CN104241670A - Perchloric acid system sedimentary full-lead flow battery - Google Patents
Perchloric acid system sedimentary full-lead flow battery Download PDFInfo
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- CN104241670A CN104241670A CN201410518147.XA CN201410518147A CN104241670A CN 104241670 A CN104241670 A CN 104241670A CN 201410518147 A CN201410518147 A CN 201410518147A CN 104241670 A CN104241670 A CN 104241670A
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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
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a novel lead flow battery with high surface capacity. The novel lead flow battery comprises a sedimentary lead dioxide positive electrode with high surface capacity, an electric sedimentary lead negative electrode with high surface capacity and perchloric acid composite electrolyte for achieving electricity storage process with high surface capacity and high efficiency. The novel lead flow battery overcomes the problem that the surface capacity of a conventional lead sedimentary single flow battery is only 10-20 mAh/cm<2>, and the surface capacity of 100-200 mAh/cm<2> can be generally achieved on an electrode substrate, so that the energy storage density and the efficiency of the single flow battery in the unit capacity are greatly improved, the novel lead flow battery is applicable to energy storage of novel energy power generation such as solar and wind power generation and has the function of adjusting the peak and the trough of industrial and domestic power consumption, so that the utilization efficiency of the electric energy is improved.
Description
Technical field
The present invention relates to a kind of complete plumbous flow battery, be specifically related to the complete plumbous single flow battery of a kind of perchloric acid system sedimentation type, belong to power engineering and electrochemical energy storage field.
Background technology
Along with global industry and economic fast development, energy scarcity problem more and more becomes the key issue of restriction human kind sustainable development, and development of new regenerative resource becomes with the efficiency utilization realizing the existing energy extenuates energy-intensive effective way.
In recent years, nuclear energy, wind energy, tidal energy, solar energy achieve scale development and utilization in succession.Relative to stable lasting firepower and nuclear power, the generating of the renewable new forms of energy such as wind energy, tidal energy and solar energy by weather and the impact of time period larger, there is obvious instability, discontinuous and uncontrollable characteristic, therefore need the supporting electrical power storage of development and construction (energy storage) device to ensure the stability generating electricity and power.In addition, also different time sections power consumption is there is uneven in existing electrical network, the problem of electricity consumption peak difference round the clock, also in the urgent need to building large-scale energy storage device to realize " peak load shifting " of electric energy, idle electrical energy during low power consumption at night is stored and drops into peak of power consumption use between daytime, thus realize the effective use of electric power.
Current scale energy storage technology that can be practical mainly contains the physics such as energy storage power generation, the compressed-air energy storage energy storage method that pumps up water, although they can accomplish that scale is large, the life-span is long, but harsh to geographical conditional request, expenditure of construction is high, and efficiency also needs to be improved further.By contrast, then have comparatively ideal effect with the electrochemical energy storage technology that lead acid accumulator and flow battery are representative, wherein flow battery has advantage in stability and safety, cycle efficieny and price etc., becomes the first-selected device being more suitable for scale energy storage.
Early stage liquid flow energy storage battery concept taught proposition under the subsidy of NASA (NASA) is studied in 1974 by Thaller L.H., and had applied for Fe
3+/ Cr
2+flow battery patent, which utilizes Cr
2+reproducibility and Fe
3+oxidizability, discharge in the acid battery that cationic membrane separates.Flow battery is different from traditional secondary cell, and its core is that the active material realizing charge and discharge cycles process is present in electrolyte, and monocell or half-cell electrode are just as the place that oxidation-reduction reaction occurs, instead of the place that active material stores.Flow battery operationally has pump to promote circulate electrolyte flowing, and active material during discharge and recharge in electrolyte, in electrode surface generation electrochemical reaction, stores or release electric energy.Flow battery can be divided into double flow battery (containing two kinds of electrolyte, having amberplex between two kinds of electrolyte) and single flow battery (only containing a kind of electrolyte, not having amberplex), wherein early stage Fe according to using the quantity of electrolyte
3+/ Cr
2+flow battery just belongs to double flow battery.
