CN108400364A - Inhibit electrolysis additive of the dendritic lead generation of lead flow battery and preparation method thereof, lead fluid cell electrolyte and lead flow battery - Google Patents
Inhibit electrolysis additive of the dendritic lead generation of lead flow battery and preparation method thereof, lead fluid cell electrolyte and lead flow battery Download PDFInfo
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- CN108400364A CN108400364A CN201810092489.8A CN201810092489A CN108400364A CN 108400364 A CN108400364 A CN 108400364A CN 201810092489 A CN201810092489 A CN 201810092489A CN 108400364 A CN108400364 A CN 108400364A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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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
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
Electrolysis additive generated the invention discloses a kind of dendritic lead of inhibition lead flow battery and preparation method thereof, the lead fluid cell electrolyte comprising the electrolysis additive, and the lead flow battery comprising the lead fluid cell electrolyte.The electrolysis additive for inhibiting the dendritic lead of lead flow battery to generate is tin methane sulfonate, and preparation method is：Metallic tin and pyrovinic acid are reacted into 15 17h at 140 150 DEG C, gained filter residue is tin methane sulfonate.Additive can effectively inhibit cathode dendritic morphology, avoid cathode dendrite and fall, and to increase the charge/discharge capacity of pyrovinic acid lead flow battery, improve the coulombic efficiency of battery, also avoid short circuit of the battery in charging process, extend the service life of battery.
Description
Technical field
The present invention relates to pyrovinic acid lead flow battery technology field more particularly to a kind of dendritic lead of inhibition lead flow battery
Electrolysis additive of generation and preparation method thereof, lead fluid cell electrolyte and lead flow battery.
Background technology
Pyrovinic acid lead flow battery is a kind of energy-storage battery of novel high-power large capacity.Pyrovinic acid lead liquid stream electricity
Pond, positive and negative anodes electrolyte is identical, and diaphragm is not needed between battery plus-negative plate, has saved cost；Can guard station formula, scale setting spirit
It is living.By extensive concern due to it has many advantages, such as.Pyrovinic acid lead flow battery is electrolysis with pyrovinic acid lead and pyrovinic acid
Electrolyte is transported to from fluid reservoir in battery by external pump, carries out sufficient electrochemical reaction by liquid, wherein two when charging
Valence lead ion is with PbO2Form be deposited on anode, the cathode of battery, the PbO of discharge process anode are deposited on metallic lead2With
The lead of cathode is again with Pb2+Form come back in electrolyte, so circulate.Pyrovinic acid lead flow battery is anti-
The principle is answered to be：
Anode：Pb2++2H2O-2e-→PbO2++4H+
Cathode：Pb2++2e→Pb
Overall reaction：2Pb2++2H2O→Pb+PbO2+4H+；
Although pyrovinic acid lead flow battery has the advantages that flexible design, at low cost etc., but after charge and discharge for several times, bears
The Pb of pole2+It can be deposited on negative plates in the form of dendrite, lead to battery：
(1) capacity is low, and because it generates dendrite in charge and discharge process, dendrite is easy to fall off during charge and discharge cycles,
Battery capacity is caused to decline, coulombic efficiency reduces.
(2) short life, in battery certain charging process, the dendrite of the lead growth of cathode may be in charging process
Anode is in contact, and battery short circuit is caused to fail, and cycle life shortens.
Invention content
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, and it is negative to provide one kind improvement in charging process
The form of pole lead dendritic crystal, to improve the cycle life of pyrovinic acid lead flow battery, the electrolyte of energy efficiency and coulombic efficiency
Additive and preparation method thereof, lead fluid cell electrolyte and lead flow battery.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of electrolysis additive for inhibiting the dendritic lead of lead flow battery to generate, the electrolysis additive are pyrovinic acid
Tin.
The inventive concept total as one is generated the present invention also provides a kind of above-mentioned dendritic lead of inhibition lead flow battery
The preparation method of electrolysis additive, includes the following steps：
Metallic tin and pyrovinic acid are reacted into 15-17h at 140-150 DEG C, reaction solution is filtered, gained filter residue is first
Base sulfonic acid tin.
The inventive concept total as one, the present invention also provides a kind of lead fluid cell electrolyte, including pyrovinic acid lead,
Pyrovinic acid and deionized water further include such as the above-mentioned electrolysis additive for inhibiting the dendritic lead of lead flow battery to generate or above-mentioned
Preparation method obtained by inhibit the electrolysis additive that the dendritic lead of lead flow battery generates.
The pyrovinic acid lead flow battery dendrite lead that cathode generates in charging process, experiments have shown that, add in the electrolytic solution
The ratio of the electroactive substance in additive and electrolyte is considered as when doping.Preferably, the tin methane sulfonate
A concentration of 0.5-1.5mmol/L.
Preferably, a concentration of 0.6-1.0mmol/L of the tin methane sulfonate.
