CN102637892B - Preparation method of all-vanadium-ion redox flow battery solution - Google Patents
Preparation method of all-vanadium-ion redox flow battery solution Download PDFInfo
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- CN102637892B CN102637892B CN201210103879.3A CN201210103879A CN102637892B CN 102637892 B CN102637892 B CN 102637892B CN 201210103879 A CN201210103879 A CN 201210103879A CN 102637892 B CN102637892 B CN 102637892B
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Abstract
The invention relates to the field of battery manufacturing and energy storage, particularly relates to a preparation method of all-vanadium-ion redox flow battery (vanadium battery) solution with high concentration and good temperature stability, and solves the problems of low concentration and poor temperature stability of the conventional vanadium battery solution in the prior art. According to the preparation method, vanadyl sulfate, sulfuric acid and water serve as raw materials, a proper proportion of carbohydrate organic matters are added into the raw materials, the concentration of the vanadyl sulfate in the solution is 2mol/L to 4mol/L, the concentration of the sulfuric acid in the solution is 1mol/L to 3mol/L, the concentration of the carbohydrate organic matters in the solution is 0.5mol/L to 3mol/L, and one or more of monosaccharide, disaccharide and polysaccharide serve as the carbohydrate organic matters. The preparation method is simple in technique and easy to operate, the raw materials are easy to obtain, and the vanadium battery solution with good temperature stability can be obtained. The solution is good in electrochemical reversibility and high in conductivity and can realize the charge and discharge of a battery.
Description
Technical field
The present invention relates to battery manufacture and stored energy field, be specially the preparation method of all vanadium ion redox flow battery (vanadium cell) electrolyte of a kind of high concentration, good stability.
Background technology
Vanadium oxide reduction flow battery, is called for short vanadium cell.A kind of novel electrochemical energy storage system, compared with traditional storage battery, the feature such as having can be fast, large capacity discharges and recharges, self-discharge rate is low and battery structure is simple, it is the ideal source form that meets the extensive energy storage of the novel energy such as wind energy, solar energy.Vanadium cell both positive and negative polarity electrolyte is for containing VO
2+/ VO
2 +with V
2+/ V
3+the sulfuric acid solution of oxidation-reduction pair, it is not only conducting medium, realizes especially the electroactive material of stored energy, is the core of vanadium cell energy storage and Conversion of Energy.The concentration of vanadium ion is the greatest factor that determines this energy content of battery density.The precipitation that occurs vanadium species in using due to the reality phenomenon such as condense, makes the current working concentration of electrolyte of vanadium redox battery in 1.5mol/L left and right, energy density lower (25Wh/kg).Therefore, both needed the electrolyte solution of high concentration to realize the high-energy-density of battery in reality, and required again it to have high stability, this is the key technical problem that vanadium cell enters the urgent need solution of practical stage.
At present, the preparation method of electrolyte of employing mainly contains:
1. by V
2o
5mix with a certain amount of concentrated sulfuric acid, after electrolysis, obtain VOSO
4solution, then carries out discharging and recharging of battery.
2. the part by weight dilution by 1: 1 with distilled water by the concentrated sulfuric acid, adds V
2o
3, more progressively add V
2o
5, cooled and filtered, that obtain blueness is VOSO
4acid solution, then carries out discharging and recharging of battery.
3. by VOSO
4directly be dissolved in (1～9mol/L) in sulfuric acid, then carry out discharging and recharging of battery.
4. by NH
4vO
3be dissolved in the certain density concentrated sulfuric acid, obtain VO
2+, V
3+, NH
4 +, SO
4 2-the system coexisting, this system can directly be carried out discharging and recharging of battery, obtains the required electrolyte of both positive and negative polarity.
Have research to improve the stability of electrolyte and the solubility of vanadium ion by adding glycerine and sodium sulphate (2%), but the raising of concentration and warm stability is not fairly obvious.
Said method all fails the concentration of electrolyte of vanadium redox battery and warm stability significantly to improve.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of all vanadium ion redox flow battery electrolyte, solve the problems such as the lower and warm less stable of the concentration of the electrolyte of vanadium redox battery existing in prior art.
Technical scheme of the present invention is:
A kind of preparation method of all vanadium ion redox flow battery electrolyte, taking vanadic sulfate, sulfuric acid and water as raw material, add the carbohydrate organic substance of proper proportion, the concentration of vanadic sulfate in electrolyte is 2～4mol/L, the concentration of sulfuric acid in electrolyte is 1～3mol/L, and the concentration of carbohydrate organic substance in electrolyte is 0.5mol/L～3mol/L (being preferably 1mol/L～2mol/L).
