CN102646835A - Oxidizability and reducibility conducting polymer flow anode used for flow battery - Google Patents
Oxidizability and reducibility conducting polymer flow anode used for flow battery Download PDFInfo
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- CN102646835A CN102646835A CN2012101219604A CN201210121960A CN102646835A CN 102646835 A CN102646835 A CN 102646835A CN 2012101219604 A CN2012101219604 A CN 2012101219604A CN 201210121960 A CN201210121960 A CN 201210121960A CN 102646835 A CN102646835 A CN 102646835A
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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
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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
- Y02E60/50—Fuel cells
Abstract
The invention discloses an oxidizability and reducibility conducting polymer flow anode with used for a flow battery. An oxidizability and reducibility conducting polymer or a conducting polymer and an inorganic substance composite material are dispersed in electrolyte solution to form electrolyte of the flow battery, the electrolyte and a three-dimensional mesh current-collection body commonly constitute an emulsus flow electroactive polymer anode, and anode flow passes an anode chamber in a flowing form in the charging and discharging processes and is used for forming a flow battery system. As the dimension of the conducting polymer and the dimension of the inorganic substance composite material of the conducting polymer are large, the battery can adopt a common porous diaphragm; in addition, the corrosion of a medium system of the electrolyte of the battery used for an electroactive material to a solid current collector is small, and therefore, the environmental pollution is small in the production and using processes; the conducting polymer is rich in source, so as to be prepared on a large scale by an organic synthesis method; and the cost of the flow battery can be greatly lowered.
Description
Technical field
The present invention relates to high-power second liquid flow field of batteries, what specially refer to that MH secondary battery, vanadium secondary cell, lithium secondary battery use is the emulsus of the main body composition positive electrode material preparation method that can flow with conducting polymer polyaniline, polypyrrole and composite material of inorganic matter thereof.
Technical background
Along with the continuous deterioration of global environment and people attention to environmental problem; Development of new environmental friendliness clean energy resource is extremely urgent, and redox flow batteries is a kind of energy-storage system of rising in recent years, and it has common batteries and fuel cell performance concurrently; There are working life and storage life long; Advantages such as fast charging and discharging, depth of discharge performance are good, airtight circulating system has been avoided contacting with the external world simultaneously, and environmental pollution is little.Select suitable oxidation-reduction pair that battery is not produced oxygen and hydrogen in running basically; Electrode material needn't use valuable metallic catalyst etc.; Be expected to realize the scale high-efficiency energy-storage, can be used for fields such as renewable energy system, power peak regulation, UPS emergency power supply, electric automobile and military power supply.The oxidation-reduction pair that can be used in flow battery should have that solubility is big, chemical property is stable, the electrode reaction invertibity is high, do not have analyse oxygen/liberation of hydrogen side reaction, electricity to characteristics such as potential difference is big.Carry out more flow battery system at present all-vanadium flow battery, sodium polysulfide/bromine flow battery, zinc/bromine flow battery are arranged.Vanadium redox battery is the cell reaction active material with the vanadium ion solution of different valence state, and anode is V
5+/ V
4+Electricity is right, and negative pole is V
3+/ V
2+Electricity is right, selects for use sulfuric acid as supporting electrolyte, though the research of vanadium cell has obtained remarkable progress; But its development still receives the restriction of some key technologies, and vanadium cell is if want large-scale commercial applicationsization, need further raising critical material performance, reduce cost; Wherein battery diaphragm is wanted acid resistance, non-oxidizability, and the perfluoro sulfonic acid membrane price of using at present is high; Heating is big during high-power discharging and recharging, the life-span is short, and the commercialization of fancy price restriction all-vanadium flow battery is promoted.Taking cost into account sodium polysulfide/bromine flow battery, zinc/bromine flow battery have advantage than all-vanadium flow battery; In the flow battery system that with bromine is anodal liquid when charging bromide ion lose electronics and become simple substance bromine; Bromine is dissolved in the bromine salting liquid of high concentration, becomes Br
3 -, Br
5 -Ion, and spread to negative pole from positive pole when being diffused near the negative pole, reacts with negative electrode active material, causes self discharge.The aqueous solution of bromine and bromine salt has corrosivity to battery material, and the long-time running of battery causes the aging distortion of battery material, has influenced the performance and the useful life of battery greatly.