Because double flow battery has two fluid reservoirs, Comparatively speaking its volume is comparatively large with single flow battery, and specific energy is low, and amberplex used is expensive, there is the problem that phase counterdiffusion causes cross pollution in both positive and negative polarity electrolyte, this makes early stage Fe in charge and discharge process
3+/ Cr
2+flow battery is because adopting Fe
3+and Cr
2+two kinds of elements and cause serious electrolyte contamination and self discharge problem.In order to overcome Fe
3+/ Cr
2+the self discharge of flow battery and electrolyte cross-contamination issue, propose the new ideas of all-vanadium flow battery by the MarriaKazacos of University of New South Wales in 1985.The both positive and negative polarity of this all-vanadium flow battery adopts V respectively
2+/ V
3+and VO
2 +/ VO
2+as both positive and negative polarity active material, by external pump solution pumped in cell stack from reservoir and complete electrochemical reaction, after reaction, solution gets back to reservoir again, and active material constantly with circulate electrolyte flowing, completes charge and discharge process thus.Its exoelectrical reaction formula is as follows:
(1) negative reaction: V
2+-e
-=V
3+
(2) positive pole reaction: VO
2 ++ 2H
++ e
-=VO
2++ H
2o
All-vanadium flow battery owing to have employed the both positive and negative polarity active material of different valence state as battery of single v element, thus decreases Fe to a great extent
3+/ Cr
2+the cross-contamination issue that flow battery adopts different element to exist.Although still there is the diffusion problem between both positive and negative polarity two kinds of different valence state vanadium ions in all-vanadium flow battery, but the energy loss that the self discharge that this diffusion problem generally can regard all-vanadium flow battery self as brings, and the change not large to electrolyte composition.
All-vanadium flow battery has started preliminary commercialization as the model of double flow battery system in Japan, Canada, Australia.Vanadium is as a kind of metal of scarcity of resources, and along with the increase of high temperature resistant vanadium alloy demand, price constantly rises, and adds that high price vanadium ion has certain toxicity, applies bringing very large limitation to it.For double flow batteries such as current Quan Fan, the use of expensive perfluorinated sulfonic acid cation-exchange membrane, not only reduces the energy efficiency of battery, too increases the manufacturing cost of battery.
The appearance of appositional pattern flow battery improves above-mentioned situation.Appositional pattern flow battery is filling in (putting) electric process, and both positive and negative polarity electricity centering has the right active material of one (or two) individual electricity to be deposited on (or originally existing) both positive and negative polarity electrode owing to being insoluble in electrolyte, and during battery discharge, active material dissolves to be got back in solution.The activity of this system both positive and negative polarity reaction is high, good reversibility, and because of its single fluidity, without film or common micro-pore septum that only call for bids is honest and clean, appositional pattern liquid energy-storage system becomes the new developing direction of flow battery one.
Pletcher seminar of south University of Cape Town of Britain is based on conventional lead acid secondary cell concept, a kind of full appositional pattern liquid flow energy storage battery system (Ahmed Hazza is completely newly proposed, Derek Pletcher, Richard Wills. Phys. Chem. Phys, (6): 1773-1778,2004).This battery system adopts acidic methylene sulfonic acid lead (II) solution, and in certain temperature range, plumbous and brown lead oxide is all insoluble to pyrovinic acid solution, and divalence lead during charging in solution is deposited as metallic lead on negative pole, and positive pole is deposited as brown lead oxide.Negative electricity is to being Pb
2+/ Pb, E
0=-0.146V(vs. SHE); Positive pole electricity is to being PbO
2/ Pb
2+, E
0=1.586V(vs. SHE).The activity of this system negative reaction is higher, good reversibility, but positive pole brown lead oxide becomes the overpotential of nuclear reaction higher.In charge and discharge process except face amount is less, and easily analyse oxygen side reaction, active material brown lead oxide is come off and causes energy loss, after so also causing battery discharge, negative pole has plumbous remaining problem, repeatedly cause plumbous accumulation after circulation, have impact on battery life and stable circulation performance further.
