CN101901937B - Cerium ion electrolyte using silver ion as anode catalyst and preparation method thereof - Google Patents

Cerium ion electrolyte using silver ion as anode catalyst and preparation method thereof Download PDF

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CN101901937B
CN101901937B CN2010102551068A CN201010255106A CN101901937B CN 101901937 B CN101901937 B CN 101901937B CN 2010102551068 A CN2010102551068 A CN 2010102551068A CN 201010255106 A CN201010255106 A CN 201010255106A CN 101901937 B CN101901937 B CN 101901937B
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electrolyte
acid
cerium ion
ion
solution
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CN101901937A (en
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周德璧
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TIANJIN JIUJU ENERGY TECHNOLOGY DEVELOPMENT Co Ltd
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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
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract

The invention discloses cerium ion electrolyte using a silver ion as an anode catalyst and a preparation method thereof and aims to provide electrolyte capable of effectively improving the reaction rate of oxidation reduction of Ce3+/Ce4+ electron pairs and improving the charging and discharging efficiency and cycle performance of cells and a preparation method thereof. The electrolyte comprises organic acid-containing or inorganic acid-containing aqueous solution using a cerium ion as a cation, wherein Ag+ content of the aqueous solution is 0.001 to 0.01mol/L. The organic acid is methylsulfonic acid, and the inorganic acid is sulfuric acid or nitric acid. The Ag+ added in the electrolyte is used as the anode catalyst. The cerium ion is a rare-earth element ion and forms a complex with acid radicals and solvent molecules in the solution. The addition of the Ag+ can influence the coordination of the cerium ion, promote the electron transport of the cerium ion on the surface of an electrode, improve the electrochemical performance of the Ce3+/Ce4+ electron pairs, and effectively improve the charging and discharging efficiency and cycle performance of cells.

Description

Silver ion is as cerium ion electrolyte of anode catalyst and preparation method thereof
Technical field
The present invention relates to electrochemical field, in particular, relate to a kind of being used for cerium ion Ce 3+/ Ce 4+Redox couple is the interpolation Ag of the redox cell of positive active material +As electrolyte of catalyst and preparation method thereof, and Ag +At Ce 3+/ Ce 4+Electricity is to the application in the redox reaction.
Background technology
At current energy field, regenerative resources such as development and use solar energy, wind energy more and more receive people's attention, for the stability that realizes supplying power, need the extensive efficiently energy storage technology of exploitation.Secondary cell is important energy storage technology.Wherein redox flow batteries is zinc-bromine bettery, sodium polysulfide/bromine battery, vanadium cell etc., obtains research and development owing to have the special benefits face in extensive electric power storage direction, will progressively invest market.
Cerium is a kind of abundant rare earth element.Cerium in acid solution usually with Ce 3+And Ce 4+Exist.In industry, with the method for electrolysis from Ce 3+Preparation Ce 4+Be used for other fields such as organic synthesis as oxidant.Ce 4+As oxidant, can be used for handling waste water and organic synthesis.In addition, cerium is catalyst based is important cleaning catalyst for tail gases of automobiles.
Ce 3+/ Ce 4+Oxidation-reduction pair has very high standard electrode potential (1.61V), far above the current potential of the positive pole of several kinds of batteries of developing at present both at home and abroad.Ce 3+/ Ce 4+Electricity can be assembled into the redox cell of high-energy-density with zinc or other negative materials to as positive active material.Plurion Systems company studies and developed with pyrovinic acid is electrolytical zinc cerium battery, and theoretical voltage is 2.4V.
At Ce 3+/ Ce 4+Electricity is in the charging and discharge process as the battery of positive active material, and anodal the reaction is respectively Ce 3+Oxidation and Ce 4+Reduction, the reaction rate of these two reactions is lower, causes the loss of voltage higher, has restricted Ce 3+/ Ce 4+Electricity is to the exploitation as the cerium battery of positive active material.
Summary of the invention
The present invention is in order to overcome weak point of the prior art, to provide a kind of and can effectively improve Ce 3+/ Ce 4+Electricity improves electrolyte of battery efficiency and cycle performance and preparation method thereof to redox reaction rate.