There is following several problem in the redox flow batteries commercial applications at present: (1) material cost; Vanadium redox battery particularly; Because the vfanadium compound that uses is rare material, use not only cost high but also be difficult to reduce its cost significantly in a large number through technological approaches.With bromine is the bromide and the Br of the flow battery use of anodal liquid
3 -, Br
5 -The stabilizer of ion makes cost also higher; (2) environmental issue, water-soluble vanadium compound toxicity is very strong, and the environment control criterion is high, has a big risk in production and use environmental pollution.It is big to be with bromine that the flow battery of anodal liquid also exists the molecular bromine smell that use produces; (3) high to the requirement of ion diaphragm, ion diaphragm is wanted acidproof resistance to oxidation (4) the battery lead plate life-span, in order to improve V in the anodal liquid of vanadium flow battery
5+Solubility is used the above H of 2mol/L now
2SO
4As supporting electrolyte, high acid medium requires high to battery lead plate.In addition, the anodal liquid of bromine flow battery is very big to the graphite electrode plate corrosion, and the battery lead plate life problems does not also have fine solution.
Summary of the invention
It is low that technical problem to be solved by this invention provides a kind of flow battery cost, to the corrosion minimizing of battery lead plate, requires the oxidation-reduction quality conducting polymer flow that is used for flow battery of reduction anodal to amberplex.
In order to solve the problems of the technologies described above; The oxidation-reduction quality conducting polymer flow positive pole that is used for flow battery provided by the invention; Conducting polymer or conducting polymer and composite material of inorganic matter with redox characteristic are dispersed in the electrode solution that constitutes flow battery in the electrolyte solution; Form emulsus flow electroactive polymer positive pole jointly with solid netted collector body, anodal liquid through cathode chamber, is used to constitute the flow battery system with the type of flow in the charge and discharge process.
Described conducting polymer is polyaniline, polypyrrole, polythiophene, gathers benzene, coalescence benzene, polyethylene ferrocene, gathers naphthols, polyamino anthaquinone and their derivative.
Described conducting polymer and composite material of inorganic matter mainly are conducting polymer and multivalence attitude metal oxide MnO
2, V
2O
5Or WO
3, or the anode material of lithium battery LiMn of conducting polymer parcel
2O
4, LiV
3O
8Or LiFePO
4
Described electrolyte solution main component is respectively: lithium/polymer liquid galvanic battery electrolyte solution main component is LiNO
3, LiClO
4, LiBF
4Or their mixture; Zinc/polymer liquid galvanic battery electrolyte solution main component is ZnCl
2Or ZnBr
2Or ZnSO
4Or ZnClO
4Or Zn (NO
3)
2Or their mixture, vanadium/polymer liquid galvanic battery electrolyte solution main component is VOCl
2, VOBr
2, VOSO
4Or their mixture.
Adopt the oxidation-reduction quality conducting polymer flow that is used for flow battery of technique scheme anodal; The conducting polymer of at first synthetic oxidation-reduction quality; Mainly comprise polyaniline, polypyrrole, polythiophene, gather, gather naphthols or polyamino anthaquinone and their derivative benzene, coalescence benzene, polyethylene ferrocene; It is synthetic to pass through oxidations such as chemical oxidizing agent such as persulfate (potassium peroxydisulfate, ammonium persulfate), potassium permanganate, iron chloride, hydrogen peroxide, also can be synthetic through electrochemical oxidation method.
The synthetic concrete grammar of polyaniline and derivative is following: with a certain amount of aniline monomer and inorganic acid example hydrochloric acid, be made into aniline solution; Take by weighing in the water-soluble solution of a certain amount of ammonium persulfate, reaction system is placed under the ultrasonic wave effect, the control temperature is at 20～23 ℃; Ammonium persulfate solution slowly is added drop-wise in the solution of aniline, reaction is carried out suction filtration to product after finishing; Water-solubility impurity is removed in washing.Earlier once, more once with hydrochloric acid solution washing suction filtration with ethanolic solution washing suction filtration.By above-mentioned same method, respectively other various inorganic (hydrochloric acid, sulfuric acid, phosphoric acid) or organic acid (p-methyl benzenesulfonic acid, DBSA, camphorsulfonic acid) are mixed to aniline, can obtain inorganic acid and organic acid doped polyaniline.The polyaniline derivative preparation method is identical with polyaniline.