In order to overcome the shortcoming of pyrovinic acid electrolyte, Patent Office of the People's Republic of China discloses the patent (Yang Yusheng being entitled as " a kind of complete plumbous flow battery ", a kind of complete plumbous flow battery, China, CN102723518A, [P]. 2012,10,10) and the patent of " a kind of plumbous fluid cell electrolyte " (Yang Yusheng, a kind of plumbous fluid cell electrolyte, China, CN102723519A, [P]. 2012,10,10)), these two inventions disclose and utilize lead（II） ion to prepare several examples of complete plumbous flow battery in the fluoborate aqueous solution of lead fluoborate.They discuss the factors such as both positive and negative polarity electrode material, electrode surface support materials, zwitterion additive to the impact of battery performance, and give suitable kind and the concentration values scope of these factors.Positive pole PbO is found in these researchs
2electrodeposition weight be an important factor, when the face volume controlled of brown lead oxide is at 10-15mAh/cm
2time, whole battery has higher volumetric efficiency.Due to electro-deposition PbO
2face amount lower, when this makes to store large-scale electricity, need to adopt very large electrode area.In order to improve the storage volume of battery, the people such as Liu Dongyang (Liu Dongyang, Cheng Jie etc., HBF
4complete plumbous flow battery in solution, Acta PhySico-Chimica Sinica, 2011,27(11), 2571-2576) and in fluoboric acid electrolyte, carried out large quantifier elimination, disclose the complete plumbous flow battery system that employing fluoboric acid is electrolyte.Research shows, new research work adopts the new substrates materials such as TaC, makes the face amount of battery bring up to 15-20mAh/cm further
2, visible, in complete plumbous single flow battery, the lifting of positive pole face amount is a crucial problem, and it directly constrains the increase of whole battery storage capacity.The complete plumbous flow battery how studying and invent a kind of high face amount newly becomes current solar energy and wind power generation problem demanding prompt solution.
In addition, some researchers also propose Zn-NiOOH(J. Cheng, L. Zhang, Y. S. Yang, Y. H. Wen, G. P. Cao, X. D. Wang, Electrochem. Commun., 2007,9,2639-2642), Cd-PbO
2(Jia Xu. based on PbO
2positive pole novel acid single flow battery research [D]. Beijing University of Chemical Technology, 2011.), Cu-PbO
2(J. Q. Pan, Y. Z. Sun, J. Cheng, Y. H. Wen, Y. S. Yang, P. Y. Wan, [J]. Electroehem. Commun. 2008,10,122) single liquid flow energy storage battery such as, this kind of flow battery positive pole belongs to the electrode of fixed capacity, there is not active material by the process (be not namely deposition type electrode) of bath deposition to anode electrode, therefore will be subject to the quantitative limitation of positive pole face when extensive energy storage.Existing result of study shows, PbO
2easily analyse oxygen side reaction at electrodeposition process, and the stress produced in growth course with oxygen bubbles to the PbO deposited
2there is certain souring, (such as existing 15-20 mAh/cm after this causes complete plumbous flow battery face amount to be increased to certain numerical value
2), the PbO of positive pole deposition
2there will be situation about coming off, which greatly limits the energy storage capacity of complete plumbous flow battery.Visible, the bottleneck of the storage volume of existing complete plumbous flow battery is the face amount improving positive pole, solves positive pole deposition PbO
2with the problem that adhesion difference in electrodeposition process causes face amount too low, need the restriction breaking through each side such as positive electrode, negative material, electrolyte, thus improve the face amount of the complete plumbous single flow battery of appositional pattern.
Summary of the invention
Main purpose of the present invention is that research and develop a kind of novel complete plumbous single flow battery, it comprises newly-designed positive electrode substrate and negative pole matrix, and brand-new perchloric acid composite electrolyte for the too low shortcoming of the face amount of existing novel complete plumbous single flow battery.
First aspect present invention adopts newly-designed anode floor load conductive intermediate layer as the matrix of brown lead oxide positive pole, improve the problem that positive pole brown lead oxide easily analyses oxygen side reaction in electrodeposition process, and adopt perchloric acid composite electrolyte to improve the adhesion of brown lead oxide in positive electrode substrate, reach high deposition efficiency and stronger adhesive force, significantly eliminate existing pyrovinic acid, the oxygen that fluosilicic acid or these three kinds of electrolyte of fluoboric acid produce owing to analysing oxygen side reaction in charge and discharge process washes away obscission to positive active material, thus greatly improve the low problem of complete plumbous single flow battery positive pole charge efficiency.