In the present invention, carbohydrate organic substance is dissolved in the aqueous solution in advance, and preparation contains the organic aqueous solution of carbohydrate, then takes the sulfuric acid of aequum and vanadic sulfate crystal and join and contain in the organic aqueous solution of carbohydrate, this solution is carried out to constant volume and obtain desired concn; Or sulfuric acid and vanadic sulfate crystal are dissolved in the aqueous solution in advance, then add carbohydrate organic substance, constant volume obtains desired concn.The obtained effect of these two kinds of addition manners is identical.
In the present invention, in vanadic sulfate course of dissolution, carry out ultrasonic wave processing, processing time 30～90min.
In the present invention, in carbohydrate organic substance course of dissolution, carry out ultrasonic wave processing, processing time 10～20min.
In the present invention, vanadic sulfate carries out heat treated in course of dissolution, and heating-up temperature is between 80 DEG C～100 DEG C.
In the present invention, carbohydrate organic substance is monosaccharide and disaccharide or polysaccharide.Wherein, monose is glucose, fructose or galactolipin; Disaccharide is sucrose, lactose or maltose; Polysaccharide is by more than 10 monose molecular composition.
Carbohydrate organic substance be following one or more: glucose, fructose, galactolipin, lactose, maltose, starch, dextrin, glycogen sucrose, brown sugar, white sugar, granulated sugar.
In the present invention, the purity requirement of vanadic sulfate is at 97wt%～98wt%, as lower in raw material sulphuric acid vanadyl crystal purity, needs solution to carry out filtration treatment.
Advantage of the present invention:
1, the present invention is taking vanadic sulfate, sulfuric acid and water as raw material, adopt and add the organic method of proper proportion carbohydrate, process is simple, processing ease, raw material is easy to get, and can obtain the electrolyte of vanadium redox battery of high concentration, good stability, can prepare the electrolyte of vanadium redox battery of 2～4mol/L, and can stablize and deposited phenomenon did not occur above in 6 months, and complete the preliminary test that discharges and recharges.The effect of carbohydrate organic substance is to suppress vanadium plasma and Precipitation of the same race and that association xenogenesis ion causes.Discharge and recharge test and show, the charge/discharge capacity of electrolyte of the present invention is the twice of conventional 1.5mol/L electrolyte, and voltage efficiency, coulombic efficiency and energy efficiency and conventional 1.5mol/L electrolyte basic identical, be improved the potentiality of vanadium cell specific energy and specific power.
2, carbohydrate organic substance of the present invention, its main component is environmentally friendly material, can not produce adverse effect to environment, meets the feature of the environmental protection of vanadium cell.And consumption is low, can not affect greatly the cost of vanadium cell.
Embodiment
Embodiment 1
0.5mol glucose, 0.5mol lactose and 0.5mol sucrose dissolved, in the aqueous solution, are made and contain the organic aqueous solution of carbohydrate.Carbohydrate organic substance carries out ultrasonic wave processing, processing time 10min in course of dissolution.Then, taking the sulfuric acid of 2mol and 3mol and vanadic sulfate crystal joins and contains in the organic aqueous solution of carbohydrate, in vanadic sulfate course of dissolution, carry out heat treated, 80 DEG C of heating-up temperatures, after all dissolving, it pours in volumetric flask, be settled to 1000mL, obtain the vanadic sulfate solution of 3mol/L.Taking graphite as positive and negative pole material, both positive and negative polarity solution concentration is the aqueous sulfuric acid that contains the organic 3mol/L vanadic sulfate of carbohydrate, and the density of charging current is 50mA/cm
2, discharge current density is 50mA/cm
2, voltage efficiency is 84%, and coulombic efficiency is 91%, and energy efficiency is 76%.This electrolyte electrochemical reversibility is good, and conductivity is high, can realize battery charging and discharging.
Embodiment 2
0.5mo galactolipin and 0.5mol maltose are dissolved in the aqueous solution, make and contain the organic aqueous solution of carbohydrate.Carbohydrate organic substance carries out ultrasonic wave processing, processing time 15min in course of dissolution.Then, taking the sulfuric acid of 2mol and 3mol and vanadic sulfate crystal joins and contains in the organic aqueous solution of carbohydrate, in vanadic sulfate course of dissolution, carry out heat treated, 90 DEG C of heating-up temperatures, after all dissolving, it pours in volumetric flask, be settled to 1000mL, obtain the vanadic sulfate solution of 3mol/L.Taking graphite as positive and negative pole material, both positive and negative polarity solution concentration is the aqueous sulfuric acid that contains the organic 3mol/L vanadic sulfate of carbohydrate, and the density of charging current is 50mA/cm
2, discharge current density is 50mA/cm
2, voltage efficiency is 82%, and coulombic efficiency is 93%, and energy efficiency is 76%.This electrolyte electrochemical reversibility is good, and conductivity is high, can realize battery charging and discharging.