The synthetic concrete grammar of polypyrrole and derivative is following: with a certain amount of pyrrole monomer and inorganic acid example hydrochloric acid, be made into pyrroles's solution; Take by weighing in the water-soluble solution of a certain amount of ammonium persulfate, the control temperature adds N at 20～23 ℃
2Protection slowly is added drop-wise to ammonium persulfate solution in pyrroles's solution down, and reaction is carried out suction filtration to product after finishing, and deposition is used a large amount of deionized waters successively, methyl alcohol and ether washing.Products therefrom obtains black polypyrrole powder at 60 ℃ of following vacuumize 24h after grinding.The polypyrrole derivative preparation method is identical with polypyrrole.
The synthetic concrete grammar that gathers 3 methyl thiophene is following: a certain amount of 3 methyl thiophene is dissolved in the chloroform, goes into N
2To be added in the liquor ferri trichloridi under the protection, reaction is carried out suction filtration to product after finishing, and will precipitate successively with methyl alcohol and ether washing.Products therefrom obtains gathering 3 methyl thiophene at 60 ℃ of following vacuumize 24h after grinding.
In order to improve the oxidizing potential of conducting polymer, prepare above-mentioned conducting polymer and metal oxide (like MnO
2Or V
2O
5) composite material.Synthetic method can be directly with above-mentioned conducting polymer powder and MnO after grinding
2Or V
2O
5Powder mixes, and oxide amount is controlled between 4% to 9% in the mixture.In-situ synthesis is higher with stability than the compound good uniformity that direct mixing method obtains.Polyaniline-V
2O
5It is following that the complex substance in-situ synthetic method prepares concrete grammar: at first prepare V
2O
5Gel takes by weighing a certain amount of V
2O
5Add the people to 10%H
2O
2Fully react in the solution to orange V
2O
5Powder disappears and obtains wine-colored liquid, and the kermesinus gel of solution left standstill ageing thickness is added to V with polyaniline powder
2O
5Gel, stirring is mixed, filter the back with water and absolute ethanol washing several times after, 60 ℃ of vacuumizes.Polyaniline derivative-V
2O
5Compound, polypyrrole and derive and V
2O
5The compound preparation method is identical with said method.
Polyaniline-MnO
2Composite material synthetic: respectively with in polyaniline salt acid solution and the ammonium persulfate solution, then with ammonium persulfate solution all to the hydrochloric acid solution of polyaniline, after both mix with the MnO that measures
2Join in the reaction system.After reaction finished, product was collected after filtration.Filter cake is earlier colourless to filtrating with hydrochloric acid solution drip washing, filters with containing the static immersion of aniline salt acid solution back at last.Again through hydrochloric acid solution, acetone drip washing, 3 times repeatedly.Product obtains the polyaniline-manganese dioxide composite material of emeraldine salt form 60 ℃ of vacuumizes.Polyaniline derivative-MnO
2Compound, polypyrrole and derive and MnO
2The compound preparation method is identical with said method.
The LiFePO that polyaniline coats
4Composite material is synthetic: a certain amount of neopelex is joined in the deionized water stirs, fully after the dissolving with LiFePO
4Powder joins in the solution, injects aniline monomer behind the stirring 30min, splashes into a certain amount of FeCl then
3Under nitrogen protection, stir 6h, filtration product water and absolute ethanol washing several times after, dry 24h in 60 ℃ of vacuum drying ovens.Change LiFePO
4With the amount of aniline, can synthesize the LiFePO that the different content polyaniline coats
4Polyaniline coats LiMn
2O
4, polyaniline coats LiV
3O
8, polypyrrole and derivative coat LiFePO
4Or LiMn
2O
4Or LiV
3O
8The preparation method is identical with said method.