Second aspect present invention adopts conducting metal as negative pole matrix, by adding the adhesion that specific additive improves negative electricity deposit lead in perchloric acid composite electrolyte, and eliminate the plumbous dendrite problems easily produced of electro-deposition, thus increase substantially the face amount of complete plumbous single flow battery negative electricity deposit lead.
A third aspect of the present invention adopts the NEW TYPE OF COMPOSITE electrolyte based on perchloric acid, this electrolyte not only combines the characteristic that perchloric acid has high conductance, significantly can reduce polarization and the internal resistance of cell of charge and discharge process, and under the acting in conjunction of new additive agent, can eliminate positive pole electro-deposition brown lead oxide and negative electricity deposit lead and electrode matrix in conjunction with stress.In addition, perchloric acid as electrolyte main body compared with pyrovinic acid, fluosilicic acid or fluoboric acid electrolyte, not only avoid the problem of electrolyte muddiness, but also eliminate the fluoride pollution problem applied fluorine-containing electrolyte and bring, more meet the requirement of society and environment facies harmony.
The object of the invention is to be realized by following step:
(1) on anode floor, load conductive intermediate layer is as the matrix of brown lead oxide positive pole, and wherein, anode floor can be titanium plate or titanium alloy sheet, also can be easy and PbO
2form the conducting metal oxide SnO of solid solution
2plate, can by a small amount of Sb of doping
2o
3, Sb
2o
5, Bi
2o
3, Bi
2o
5deng other metal oxides, modification is carried out to it; The conductive intermediate layer of load can be reduce PbO
2the deposition Pt metal of overpotential or the alloy of Pt; Also can be SnO
2, Sb
2o
3, Sb
2o
5, Bi
2o
3, Bi
2o
5deng easy and PbO
2form the conducting metal oxide of solid solution.These metal or alloy or metal oxide can independently use as conductive intermediate layer, also they can be mixed back loading mutually by different proportion and use as conductive intermediate layer on anode floor.
(2) negative pole matrix can be the copper, silver or the lead metal that conduct electricity, can be also inactive, conductive material, or in inactive, conductive material, be electroplate with copper, silver or lead metal layer.Wherein inactive, conductive material can be graphite, platinized platinum and carbon fiber etc.Research shows, copper, silver and plumbous three kinds of basis materials can have better electro-deposition face amount relative to other metal material in perchloric acid composite electrolyte of the present invention.
(3) the NEW TYPE OF COMPOSITE electrolyte based on perchloric acid is adopted.Electrolyte of the present invention contains with the bath composition of perchloric acid position main body, with the addition of the lead（II） ion needed for electrodeposition process and the multiple compound additive improving positive pole and negative electricity deposition process simultaneously.Wherein, perchloric acid concentration is 0.5-3 mol/L, and lead perchlorate concentration is 0.1-2 mol/L, and in solution, the source of lead（II） ion can be divalence lead oxides, divalence plumbous hydroxide, ceruse, basic lead carbonate, Pb (CH
3cOO)
2, Na
2pb0
2, K
2pb0
2or one or more the mixture in them; The temperature of electrolyte can be generally 10-80 DEG C.
In order to improve the adhesion of both positive and negative polarity electro-deposition active material and electrode matrix, reduce the stress of electrodeposition process, thus improve the face amount of both positive and negative polarity, in perchloric acid composite electrolyte, add specific additive.The anode additive wherein added can be La
3+, Eu
3+, Pm
3+, Th
3+, Yb
3+, Sm
3+, Gd
3+and Ce
3+etc. the rare earth element ion with special 4f electronic structure, improve positive pole deposition Pb0
2adhesion difference and caducous problem.These special 4f structure rare earth elements are to raising positive pole electro-deposition Pb0
2face amount and the charge-discharge performance improving battery provides new guarantee.The addition of these anode additives is the 0.01-10% of electrolyte weight degree.Simultaneously, the present invention finds through the great many of experiments of hundreds of negative electricity depositing additives, in new perchloric acid composite electrolyte, add the one or any two or more combination in following additive, can make the plumbous negative pole of electro-deposition in perchloric acid composite electrolyte, have best electro-deposition face amount, these cathode additive agents can be the one or any two or more combinations in gelatine, sodium lignosulfonate, naphthols and DPE-3, and its addition is the 0.01-10% of electrolyte weight degree.The present invention not only improves the adhesion of negative electricity deposit lead by the perchloric acid combined electrolysis solution additive realizing finding, and contribute to eliminating the plumbous dendrite problems easily produced of electro-deposition, make electro-deposition lead finer and close, in unit are, effectively obtain very high electro-deposition face amount.