Embodiment 3
Take sulfuric acid and the vanadic sulfate crystal of 2mol and 3.5mol, join in the 500mL aqueous solution, 80 DEG C of heating-up temperatures, after all dissolving, it adds 1mol fructose, 1mol maltose, continue to stir, after dissolving completely, add deionized water and be settled to 1000mL, obtain the vanadic sulfate solution of 3.5mol/L.In vanadic sulfate course of dissolution, carry out ultrasonic wave processing, processing time 90min.Taking graphite as positive and negative pole material, both positive and negative polarity solution concentration is the aqueous sulfuric acid that contains the organic 3.5mol/L vanadic sulfate of carbohydrate, and the density of charging current is 50mA/cm
2, discharge current density is 50mA/cm
2, voltage efficiency is 87%, and coulombic efficiency is 93%, and energy efficiency is 81%.This electrolyte electrochemical reversibility is good, and conductivity is high, can realize battery charging and discharging.
Embodiment 4
The sulfuric acid and the vanadic sulfate crystal that take 3mol and 4mol, join in the 500mL aqueous solution, 90 DEG C of heating-up temperatures, after all dissolving, it adds: 1mol lactose, 1mol glucose, continue to stir, after dissolving completely, add deionized water and be settled to 1000mL, obtain the vanadic sulfate solution of 4mol/L.In vanadic sulfate course of dissolution, carry out ultrasonic wave processing, processing time 90min.Taking graphite as positive and negative pole material, both positive and negative polarity solution concentration is the aqueous sulfuric acid that contains the organic 4mol/L vanadic sulfate of carbohydrate, and the density of charging current is 50mA/cm
2, discharge current density is 50mA/cm
2, voltage efficiency is 80%, and coulombic efficiency is 90%, and energy efficiency is 72%.This electrolyte electrochemical reversibility is good, and conductivity is high, can realize battery charging and discharging.
The electrolyte of vanadium redox battery concentration that the present invention obtains can reach 2～4mol/L, leave standstill and do not precipitate for 6 months, the charge/discharge capacity that discharges and recharges test demonstration electrolyte of the present invention is the twice of conventional 1.5mol/L electrolyte, and voltage efficiency, coulombic efficiency and energy efficiency and conventional 1.5mol/L electrolyte are basic identical, illustrate that this electrolyte is in improving capacity, battery still has good charging and discharging capabilities.
Claims (4)
1. a preparation method for all vanadium ion redox flow battery electrolyte, is characterized in that, 0.5mol glucose, 0.5mol lactose and 0.5mol sucrose dissolved, in the aqueous solution, are made and contain the organic aqueous solution of carbohydrate; Carbohydrate organic substance carries out ultrasonic wave processing, processing time 10min in course of dissolution; Then, take 2mol sulfuric acid and 3mol vanadic sulfate crystal and join and contain in the organic aqueous solution of carbohydrate, in vanadic sulfate course of dissolution, carry out heat treated, 80 DEG C of heating-up temperatures, after it all dissolves, pour in volumetric flask, be settled to 1000mL, obtain the vanadic sulfate solution of 3mol/L; Taking graphite as positive and negative pole material, both positive and negative polarity solution is the aqueous sulfuric acid that contains the organic 3mol/L vanadic sulfate of carbohydrate, and the density of charging current is 50 mA/cm
2, discharge current density is 50 mA/cm
2, voltage efficiency is 84%, and coulombic efficiency is 91%, and energy efficiency is 76%.
2. a preparation method for all vanadium ion redox flow battery electrolyte, is characterized in that, 0.5mol galactolipin and 0.5mol maltose are dissolved in the aqueous solution, makes and contains the organic aqueous solution of carbohydrate; Carbohydrate organic substance carries out ultrasonic wave processing, processing time 15min in course of dissolution; Then, take 2mol sulfuric acid and 3mol vanadic sulfate crystal and join and contain in the organic aqueous solution of carbohydrate, in vanadic sulfate course of dissolution, carry out heat treated, 90 DEG C of heating-up temperatures, after it all dissolves, pour in volumetric flask, be settled to 1000mL, obtain the vanadic sulfate solution of 3mol/L; Taking graphite as positive and negative pole material, both positive and negative polarity solution is the aqueous sulfuric acid that contains the organic 3mol/L vanadic sulfate of carbohydrate, and the density of charging current is 50 mA/cm
2, discharge current density is 50 mA/cm
2, voltage efficiency is 82%, and coulombic efficiency is 93%, and energy efficiency is 76%.