Gather 3 methyl thiophene and other conducting polymer and MnO
2, V
2O
5, LiMn
2O
4, LiFePO
4, LiV
3O
8Method for synthesizing composite material is identical with polyaniline/composite material of inorganic matter preparation technology.
With above-mentioned conducting polymer powder or conducting polymer and MnO
2, V
2O
5, LiFePO
4Composite powder, electron mediator, stabilizer are added to the anodal liquid that just constitutes flow battery in the electrolyte, and collector body adopts carbon fibre web or graphite felt.The negative pole oxidation-reduction pair adopts existing Li
+/ Li, Zn
2+/ Zn, V
3+/ V
2+, Fe
2+/ Fe, Cr
3+/ Cr, Cd
2+/ Cd, Pb
2+/ Pb, Sn
2+/ Sn/, Mn
2+/ Mn metal/metal ion redox couple.The electrolyte solution main component is respectively: lithium/polymer liquid galvanic battery electrolyte main component is LiNO
3, LiClO
4, LiBF
4Or their mixture; Zinc/polymer liquid galvanic battery electrolyte main component is ZnCl
2Or ZnBr
2Or ZnSO
4Or ZnClO
4Or Zn (NO
3)
2Or their mixture; Vanadium/polymer liquid galvanic battery electrolyte main component is VOCl
2, VOBr
2, VOSO
4Or their mixture.Constitute redox flow batteries and be mainly lithium/polymer liquid galvanic battery, zinc/polymer liquid galvanic battery, vanadium/polymer liquid galvanic battery, manganese/polymer liquid galvanic battery.
Adopt the oxidation-reduction quality conducting polymer flow that is used for flow battery of technique scheme anodal; Conducting polymer (like polyaniline, polypyrrole) or conducting polymer and composite material of inorganic matter that employing has redox characteristic are dispersed in the anodal liquid that constitutes flow battery in the electrolyte solution, and negative pole adopts existing Li
+/ Li, Zn
2+/ Zn, V
3+/ V
2+Constitute redox flow batteries etc. the metal/metal ion redox couple; Since the conductive polymer molecules size greatly to battery diaphragm require low; Only need common porous septum; And the battery medium is little to the solid current collector corrodes, and the conducting polymer source is abundant, preparation is simple, production use environmental pollution is little.Because conducting polymer can pass through the methodology of organic synthesis mass preparation, the battery cost can significantly reduce.
Embodiment
Below in conjunction with embodiment the present invention is described further.
Embodiment 1
Zinc/polyaniline flow battery
Positive electrode collector adopts graphite felt, and battery electrolyte is formed 2mol/L ZnCl
2, 2mol/LNH
4Cl, active matter polyaniline content is that 100g/L, additive are 1g/L in the anodal liquid.Anode chamber and cathode chamber volume are 2.5cm * 5cm * 0.3cm (wide * long * thick), and the barrier film of both positive and negative polarity adopts the polyethylene film of 0.6 millimeters thick.The negative pole of battery adopts zine plate, and negative pole liquid is 2mol/LZnCl
2, 2mol/L NH
4Cl.Battery open circuit voltage is 1.1 volts, battery charging voltage scope 0.8V-1.8V, battery discharge voltage range 1.8V-0.8V, charging and discharging currents density 2mA/cm
2, mobile electrolyte flow rate is 20ml/min, coulombic efficiency is 73%.
Embodiment 2
Manganese/polyaniline flow battery
Positive electrode collector adopts graphite felt, and battery electrolyte is formed 1mol/L MnSO
4, 1mol/L (NH
4)
2SO
4, active matter polyaniline content is that 100g/L, additive are 1g/L in the anodal liquid.Anode chamber and cathode chamber volume are 2.5cm * 5cm * 0.3cm (wide * long * thick), and the barrier film of both positive and negative polarity adopts the polyethylene film of 0.6 millimeters thick.The negative pole of battery is the manganese sheet, and negative pole liquid is 1mol/L MnSO
4, 1mol/L (NH
4)
2SO
4Battery open circuit voltage is 1.3 volts, battery charging and discharging voltage range 1.2V-2.6V, charging and discharging currents density 1mA/cm
2, mobile electrolyte flow rate is 20ml/min, coulombic efficiency is 64%.