Preferably, in the lead fluid cell electrolyte, a concentration of 1-1.8mol/L of lead ion, hydrionic concentration
0.3-0.9mol/L。
The inventive concept total as one, the present invention also provides a kind of lead flow battery, the electrolysis of the lead flow battery
Liquid is above-mentioned lead fluid cell electrolyte.
Compared with the prior art, the advantages of the present invention are as follows：
1, the present invention uses additive of the tin methane sulfonate as pyrovinic acid lead flow battery, can effectively inhibit negative
Pole dendritic morphology, due to, due to inhibiting cathode dendritic morphology, avoiding cathode dendrite in charging process and falling, to increase
The charge/discharge capacity of pyrovinic acid lead flow battery, improves the coulombic efficiency of battery；And battery is avoided in charging process
In short circuit, extend the service life of battery.
2, inhibit the mechanism of action of cathode dendritic morphology in electrolyte using tin methane sulfonate additive：1) promote the electricity of lead
Deposition improves Pb/Pb2+The invertibity and Pb of electricity pair2+In the diffusion coefficient of electrode surface；2) the electrocrystallization mode for changing lead, by
" three-dimensional instantaneous nucleation " is changed into " three-dimensional continuous nucleation ", and the nucleation density of lead is made to improve；3) make lead and tin be co-deposited to generate
Growth of the PbSn solid solution prior to lead on (111) face, to inhibit the dendritic morphology of negative electrode lead.
Description of the drawings
Fig. 1 is the coulombic efficiency and cycle-index relational graph of the lead flow battery of comparative example 1.
Fig. 2 is the coulombic efficiency and cycle-index relational graph of the lead flow battery of embodiment 1.
Fig. 3 is the coulombic efficiency and cycle-index relational graph of the lead flow battery of comparative example 2.
Fig. 4 is the coulombic efficiency and cycle-index relational graph of the lead flow battery of embodiment 2.
Specific implementation mode
Below in conjunction with specific preferred embodiment, the invention will be further described, but not thereby limiting the invention
Protection domain.
Pyrovinic acid lead flow battery used by embodiment 1-2, comparative example 1-2 consists of the following parts：
Bottom plate：Bottom plate uses aluminum alloy plate materials, for fastening pile, prevents electrolyte from revealing, size is：12.5cm
×10.5cm。
Positive and negative electrode sheet frame：Positive and negative anodes sheet frame is using PP materials, size：12cm × 10cm, among positive/negative plate
Milling out size is：3.2cm × 1.7cm, thickness is the slot of 4mm, for being embedded in conducting polymer based composites electrode.
Runner：The exterior contour of runner is identical as the area of positive and negative pole plate, the area of inner flow passage and conductive plate it is effective
Area is identical.
Positive and negative electrode conductive plate：The conducting polymer based composites that positive and negative electrode conductive plate is all made of, by conducting polymer
Base composite board and copper mesh are tailored into 3cm × 1.5cm sizes together with conducting wire in 200-250 DEG C and 5-10kgf/cm2It is hot pressed into
Type simultaneously takes out after cooling to room temperature with the furnace.Conductive plate after hot pressing is further trimmed to original size 1.5cm × 3cm, it is thick
Degree is 3.5mm.
Battery assembles：In groove by positive and negative conductive plate with silica gel sealing to positive and negative electrode sheet frame, to prevent electrolyte
Leakage.According to aluminum alloy bottom plate-anode sheet frame (being embedded with conductive plate)-runner-cathode sheet frame (being embedded with conductive plate)-aluminum alloy bottom plate
Sequence assembled with screw rod.
Embodiment 1：
Pyrovinic acid lead flow battery assembles in the manner described above, is attached, is filled with pipe with electrolyte and pump
Discharge test, positive and negative anodes effective area are respectively 3cm × 1.5cm.
Prepare the electrolyte of the pyrovinic acid lead flow battery of the present embodiment, wherein pyrovinic acid lead and pyrovinic acid mole
Concentration is respectively 1.8mol/L and 0.3mol/L, and the molar concentration of tin methane sulfonate is 1mmol/L, prepares electrolyte 350ml altogether.
Comparative example 1：
The pyrovinic acid lead flow battery of this comparative example is substantially the same manner as Example 1, only difference is that：In electrolyte
It does not include tin methane sulfonate.
It is 10mA/cm with current density2, charging time 120min, the line flow velocity of electrolyte in the battery is 0.5-
5cm/s.Charge-discharge test is carried out to the battery of embodiment 1 and comparative example 1.The battery of its final result display comparison example 1 (is free of
Having additive tin methane sulfonate) significant cyclic number is to 350 times, as shown in Figure 1, coulombic efficiency is in 85-95%.And embodiment 1
Battery (containing 1mmol/L tin methane sulfonates), significant cyclic number reaches 1000 times, as shown in Fig. 2, coulombic efficiency maintains
90% or so.