3. the preparation method of an all vanadium ion redox flow battery electrolyte, it is characterized in that, take 2mol sulfuric acid and 3.5mol vanadic sulfate crystal, join in the 500mL aqueous solution, 80 DEG C of heating-up temperatures add 1mol fructose, 1mol maltose after it all dissolves, continue to stir, after dissolving completely, add deionized water and be settled to 1000mL, obtain the vanadic sulfate solution of 3.5mol/L; In vanadic sulfate course of dissolution, carry out ultrasonic wave processing, processing time 90min; Taking graphite as positive and negative pole material, both positive and negative polarity solution is the aqueous sulfuric acid that contains the organic 3.5mol/L vanadic sulfate of carbohydrate, and the density of charging current is 50 mA/cm
2, discharge current density is 50 mA/cm
2, voltage efficiency is 87%, and coulombic efficiency is 93%, and energy efficiency is 81%.
4. the preparation method of an all vanadium ion redox flow battery electrolyte, it is characterized in that, take 3mol sulfuric acid and 4mol vanadic sulfate crystal, join in the 500mL aqueous solution, 90 DEG C of heating-up temperatures add: 1mol lactose, 1mol glucose after it all dissolves, continue to stir, after dissolving completely, add deionized water and be settled to 1000mL, obtain the vanadic sulfate solution of 4mol/L; In vanadic sulfate course of dissolution, carry out ultrasonic wave processing, processing time 90min; Taking graphite as positive and negative pole material, both positive and negative polarity solution is the aqueous sulfuric acid that contains the organic 4mol/L vanadic sulfate of carbohydrate, and the density of charging current is 50 mA/cm
2, discharge current density is 50 mA/cm
2, voltage efficiency is 80%, and coulombic efficiency is 90%, and energy efficiency is 72%.
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|---|---|---|---|
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| JP2014216203A (en) * | 2013-04-25 | 2014-11-17 | 住友電気工業株式会社 | Electrolyte for redox flow battery and redox flow battery |
| CN111477925B (en) * | 2020-06-08 | 2023-01-10 | 雅安市中甫新能源开发有限公司 | Additive for preparing high-concentration vanadium battery electrolyte and preparation method |
| CN114497664A (en) * | 2022-01-17 | 2022-05-13 | 武汉科技大学 | Vanadium battery negative electrode electrolyte and preparation method thereof |
| CN114497665A (en) * | 2022-01-17 | 2022-05-13 | 武汉科技大学 | Method for reducing capacity attenuation of vanadium battery |
| CN117558956B (en) * | 2023-12-29 | 2024-04-05 | 山西国润储能科技有限公司 | Preparation method of high-stability vanadium electrolyte |
Citations (3)
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|---|---|---|---|---|
| CN1507103A (en) * | 2002-12-12 | 2004-06-23 | 肖玉璋 | High-energy static vanadium cell |
| CN1719655A (en) * | 2005-03-29 | 2006-01-11 | 攀钢集团攀枝花钢铁研究院 | All-vanadium ion flow battery electrolyte and preparation method thereof |
| CN102376970A (en) * | 2010-08-11 | 2012-03-14 | 中国科学院金属研究所 | Method for preparing all-vanadium ion redox flow battery electrolyte |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1507103A (en) * | 2002-12-12 | 2004-06-23 | 肖玉璋 | High-energy static vanadium cell |
| CN1719655A (en) * | 2005-03-29 | 2006-01-11 | 攀钢集团攀枝花钢铁研究院 | All-vanadium ion flow battery electrolyte and preparation method thereof |
| CN102376970A (en) * | 2010-08-11 | 2012-03-14 | 中国科学院金属研究所 | Method for preparing all-vanadium ion redox flow battery electrolyte |
Non-Patent Citations (2)
| Title |
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| "全钒液流电池阴极电解液稳定性";李小山等;《化工学报》;20111231;第62卷(第S2期);第140-141页 * |
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Effective date of registration: 20220829 Address after: 110172 doors 1, 2 and 3, No. 189-28, JINZI street, Shenfu demonstration zone, Shenyang City, Liaoning Province Patentee after: Liaoning kejing New Material Co.,Ltd. Address before: 1st Floor, Standard Workshop, No. 29, High-tech Park, Chaoyang City, Liaoning Province, 122005 Patentee before: CHAOYANG HUADING ENERGY STORAGE TECHNOLOGY Co.,Ltd. |