Embodiment 3
Zinc/polypyrrole flow battery
Positive electrode collector adopts graphite felt, and battery electrolyte is formed 2mol/L ZnCl
2, 2mol/LNH
4Cl, active matter polypyrrole content is that 100g/L, additive are 1g/L in the anodal liquid.Anode chamber and cathode chamber volume are 2.5cm * 5cm * 0.3cm (wide * long * thick), and the barrier film of both positive and negative polarity adopts the polyethylene film of 0.6 millimeters thick.The negative pole of battery adopts zine plate, and negative pole liquid is 2mol/LZnCl
2, 2mol/L NH
4Cl.Battery open circuit voltage is about 1.2 volts, battery charging voltage scope 1.2V-2.0V, battery discharge voltage range 1.8V-0.8V, charging and discharging currents density 2mA/cm
2, mobile electrolyte flow rate is 20ml/min, coulombic efficiency is 70%.
Embodiment 4
Vanadium/polyaniline-V
2O
5Flow battery
Positive electrode collector adopts graphite felt, and battery electrolyte is formed 2mol/L VOCl
2, 0.2mol/L HCl, active matter polyaniline-V in the anodal liquid
2O
5Content is that 200g/L, additive are 2g/L.Anode chamber and cathode chamber volume are 2.5cm * 5cm * 0.3cm (wide * long * thick), and the barrier film of both positive and negative polarity adopts the polyethylene film of 0.6 millimeters thick.The negative electricity body of battery adopts graphite felt, and negative pole liquid is 2mol/L VCl
3, 0.2mol/L HCl.Battery open circuit voltage is 0.9 volt, battery charging voltage scope 0.8V-2.2V, battery discharge voltage range 0.9V-0.6V, charging and discharging currents density 1mA/cm
2, mobile electrolyte flow rate is 20ml/min, coulombic efficiency is 67%.
Embodiment 5
Lithium/polyaniline-LiFePO
4Flow battery
It is 1mol/L LiBF that positive electrode collector adopts graphite felt, electrolyte
4Propene carbonate liquid, active matter polyaniline-LiFePO in the anodal liquid
4Content is 150g/L.Anode chamber and cathode chamber volume are 2.5cm * 5cm * 0.3cm (wide * long * thick), and the barrier film of both positive and negative polarity adopts the polyethylene film of 0.6 millimeters thick.The negative pole of battery adopts the lithium sheet, and negative pole liquid is that electrolyte is 1mol/LLiBF
4Propene carbonate.Battery open circuit voltage is about 3.2 volts, battery charging and discharging voltage range 2.2V-4.5V, charging and discharging currents density 2mA/cm
2, mobile electrolyte flow rate is 20ml/min, coulombic efficiency is 70%.
Claims (5)
1. an oxidation-reduction quality conducting polymer flow that is used for flow battery is anodal; It is characterized in that: conducting polymer or conducting polymer and composite material of inorganic matter with redox characteristic are dispersed in the electrode solution that constitutes flow battery in the electrolyte solution; Form emulsus flow electroactive polymer positive pole jointly with solid netted collector body; Anodal liquid through cathode chamber, is used to constitute the flow battery system with the type of flow in the charge and discharge process.
2. the oxidation-reduction quality conducting polymer flow positive pole that is used for flow battery according to claim 1, it is characterized in that: described conducting polymer is polyaniline, polypyrrole, polythiophene, gathers benzene, coalescence benzene, polyethylene ferrocene, gathers naphthols, polyamino anthaquinone and their derivative.
3. the oxidation-reduction quality conducting polymer flow positive pole that is used for flow battery according to claim 1 and 2, it is characterized in that: described conducting polymer and composite material of inorganic matter mainly are conducting polymer and multivalence attitude metal oxide MnO
2, V
2O
5Or WO
3, or the anode material of lithium battery LiMn of conducting polymer parcel
2O
4, LiV
3O
8Or LiFePO
4
4. want the 1 or 2 described oxidation-reduction quality conducting polymer flow positive poles that are used for flow battery according to right, it is characterized in that: flow battery system negative pole oxidation-reduction pair adopts Li
+/ Li, Zn
2+/ Zn, V
3+/ V
2+, Mn
2+/ Mn metal/metal ion redox couple constitutes redox flow batteries.