Embodiment 2：
Pyrovinic acid lead flow battery assembles in the manner described above, is attached, is filled with pipe with electrolyte and pump
Discharge test, positive and negative anodes effective area are respectively 3cm × 1.5cm.
Prepare the electrolyte of the pyrovinic acid lead flow battery of the present embodiment, wherein pyrovinic acid lead and pyrovinic acid mole
Concentration is respectively 1.5mol/L and 0.9mol/L, and the substance withdrawl syndrome of tin methane sulfonate is 0.8mmol/L, prepares electrolyte altogether
150ml。
Comparative example 2：
The pyrovinic acid lead flow battery of this comparative example is substantially the same manner as Example 2, only difference is that：In electrolyte
It does not include tin methane sulfonate.
It is 10mA/cm with current density2, charging time 600min, the line flow velocity of electrolyte in the battery is 0.5-
5cm/s.Charge-discharge test is carried out to the battery of embodiment 2 and comparative example 2.The battery of final result display comparison example 2 is not
There is short circuit phenomenon to battery at 100 times, significant cyclic number is 75 times, as shown in figure 3, and battery coulombic efficiency fluctuation compared with
Greatly, it is 62-98%.And the battery significant cyclic number of embodiment 2 reaches 150 times, coulombic efficiency is more steady, is 65-98%.
The above is only the preferred embodiment of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, makes a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (7)
1. a kind of electrolysis additive for inhibiting the dendritic lead of lead flow battery to generate, which is characterized in that the electrolysis additive
For tin methane sulfonate.
2. a kind of preparation method of the electrolysis additive as described in claim 1 for inhibiting the dendritic lead of lead flow battery to generate,
Include the following steps：
Metallic tin and pyrovinic acid are reacted into 15-17h at 140-150 DEG C, reaction solution is filtered, gained filter residue is methyl sulphur
Sour tin.
3. a kind of lead fluid cell electrolyte, including pyrovinic acid lead, pyrovinic acid and deionized water, which is characterized in that also wrap
Include the electrolysis additive as described in claim 1 for inhibiting the dendritic lead of lead flow battery to generate or as claimed in claim 2
Inhibit the electrolysis additive that the dendritic lead of lead flow battery generates obtained by preparation method.
4. lead fluid cell electrolyte according to claim 3, which is characterized in that the tin methane sulfonate it is a concentration of
0.5-1.5mmol/L。
5. lead fluid cell electrolyte according to claim 4, which is characterized in that the tin methane sulfonate it is a concentration of
0.6-1.0mmol/L。
6. according to Claims 1 to 5 any one of them lead fluid cell electrolyte, which is characterized in that the lead flow battery
In electrolyte, a concentration of 1-1.8mol/L of lead ion, hydrionic concentration 0.3-0.9mol/L.
7. a kind of lead flow battery, which is characterized in that the electrolyte of the lead flow battery is any one of claim 1~6 institute
The lead fluid cell electrolyte stated.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810092489.8A CN108400364A (en) | 2018-01-31 | 2018-01-31 | Inhibit electrolysis additive of the dendritic lead generation of lead flow battery and preparation method thereof, lead fluid cell electrolyte and lead flow battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810092489.8A CN108400364A (en) | 2018-01-31 | 2018-01-31 | Inhibit electrolysis additive of the dendritic lead generation of lead flow battery and preparation method thereof, lead fluid cell electrolyte and lead flow battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112786939A (en) * | 2021-01-28 | 2021-05-11 | 西安理工大学 | Electrolyte capable of inhibiting generation of dendritic lead and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100040606A (en) * | 2008-10-10 | 2010-04-20 | 한국과학기술연구원 | Electrode for soluble lead acid redox flow battery and soluble lead acid redox flow battery using the same |
| CN103715447A (en) * | 2013-11-20 | 2014-04-09 | 浩源科技有限公司 | Efficient soluble lead-acid flow battery |
-
2018
- 2018-01-31 CN CN201810092489.8A patent/CN108400364A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100040606A (en) * | 2008-10-10 | 2010-04-20 | 한국과학기술연구원 | Electrode for soluble lead acid redox flow battery and soluble lead acid redox flow battery using the same |
| CN103715447A (en) * | 2013-11-20 | 2014-04-09 | 浩源科技有限公司 | Efficient soluble lead-acid flow battery |
Non-Patent Citations (2)
| Title |
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| DEREK PLETCHER ETAL.: "A novel flow battery—A lead acid battery based on an electrolyte with soluble lead(II) IV. The influence of additives", 《JOURNAL OF POWER SOURCES》 * |
| 叶为辉: "甲基磺酸锡合成新工艺的研究", 《城市建设理论研究：电子版》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112786939A (en) * | 2021-01-28 | 2021-05-11 | 西安理工大学 | Electrolyte capable of inhibiting generation of dendritic lead and preparation method thereof |
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Application publication date: 20180814 |