Another object of the present invention provides a kind of Ag +At Ce 3+/ Ce 4+Electricity is to the application in the redox reaction.
A kind of silver ion comprises that as the cerium ion electrolyte of anode catalyst with cerium ion be cationic organic acid or the inorganic aqueous acid of containing, and the cerium ion in this aqueous solution is 3 valencys and 4 valencys, Ce 3+/ Ce 4+Constitute redox couple, it is characterized in that, contain Ag in this aqueous solution +, said Ag +Content 0.001-0.01mol/L.
Said organic acid is a pyrovinic acid, and said inorganic acid is a sulfuric acid.
Said Ag +Obtain through in solution, adding silver salt.Said silver salt is silver carbonate or silver nitrate or other solvable silver salt.
A kind of silver ion is characterized in that as the preparation method of the cerium ion electrolyte of anode catalyst, comprises the steps:
(1) organic acid or inorganic acid adding deionized water are configured to acid solution; Said organic acid is a pyrovinic acid, and said inorganic acid is a sulfuric acid.
(2) cerous carbonate is slowly joined in the above-mentioned acid solution, control reaction temperature is below 60 ℃;
(3) add silver salt behind the solution cool to room temperature that step (2) is obtained, add deionized water at last, constant volume obtains electrolyte; In this electrolyte, cerium ion concentration in pyrovinic acid is 1mol/L, and concentration is 0.5mol/L in sulfuric acid; Acid solutions is 4mol/L, Ag +Content is 0.001-0.01mol/L.
A kind of Ag +At Ce 3+/ Ce 4+Electricity is to the application in the redox reaction.Said silver salt is silver carbonate or silver nitrate or other solvable silver salt.
The present invention has following technique effect:
1, electrolyte of the present invention is in the cerium ion electrolyte of routine, to add Ag +As anode catalyst.Cerium ion is a kind of rare earth element ion, in solution, forms complex, Ag with acid group and solvent molecule +Adding can influence the coordination of cerium ion, thereby cerium ion is produced facilitation at the electron transfer of electrode surface, can improve Ce 3+/ Ce 4+The chemical property that electricity is right, thus battery efficiency and cycle performance improved effectively.
2, pass through in the electrolyte of the present invention to add excessive acid, make to exist part free sour in the electrolyte, hydrionic content is high, good conductivity.
3, cerium ion electrolysis additive Ag of the present invention +Consumption seldom, used raw material is extensive.
4, simple, the easy row of the preparation method of cerium ion electrolyte of the present invention.
Description of drawings
The Ag of Fig. 1, the different amounts of adding +The time Ce 3+/ Ce 4+The right reduction polarization curve of electricity compares;
Fig. 2, do not contain Ag +The cycle performance of battery of pyrovinic acid cerium electrolyte;
Fig. 3, Ag +Concentration is 0.001mol * L -1The time pyrovinic acid cerium electrolyte cycle performance of battery;
Fig. 4, Ag +Concentration is 0.006mol * L -1The time pyrovinic acid cerium electrolyte cycle performance of battery;
Fig. 5, Ag +Concentration is 0.01mol * L -1The time pyrovinic acid cerium electrolyte cycle performance of battery;
Fig. 6, do not contain Ag +Cerous sulfate electrolyte battery cycle performance;
Fig. 7, Ag +Concentration is 0.006mol * L -1Cerous sulfate electrolyte battery cycle performance.
Embodiment
Below in conjunction with specific embodiment the present invention is elaborated.
Silver carbonate or silver nitrate can directly add, and for the ease of experiment, can add by wiring solution-forming.
Wherein, the mass fraction of pyrovinic acid is 99.0%, and the mass fraction of sulfuric acid is 98%.The weight percent concentration of cerous carbonate is 99.5%.
Comparative Examples 1
Taking by weighing pyrovinic acid 38.79g joins and is configured to pyrovinic acid solution in the 30mL deionized water; Cerous carbonate 22.11g is slowly joined in the above-mentioned pyrovinic acid solution, and control reaction temperature is cooled to room temperature below 60 ℃; Add deionized water and be settled to 100mL, do not contained Ag +Pyrovinic acid cerium electrolyte.