After above-mentioned electrolyte, positive electrode substrate, negative pole matrix are assembled into battery cell, charge and discharge cycles can be carried out.During charging, the electric energy of input is by the Pb in electrolyte
2+on negative pole matrix, reduction is deposited as metal Pb, simultaneously by the Pb in electrolyte
2+in positive electrode substrate, oxide deposition is PbO
2.During electric discharge, the active material of both positive and negative polarity substrate deposit and electrolyte composition battery, electrode reaction and charging process are just contrary, and the active material of deposition all dissolves to be got back in electrolyte, thus constantly move in circles and carry out discharge and recharge.
Technical scheme of the present invention: Fig. 1 is shown in by device schematic diagram, the complete plumbous single flow battery monomer (1) of perchloric acid system is by positive electrode substrate (2), negative pole matrix (3) and electrolyte (4) are formed, electrolyte (4) flows between storage tank (7) and battery cell (1) along pipeline (6) under pump (5) promotes, electrolyte (4) flows through the surface of positive electrode substrate (2) and negative pole matrix (3) and separates positive electrode substrate (2) and negative pole matrix (3) in battery cell (1), at the upper deposited silicon dioxide lead (8) of positive electrode substrate (2) during charging, at the upper plated metal lead (9) of negative pole matrix (3), during electric discharge, brown lead oxide (8) and metallic lead (9) composition cell active materials are all dissolved and are got back in electrolyte (4), charging and discharging is carried out in circulation like this.
Simultaneously, as shown in Figure 1, the complete plumbous single flow battery of perchloric acid system can carry out serial or parallel connection by multiple battery cell (1) or mixed connection is combined into pile, and wherein multiple battery cell can share same electrolyte (4), pump (5), pipeline (6) and electrolyte storage tank (7).Also will the complete electrolysis of lead（II） ion or both positive and negative polarity active matter quality not reach most great talent and start electric discharge in electrolyte in charge and discharge process, also by the time need not discharge in discharge process and could start charging completely.Namely whole battery system charge and discharge process can freely switch flexibly, and realistic demand is applied widely.
In addition, the flowing velocity of electrolyte also can be regulated by valve (11) and pump (5) according to the change of the factors such as current density, concentration of electrolyte, ambient temperature.Electrolyte circulate the mass transfer rates increasing electrode interface in solution, greatly reduce concentration polarization, the charging voltage of battery can be reduced, improve energy efficiency.There is not lamination because electrolyte is in homogeneous flow regime all the time, thus also eliminate the uneven problem causing electrode deformation of active material deposition.
The complete plumbous single flow battery of this brand-new perchloric acid system that the present invention proposes, have employed newly-designed anode floor load intermediate layer conducting objects as brown lead oxide positive pole matrix, employ the NEW TYPE OF COMPOSITE electrolyte based on perchloric acid and with the addition of specific multiple additives in the electrolytic solution, finally in all its bearings significant improvement has been carried out to the face amount of complete plumbous single flow battery and energy efficiency.These work finally make the 10-20 mAh/cm of positive pole lead dioxide electrode face amount by these three kinds of electrolyte systems of existing pyrovinic acid, fluosilicic acid or fluoboric acid of complete plumbous single flow battery
2bring up to present 150-200 mAh/cm
2, this is that the extensive energy storage carrying out new forms of energy from now on provides highdensity energy-storage travelling wave tube.
Accompanying drawing explanation
The complete plumbous single flow battery of a kind of perchloric acid system sedimentation type of Fig. 1
1. battery cell, 2. positive electrode substrate, 3. negative pole matrix, 4. electrolyte, 5. pump, 6. electrolyte pipeline, 7. electrolyte storage tank, 8. deposited silicon dioxide is plumbous, and 9. plated metal is plumbous, 10. battery cell shell, 11. valves
The complete plumbous flow battery monomer (1) of several perchloric acid system sedimentation types, electrolyte (4), pump (5) electrolyte pipeline (6) and electrolyte storage tank (7) be a composition pile jointly.
