CN101901937A - 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

Info

Publication number
CN101901937A
CN101901937A CN2010102551068A CN201010255106A CN101901937A CN 101901937 A CN101901937 A CN 101901937A CN 2010102551068 A CN2010102551068 A CN 2010102551068A CN 201010255106 A CN201010255106 A CN 201010255106A CN 101901937 A CN101901937 A CN 101901937A
Authority
CN
China
Prior art keywords
acid
electrolyte
ion
silver
cerium ion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2010102551068A
Other languages
Chinese (zh)
Other versions
CN101901937B (en
Inventor
周德壁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TIANJIN JIUJU ENERGY TECHNOLOGY DEVELOPMENT Co Ltd
Original Assignee
TIANJIN JIUJU ENERGY TECHNOLOGY DEVELOPMENT Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TIANJIN JIUJU ENERGY TECHNOLOGY DEVELOPMENT Co Ltd filed Critical TIANJIN JIUJU ENERGY TECHNOLOGY DEVELOPMENT Co Ltd
Priority to CN2010102551068A priority Critical patent/CN101901937B/en
Publication of CN101901937A publication Critical patent/CN101901937A/en
Application granted granted Critical
Publication of CN101901937B publication Critical patent/CN101901937B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Hybrid Cells (AREA)

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 are subjected to people's attention, for the stability that realizes powering, 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 having special benefits 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.Industrial, the method for using electrolysis is 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 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 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 +, described Ag +Content 0.001-0.01mol/L.
Described organic acid is a pyrovinic acid, and described inorganic acid is sulfuric acid or nitric acid etc.
Described Ag +Obtain by in solution, adding silver salt.Described 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; Described organic acid is a pyrovinic acid, and described inorganic acid is sulfuric acid or nitric acid etc.
(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.Described 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 to add Ag in the cerium ion electrolyte of routine +As anode catalyst.Cerium ion is a kind of rare earth element ion, forms complex, Ag with acid group and solvent molecule in solution +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 height, 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
The present invention is described in detail below in conjunction with specific embodiment.
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 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.As seen from Figure 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 shows Ag to kinetic current density maximum +Concentration is 0.006mol * L -1The time, chemical property the best of electrolyte.
Fig. 2-Fig. 5 is for adding the Ag of different amounts +Zn-Ce battery circulation schematic diagram.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.From Fig. 2 and table 1 as can be known, do not contain Ag +The Ce-Zn battery of annex solution only circulates 60 times, and initial discharge voltage is 2.08V, and very fast decline.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 +Cerous sulfate electrolyte and the adding Ag that obtains of embodiment 4 +0.006mol/L the Zn-Ce cycle performance of battery figure that forms of cerous sulfate electrolyte.Table 2 is the corresponding end of charge voltage of the each circulation of Comparative Examples 2 and 4 times Ce-Zn batteries of embodiment, initial discharge voltage data.From table 2 data as can be known: 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 as 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+, the art of this patent also is applicable to these technologies.
Figure 2010102551068100002DEST_PATH_IMAGE001

Claims (7)

1. a 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 it is characterized in that, contains Ag in this aqueous solution +, described Ag +Content be 0.001-0.01mol/L.
2. silver ion according to claim 1 is characterized in that as the cerium ion electrolyte of anode catalyst described organic acid is a pyrovinic acid, and described inorganic acid is sulfuric acid or nitric acid.
3. silver ion according to claim 1 is characterized in that as the cerium ion electrolyte of anode catalyst, described Ag +Obtain by in solution, adding silver salt.
4. silver ion according to claim 3 is characterized in that as the cerium ion electrolyte of anode catalyst described silver salt is silver carbonate or silver nitrate.
5. the described silver ion of claim 1 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; Described organic acid is a pyrovinic acid, and described inorganic acid is sulfuric acid or nitric 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 pyrovinic acid is 1mol/L, concentration is 0.5mol/L in sulfuric acid, and the concentration of organic acid or inorganic acid is 4mol/L, Ag +Content 0.001-0.01mol/L.
6. the preparation method of cerium ion electrolyte according to claim 5 is characterized in that, described silver salt is silver carbonate or silver nitrate.
7. Ag +At Ce 3+/ Ce 4+Electricity is to the application in the redox reaction.
CN2010102551068A 2010-08-17 2010-08-17 Cerium ion electrolyte using silver ion as anode catalyst and preparation method thereof Expired - Fee Related CN101901937B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2010102551068A CN101901937B (en) 2010-08-17 2010-08-17 Cerium ion electrolyte using silver ion as anode catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2010102551068A CN101901937B (en) 2010-08-17 2010-08-17 Cerium ion electrolyte using silver ion as anode catalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN101901937A true CN101901937A (en) 2010-12-01
CN101901937B CN101901937B (en) 2012-07-04