As anodal electrolyte, negative pole electrolyte adopts ZnSO with the electrolyte of gained 4Solution is assembled into the Zn-Ce battery.The electrolysis tank both positive and negative polarity of experiment test adopts square graphite felt and zine plate respectively.The both positive and negative polarity chamber separates with homogeneous ion-exchange membrane.
Embodiment 1
(1) taking by weighing pyrovinic acid 28.79g joins the 40mL deionized water for stirring and evenly is configured to pyrovinic acid solution.
(2) cerous carbonate 22.11g is slowly joined in the above-mentioned pyrovinic acid solution stir, control reaction temperature is below 60 ℃.
(3) take by weighing the 10.00g pyrovinic acid and join in the 10mL deionized water, add the 0.0276g silver carbonate again, stirring obtains silver carbonate solution.Join in the above-mentioned silver carbonate solution behind the solution cool to room temperature that step (2) is obtained, add deionized water again and be settled to 100mL, obtain Ag +Concentration is 0.001mol * L -1, cerium ion concentration is the pyrovinic acid cerium electrolyte of 1mol/L.
As anodal electrolyte, negative pole electrolyte adopts ZnSO with the electrolyte of gained 4Solution is assembled into the Zn-Ce battery.The electrolysis tank both positive and negative polarity of experiment test adopts square graphite felt and zine plate respectively.The both positive and negative polarity chamber separates with homogeneous ion-exchange membrane.Battery is with 40mA * cm -2Carry out constant current charge-discharge, circulate 55 times, battery performance is stable.
Embodiment 2
(1) taking by weighing pyrovinic acid 28.79g joins the 30mL deionized water for stirring and evenly is configured to pyrovinic acid solution.
(2) cerous carbonate 22.11g is slowly joined in the above-mentioned pyrovinic acid solution stir, control reaction temperature is below 60 ℃.
(3) take by weighing the 10.00g pyrovinic acid and join in the 10mL deionized water, add the 0.1656g silver carbonate again, stirring obtains silver carbonate solution.Join in the above-mentioned silver carbonate solution behind the solution cool to room temperature that step (2) is obtained, add deionized water again and be settled to 100mL, obtain Ag +Concentration is 0.006mol * L -1, cerium ion concentration is the pyrovinic acid cerium electrolyte of 1mol/L.
As anodal electrolyte, negative pole electrolyte adopts ZnSO with the electrolyte of gained 4Solution is assembled into the Zn-Ce battery.The electrolysis tank both positive and negative polarity of experiment test adopts square graphite felt and zine plate respectively.The both positive and negative polarity chamber separates with homogeneous ion-exchange membrane.Battery is with 40mA * cm -2Carry out constant current charge-discharge, circulate 110 times, battery performance is stable.
Embodiment 3
(1) taking by weighing pyrovinic acid 28.79g joins the 30mL deionized water for stirring and evenly is configured to pyrovinic acid solution.
(2) cerous carbonate 22.11g is slowly joined in the above-mentioned pyrovinic acid solution stir, control reaction temperature is below 60 ℃.
(3) take by weighing the 10.00g pyrovinic acid and join in the 10mL deionized water, add the 0.276g silver carbonate again, stirring obtains silver carbonate solution.Join in the above-mentioned silver carbonate solution behind the solution cool to room temperature that step (2) is obtained, add deionized water again and be settled to 100mL, obtain Ag +Concentration is 0.01mol * L -1, cerium ion concentration is the pyrovinic acid cerium electrolyte of 1mol/L.
As anodal electrolyte, negative pole electrolyte adopts ZnSO with the electrolyte of gained 4Solution is assembled into the Zn-Ce battery.The electrolysis tank both positive and negative polarity of experiment test adopts square graphite felt and zine plate respectively.The both positive and negative polarity chamber separates with homogeneous ion-exchange membrane.Battery is with 40 mA * cm -2Carry out constant current charge-discharge, circulate 60 times, battery performance is stable.
Comparative Examples 2
(1) taking by weighing concentration is that 98% sulfuric acid 20.00g joins the 40mL deionized water for stirring and evenly is configured to sulfuric acid solution.