Embodiment
Embodiment 1
The present embodiment is a kind of instantiation of the complete plumbous flow battery of lead perchlorate system.As Fig. 1, using the thick Cu sheet (2cm × 2cm) of 0.5mm as negative current collector and matrix, to be welded in respectively on copper conductor with the thick Ti plate (2cm × 2cm, not load intermediate layer) of 0.5mm as plus plate current-collecting body and matrix and to be fixed on battery case and form complete plumbous flow battery monomer.Electrolyte is the lead perchlorate of 0.4 mol/L of 50mL and the mixed solution of the perchloric acid of 1.2mol/L, and adds the Pm of 0.025mol/L
3+anode additive and 0.1 g/L sodium lignosulfonate and 0.5 g/L gelatine are as cathode additive agent.Under 50 DEG C of constant temperatures, with 10mA/cm
2current density carry out the test of 10 charge and discharge cycles, charging face amount restrictive condition is 20mAh/cm
2, after 10 circulations, current efficiency is stabilized in 95%-97%, and voltage efficiency is 85%, and total energy efficiency can reach 82%.
Embodiment 2
The present embodiment is a kind of instantiation of the complete plumbous flow battery of lead perchlorate system.As Fig. 1, with the Pb plate (purity 98% that 1mm is thick, 2cm × 2cm) as negative current collector and matrix, to be welded in respectively using the thick Ti plate (2cm × 2cm) of 0.5mm as plus plate current-collecting body and substrate on copper conductor and to be fixed on battery case and formed complete plumbous flow battery monomer.Wherein the substrate of positive pole Ti plate is after oxalic acid etching (the micro-2h that boils of 10% oxalic acid), 2mg/cm in roasting load
2snO
2as intermediate layer, (painting is covered with SnCl
2aqueous isopropanol after, roasting 2h at 400 DEG C).The substrate of positive pole Ti plate also can substitute, by SnO with Ti net
2be compressed on Ti net after mixing with conductive agent and ptfe emulsion and make electrode slice.Electrolyte is the lead perchlorate of the 0.3mol/L of 50mL and the perchloric acid mixed solution of 1.4mol/L, does not add any additive.Under 50 DEG C of constant temperatures, with 20mA/cm
2current density carry out the test of 10 charge and discharge cycles, charging face amount reaches 50mAh/cm
2, each time charge and discharge cycles collimation is better, and current efficiency is all more than 93%, and total energy efficiency can reach 80%.
Embodiment 3
The present embodiment is a kind of instantiation of the complete plumbous flow battery of lead perchlorate system.As Fig. 1, with the Pb plate (purity 99.994% that 1mm is thick, 2cm × 2cm) as negative current collector and matrix, to be welded in respectively using the thick Ti plate (2cm × 2cm) of 0.5mm as plus plate current-collecting body and substrate on copper conductor and to be fixed on battery case and formed complete plumbous flow battery monomer.Wherein the substrate of positive pole Ti plate is after oxalic acid etching (the micro-2h that boils of 10% oxalic acid), 5mg/cm in roasting load
2sb
2o
3as intermediate layer, (painting is covered with SbCl
3aqueous isopropanol after, roasting 2h at 400 DEG C).The substrate of positive pole Ti plate also can substitute, by Sb with Ti net
2o
3be compressed on Ti net after mixing with conductive agent and ptfe emulsion and make electrode slice.Electrolyte is the lead perchlorate of 0.35 mol/L of 50mL and the perchloric acid mixed solution of 1.3 mol/L, and the gelatine of the sodium lignosulfonate and 1.5 g/L that add 0.15 g/L is as cathode additive agent.Under 50 DEG C of constant temperatures, with 10mA/cm
2current density carry out the test of 10 charge and discharge cycles, charging face amount restrictive condition is 100mAh/cm
2, each time charge and discharge cycles collimation is better, and current efficiency is all about more than 95%, and voltage efficiency can reach more than 86%, and total energy efficiency can reach 82%.
