electrolytic cell thereof |
| 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 |
| CN106711486A (en) * | 2016-12-13 | 2017-05-24 | 华中科技大学 | Lead redox flow battery electrolyte |
| WO2018032409A1 (en) * | 2016-08-17 | 2018-02-22 | 大连融科储能技术发展有限公司 | Flow battery system and large scale flow battery energy storage device |
| CN109873191A (en) * | 2019-03-29 | 2019-06-11 | 西安理工大学 | A kind of electrolyte and preparation method thereof of the resistance to season of lead flow battery |
| CN111682288A (en) * | 2020-05-21 | 2020-09-18 | 西安理工大学 | Preparation method of lead-acid flow battery with long cycle life |
| CN112864437A (en) * | 2021-01-25 | 2021-05-28 | 上海交通大学 | Iron-lead single flow battery and preparation method thereof |
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| CN101326672A (en) * | 2005-10-11 | 2008-12-17 | 普拉里昂有限公司 | Battery with bifunctional electrolyte |
| KR101009440B1 (en) * | 2008-10-10 | 2011-01-19 | 한국과학기술연구원 | Electrode for soluble lead acid redox flow battery and soluble lead acid redox flow battery using the same |
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2011
- 2011-03-30 CN CN2011100783116A patent/CN102723518A/en active Pending
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| CN101326672A (en) * | 2005-10-11 | 2008-12-17 | 普拉里昂有限公司 | Battery with bifunctional electrolyte |
| KR101009440B1 (en) * | 2008-10-10 | 2011-01-19 | 한국과학기술연구원 | Electrode for soluble lead acid redox flow battery and soluble lead acid redox flow battery using the same |
Non-Patent Citations (1)
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103715447A (en) * | 2013-11-20 | 2014-04-09 | 浩源科技有限公司 | Efficient soluble lead-acid flow battery |
| CN103715447B (en) * | 2013-11-20 | 2015-10-28 | 浩源科技有限公司 | A kind of Efficient soluble lead-acid flow battery |
| CN104716373A (en) * | 2013-12-13 | 2015-06-17 | 中国人民解放军63971部队 | Flow battery with negative electrode of titanium pair |
| 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 |
| CN105845960A (en) * | 2016-05-06 | 2016-08-10 | 华中科技大学 | Lead liquid flow battery and electrolytic cell thereof |
| WO2018032409A1 (en) * | 2016-08-17 | 2018-02-22 | 大连融科储能技术发展有限公司 | Flow battery system and large scale flow battery energy storage device |
| US11705570B2 (en) | 2016-08-17 | 2023-07-18 | Dalian Rongkepower Co., Ltd | Flow battery system and large scale flow battery energy storage device |
| CN106711486A (en) * | 2016-12-13 | 2017-05-24 | 华中科技大学 | Lead redox flow battery electrolyte |
| CN106711486B (en) * | 2016-12-13 | 2020-05-19 | 华中科技大学 | Lead flow battery electrolyte |
| CN109873191A (en) * | 2019-03-29 | 2019-06-11 | 西安理工大学 | A kind of electrolyte and preparation method thereof of the resistance to season of lead flow battery |
| CN109873191B (en) * | 2019-03-29 | 2021-06-15 | 西安理工大学 | Lead flow battery seasonal-resistant electrolyte and preparation method thereof |
| CN111682288A (en) * | 2020-05-21 | 2020-09-18 | 西安理工大学 | Preparation method of lead-acid flow battery with long cycle life |
| CN112864437A (en) * | 2021-01-25 | 2021-05-28 | 上海交通大学 | Iron-lead single flow battery and preparation method thereof |
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Application publication date: 20121010 |