(2) cerous carbonate 11.05g is slowly joined in the above-mentioned sulfuric acid solution stir, control reaction temperature is below 60 ℃.
(3) add deionized water behind the solution cool to room temperature that step (2) is obtained and be settled to 100mL, obtaining cerium ion concentration is the cerous sulfate electrolyte of 0.5mol/L.
As anodal electrolyte, negative pole electrolyte adopts ZnSO with the electrolyte of gained 4Solution is assembled into the Zn-Ce battery.The electrolysis tank both positive and negative polarity of experiment test adopts square graphite felt and zine plate respectively.The both positive and negative polarity chamber separates with homogeneous ion-exchange membrane.Battery is with 40mA * cm -2Carry out constant current charge-discharge, battery performance is stable.
Embodiment 4
(1) taking by weighing concentration is that 98% sulfuric acid 20.00g joins the 40mL deionized water for stirring and evenly is configured to sulfuric acid solution.
(2) cerous carbonate 11.05g is slowly joined in the above-mentioned sulfuric acid solution stir, control reaction temperature is below 60 ℃.
(3) adding 6mL concentration behind the solution cool to room temperature that step (2) is obtained is the liquor argenti nitratis ophthalmicus of 0.1mol/L, adds deionized water again and is settled to 100mL, obtains Ag +Concentration is 0.006mol * L -1, cerium ion concentration is the cerous sulfate electrolyte of 0.5mol/L.
As anodal electrolyte, negative pole electrolyte adopts ZnSO with the electrolyte of gained 4Solution is assembled into the Zn-Ce battery.The electrolysis tank both positive and negative polarity of experiment test adopts square graphite felt and zine plate respectively.The both positive and negative polarity chamber separates with homogeneous ion-exchange membrane.Battery is with 40mA * cm -2Carry out constant current charge-discharge, battery performance is stable.
Laboratory report:
Add Ag +To Ce 3+/ Ce 4+Electricity adopts three-electrode system to test to the effect of chemical property.Work electrode is 1cm 2Platinized platinum, auxiliary electrode are 4cm 2Platinized platinum, saturated calomel electrode (SCE) is made reference electrode.At room temperature test the electrolyte Ce of gained on the platinum electrode 3+/ Ce 4+Electric right redox polarization curve is as shown in Figure 1.
In Fig. 1 and table 1: (a)---Comparative Examples 1 obtains does not add Ag +The cerium ion electrolyte of annex solution; (b)---the Ag that embodiment 1 obtains +Concentration is 0.001mol * L -1Cerium ion electrolyte; (c)---the Ag that embodiment 2 obtains +Content is 0.006mol * L -1Cerium ion electrolyte; (d)---the Ag that embodiment 3 obtains +Content is 0.01mol * L -1Cerium ion electrolyte.
Fig. 1 is for adding the Ag of different amounts +The time Ce 3+/ Ce 4+The reduction polarization curve that electricity is right.Visible by Fig. 1, under the same potential, add Ag +The cerium ion electrolyte Ce of annex solution (seeing curve b, c, d) 3+/ Ce 4+Electricity obviously increases kinetic current density, shows to add Ag +Increased Ce 3+/ Ce 4+The reaction rate of reduction process.Wherein, electrolyte (embodiment 2) Ce of curve c representative 3+/ Ce 4+Electricity is maximum to kinetic current density, shows Ag +Concentration is 0.006mol * L -1The time, the chemical property of electrolyte is best.
Fig. 2-Fig. 5 is for adding the Ag of different amounts +Zn-Ce battery circulation sketch map.Table 1 is the each circulation of Ce-Zn battery corresponding end of charge voltage, initial discharge voltage and energy efficiency data under each embodiment 1-3.Can know from Fig. 2 and table 1, not contain Ag +The Ce-Zn battery of annex solution only circulates 60 times, and initial discharge voltage is 2.08V, and descends very soon.Add Ag +Concentration is 0.006mol * L -1When (embodiment 2), circulate 110 times, stable performance, initial discharge voltage is 2.06V, circulating after 110 times is 2.10V.