Family

ID=43227281

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2010102551068A Expired - Fee Related CN101901937B (en) 2010-08-17 2010-08-17 Cerium ion electrolyte using silver ion as anode catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN101901937B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102427143A (en) * 2011-11-11 2012-04-25 周德璧 Electrolyte using sulfamic acid as solvent and redox battery using electrolyte
CN103794813A (en) * 2014-03-07 2014-05-14 江西理工大学 Europium cerium flow cell
CN104272513A (en) * 2012-03-05 2015-01-07 Eos控股公司 Redox flow battery for hydrogen generation
CN107674992A (en) * 2017-09-21 2018-02-09 中国科学院过程工程研究所 A kind of cleaning extracting method of argent
CN108172317A (en) * 2018-01-03 2018-06-15 燕山大学 A kind of method of electrochemical decomposition radioactive spent 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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1598063A (en) * 2003-09-18 2005-03-23 攀枝花钢铁有限责任公司钢铁研究院 Process for electrolyzing preparing electrolyte of full vanadium ion flow battery
WO2008111946A1 (en) * 2007-03-09 2008-09-18 Jd Holding, Inc. Inherently safe redox flow battery storage system

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1598063A (en) * 2003-09-18 2005-03-23 攀枝花钢铁有限责任公司钢铁研究院 Process for electrolyzing preparing electrolyte of full vanadium ion flow battery
WO2008111946A1 (en) * 2007-03-09 2008-09-18 Jd Holding, Inc. Inherently safe redox flow battery storage system

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102427143A (en) * 2011-11-11 2012-04-25 周德璧 Electrolyte using sulfamic acid as solvent and redox battery using electrolyte
CN104272513A (en) * 2012-03-05 2015-01-07 Eos控股公司 Redox flow battery for hydrogen generation
CN104272513B (en) * 2012-03-05 2017-07-18 Eos控股公司 Redox flow batteries for hydrogen manufacturing
CN103794813A (en) * 2014-03-07 2014-05-14 江西理工大学 Europium cerium flow cell
CN103794813B (en) * 2014-03-07 2015-12-02 江西理工大学 Europium cerium flow battery
CN107674992A (en) * 2017-09-21 2018-02-09 中国科学院过程工程研究所 A kind of cleaning extracting method of argent
WO2019056837A1 (en) * 2017-09-21 2019-03-28 中国科学院过程工程研究所 Clean extraction method for metal silver
CN107674992B (en) * 2017-09-21 2019-08-09 中国科学院过程工程研究所 A kind of cleaning extracting method of metallic silver
US11566333B2 (en) 2017-09-21 2023-01-31 Institute Of Process Engineering, Chinese Academy Of Sciences Method for cleanly extracting metallic silver
CN108172317A (en) * 2018-01-03 2018-06-15 燕山大学 A kind of method of electrochemical decomposition radioactive spent resin
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

Also Published As

Publication number Publication date
CN101901937B (en) 2012-07-04

Similar Documents

Publication Publication Date Title
Dong et al. A novel titanium/manganese redox flow battery
KR102410425B1 (en) All-vanadium sulfate acid redox flow battery system
CN101901937B (en) Cerium ion electrolyte using silver ion as anode catalyst and preparation method thereof
CN101593841B (en) Redox flow battery and redox flow battery pack
CN104269572B (en) The preparation method of the vanadium redox battery electrolyte that complex stabilizer optimizes
CN101572319A (en) Electrolyte for all-vanadium redox flow battery and preparation method thereof, and all-vanadium redox flow battery including the electrolyte
CN102354762A (en) Method for manufacturing high-purity vanadium battery electrolyte
CN106549179B (en) A kind of organic system lithium quinone flow battery
CN104795567A (en) Water system lithium-ion/sodium-ion battery based on iodide ion solution cathode and organic matter anode
CN103401045A (en) Flow-battery energy storage system with photoelectric effect
CN102881931A (en) Phosphorus-containing all-vanadium redox flow battery anode electrolyte
Wei et al. From spent Zn–MnO2 primary batteries to rechargeable Zn–MnO2 batteries: A novel directly recycling route with high battery performance
CN110416586A (en) Iron-based flow battery and its positive and negative anodes electrolyte and preparation method
CN105280943B (en) A kind of full manganese flow battery
CN105810891A (en) MnO2/CeO2 combined electrode with porous structure and preparation method and application thereof
CN102881932B (en) Vanadium redox flow battery electrolyte containing manganese
CN114447386A (en) Preparation method of all-vanadium redox flow battery electrolyte
JP6247778B2 (en) Quinone polyhalide flow battery
CN117586316B (en) Iron complex, preparation method thereof and application thereof in solid energy storage material of flow battery
CN101859903B (en) Carbon electrode material treating agent and method for treating electrode materials by using same
CN102427143A (en) Electrolyte using sulfamic acid as solvent and redox battery using electrolyte
CN102376970B (en) Method for preparing all-vanadium ion redox flow battery electrolyte
CN103022528B (en) Method for cleanly removing copper ions in copper-bearing vanadium solution
CN106450400A (en) All-vanadium redox flow battery
CN108123174A (en) A kind of Alkaline Zinc iron liquid galvanic battery anode electrolyte and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
PP01 Preservation of patent right

Effective date of registration: 20131203

Granted publication date: 20120704

RINS Preservation of patent right or utility model and its discharge
PD01 Discharge of preservation of patent

Date of cancellation: 20141203

Granted publication date: 20120704

RINS Preservation of patent right or utility model and its discharge
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120704

Termination date: 20160817

CF01 Termination of patent right due to non-payment of annual fee