5. want the 1 or 2 described oxidation-reduction quality conducting polymer flow positive poles that are used for flow battery according to right, it is characterized in that: described electrolyte solution main component is respectively: lithium/polymer liquid galvanic battery electrolyte solution main component is LiNO
3, LiClO
4, LiBF
4Or their mixture; Zinc/polymer liquid galvanic battery electrolyte solution main component is ZnCl
2Or ZnBr
2Or ZnSO
4Or ZnClO
4Or Zn (NO
3)
2Or their mixture; Manganese/polymer liquid galvanic battery electrolyte solution main component is MnCl
2Or MnBr
2Or MnSO
4Or MnClO
4Or Mn (NO
3)
2Or their mixture; Vanadium/polymer liquid galvanic battery electrolyte solution main component is VOCl
2, VOBr
2, VOSO
4Or their mixture.
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|---|---|---|---|
| CN201210121960.4A CN102646835B (en) | 2012-04-24 | 2012-04-24 | Oxidizability and reducibility conducting polymer flow anode used for flow battery |
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Cited By (7)
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|---|---|---|---|---|
| CN103872369A (en) * | 2012-12-11 | 2014-06-18 | 苏州宝时得电动工具有限公司 | Flow battery |
| CN104882624A (en) * | 2015-04-17 | 2015-09-02 | 大连理工大学 | Anthraquinone flow battery |
| WO2016078492A1 (en) * | 2014-11-17 | 2016-05-26 | 中国科学院大连化学物理研究所 | Quinone polyhalide flow battery |
| CN107482242A (en) * | 2017-07-16 | 2017-12-15 | 常州大学 | A kind of water system single flow battery based on metal organic complex liquid stream positive pole and preparation method thereof |
| CN108475804A (en) * | 2016-07-19 | 2018-08-31 | 松下知识产权经营株式会社 | Flow battery |
| CN108948328A (en) * | 2018-06-04 | 2018-12-07 | 东华大学 | A kind of preparation method of poly- 1,5- diamino-anthraquinone nanometer rods |
| CN112018330A (en) * | 2019-05-28 | 2020-12-01 | 中国科学院宁波材料技术与工程研究所 | Dealkalized metal ion material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103872369A (en) * | 2012-12-11 | 2014-06-18 | 苏州宝时得电动工具有限公司 | Flow battery |
| WO2016078492A1 (en) * | 2014-11-17 | 2016-05-26 | 中国科学院大连化学物理研究所 | Quinone polyhalide flow battery |
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| CN108475804A (en) * | 2016-07-19 | 2018-08-31 | 松下知识产权经营株式会社 | Flow battery |
| CN107482242A (en) * | 2017-07-16 | 2017-12-15 | 常州大学 | A kind of water system single flow battery based on metal organic complex liquid stream positive pole and preparation method thereof |
| CN107482242B (en) * | 2017-07-16 | 2019-11-12 | 常州大学 | A kind of water system single flow battery and preparation method thereof based on metal organic complex liquid stream anode |
| CN108948328A (en) * | 2018-06-04 | 2018-12-07 | 东华大学 | A kind of preparation method of poly- 1,5- diamino-anthraquinone nanometer rods |
| CN108948328B (en) * | 2018-06-04 | 2021-05-11 | 东华大学 | Preparation method of poly (1, 5-diaminoanthraquinone) nanorods |
| CN112018330A (en) * | 2019-05-28 | 2020-12-01 | 中国科学院宁波材料技术与工程研究所 | Dealkalized metal ion material and preparation method thereof |
| CN112018330B (en) * | 2019-05-28 | 2022-01-28 | 中国科学院宁波材料技术与工程研究所 | Dealkalized metal ion material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN102646835B (en) | 2014-12-10 |
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