Fig. 6 and Fig. 7 are respectively that Comparative Examples 2 obtains does not add Ag +The adding Ag that obtains of cerous sulfate electrolyte and embodiment 4 +0.006mol/L the Zn-Ce cycle performance of battery figure that forms of cerous sulfate electrolyte.Table 2 is Comparative Examples 2 and the corresponding end of charge voltage of the each circulation of 4 times Ce-Zn batteries of embodiment, initial discharge voltage data.Can know from table 2 data: add Ag +Battery charging voltage is obviously reduced, and discharge voltage significantly improves, and explanation can significantly improve anodal reactivity worth.
It is the redox cell of positive active material with the cerium that the present invention can be applicable to various, and like Zn-Ce battery, V-Ce, Cr-Ce battery etc. also can be applicable to relate to Ce 3+/ Ce 4+Other industrial circles of redox reaction.As in organic synthesis and waste water treatment, with Ce 4+Be oxidant, in these processes, with the method regeneration Ce of electrolysis 4+, patent art also is applicable to these technologies.
Figure 256725DEST_PATH_IMAGE002

Claims (5)

1. one kind is used for cerium ion Ce 3+/ Ce 4+Redox couple is the interpolation Ag of the redox cell of positive active material +As the electrolyte of catalyst, comprise that with cerium ion be cationic organic acid or the inorganic aqueous acid of containing, it is characterized in that, contain Ag in this aqueous solution +, said Ag +Content be 0.001-0.01mol/L; Said organic acid is a pyrovinic acid, and said inorganic acid is a sulfuric acid, and cerium ion concentration in containing the electrolyte of pyrovinic acid is 1mol/L, and concentration is 0.5mol/L in containing the electrolyte of sulfuric acid, and the concentration of organic acid or inorganic acid is 4mol/L.
2. according to claim 1 being used for cerium ion Ce 3+/ Ce 4+Redox couple is the interpolation Ag of the redox cell of positive active material +Electrolyte as catalyst is characterized in that, said Ag +Obtain through in solution, adding silver salt.
3. according to claim 2 being used for cerium ion Ce 3+/ Ce 4+Redox couple is the interpolation Ag of the redox cell of positive active material +Electrolyte as catalyst is characterized in that, said silver salt is silver carbonate or silver nitrate.
4. claim 1 described being used for cerium ion Ce 3+/ Ce 4+Redox couple is the interpolation Ag of the redox cell of positive active material +Preparation method as the electrolyte of catalyst is characterized in that, comprises the steps:
(1) organic acid or inorganic acid adding deionized water are configured to acid solution; Said organic acid is a pyrovinic acid, and said inorganic acid is a sulfuric acid;
(2) cerous carbonate is slowly joined in the above-mentioned acid solution, control reaction temperature is below 60 ℃;
(3) add silver salt behind the solution cool to room temperature that step (2) is obtained; Add deionized water at last, constant volume obtains electrolyte, in the electrolyte that obtains; Cerium ion concentration in containing the electrolyte of pyrovinic acid is 1mol/L; Concentration is 0.5mol/L in containing the electrolyte of sulfuric acid, and the concentration of organic acid or inorganic acid is 4mol/L, Ag +Content 0.001-0.01mol/L.
5. according to claim 4 being used for cerium ion Ce 3+/ Ce 4+Redox couple is the interpolation Ag of the redox cell of positive active material +Preparation method as the electrolyte of catalyst is characterized in that said silver salt is silver carbonate or silver nitrate.
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CN102427143A (en) * 2011-11-11 2012-04-25 周德璧 Electrolyte using aminosulfonic acid as solvent and redox cell using the same
CN104272513B (en) * 2012-03-05 2017-07-18 Eos控股公司 Redox flow batteries for hydrogen manufacturing
CN103794813B (en) * 2014-03-07 2015-12-02 江西理工大学 Europium cerium flow battery
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CN108172317B (en) * 2018-01-03 2021-07-20 燕山大学 Method for electrochemically decomposing radioactive waste resin
CN112993356A (en) * 2019-12-12 2021-06-18 中国科学院大连化学物理研究所 Method for improving electrochemical activity of cathode of all-vanadium redox flow battery

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