Embodiment 4
The present embodiment is a kind of instantiation of the complete plumbous flow battery of lead perchlorate system.As Fig. 1, using the thick Cu sheet (2cm × 2cm) of 0.5mm as negative current collector and substrate, to be welded in respectively using the thick Ti plate (2cm × 2cm) of 0.5mm as plus plate current-collecting body and substrate on copper conductor and to be fixed on battery case and formed complete plumbous flow battery monomer.Wherein the substrate of positive pole Ti plate is after oxalic acid etching (the micro-2h that boils of 10% oxalic acid), 2mg/cm in roasting load
2snO
2as intermediate layer, (painting is covered with SnCl
2aqueous isopropanol after, roasting 2h at 400 DEG C).The substrate of positive pole Ti plate also can substitute, by SnO with Ti net
2be compressed on Ti net after mixing with conductive agent and ptfe emulsion and make electrode slice.Electrolyte is the lead perchlorate of 0.3 mol/L of 50mL and the perchloric acid mixed solution of 1.4 mol/L, adds the sodium lignosulfonate of 0.1 g/L and the DPE-3 of the 2.5 g/L Ce (NO as cathode additive agent, 1.2 g/L
3)
3as anode additive.Under 50 DEG C of constant temperatures, with 10mA/cm
2current density carry out the test of 10 charge and discharge cycles, charging face amount restrictive condition is 100mAh/cm
2, each time charge and discharge cycles collimation is better, and current efficiency is all about more than 93%, and voltage efficiency can reach more than 86%, and total energy efficiency can reach 81%.
Embodiment 5
With the Cu sheet (purity 99.99% that 0.5mm is thick, 2cm × 2cm) as negative current collector and matrix, to be welded in respectively using the thick Ti plate (2cm × 2cm) of 0.5mm as plus plate current-collecting body and substrate on copper conductor and to be fixed on battery case and formed complete plumbous flow battery monomer.Wherein positive pole Ti plate surface is coated with Pt metal layer (commercially availablely to buy, does not do other pre-treatments before reaction except cleaning).Electrolyte is the lead perchlorate of 0.5 mol/L of 50mL and the perchloric acid mixed solution of 3 mol/L, adds the naphthols of 0.1 g/L and the gelatine of the 0.5 g/L Ce (NO as cathode additive agent, 1.2 g/L
3)
3as anode additive.Under 50 DEG C of constant temperatures, with 10mA/cm
2current density carry out the test of 20 charge and discharge cycles, charging face amount restrictive condition is 200mAh/cm
2, current efficiency is about 93%, and voltage efficiency reaches 88%, and energy efficiency can reach 82%.
Embodiment 6
With the Pb plate (purity 99.994% that 1 mm is thick, 2cm × 2cm) as negative current collector and matrix, to be welded in respectively using the thick Ti plate (2cm × 2cm) of 0.5mm as plus plate current-collecting body and substrate on copper conductor and to be fixed on battery case and formed complete plumbous flow battery monomer.Wherein the substrate of positive pole Ti plate is after oxalic acid etching (the micro-2h that boils of 10% oxalic acid), 2mg/cm in roasting load
2snO
2and 2mg/cm
2sb
2o
3as intermediate layer, (painting is covered with SnCl
2and Sb
2o
3aqueous isopropanol after, roasting 2h at 400 DEG C).The substrate of positive pole Ti plate also can substitute, by SnO with Ti net
2be compressed on Ti net after mixing with conductive agent and ptfe emulsion and make electrode slice.Electrolyte is the lead perchlorate of 0.5 mol/L of 50mL and the perchloric acid mixed solution of 3 mol/L, adds the sodium lignosulfonate of 0.2 g/L and the gelatine of the 0.5 g/L Eu (NO as cathode additive agent, 1.3 g/L
3)
3as anode additive.Under 50 DEG C of constant temperatures, with 10mA/cm
2current density carry out the test of 10 charge and discharge cycles, charging face amount restrictive condition is 200mAh/cm
2, with load Sb
2o
3ti plate positive pole compare, current efficiency is higher; The current efficiency of this battery charging and discharging is 95%, and voltage efficiency is 85%, and total energy efficiency can reach 81%.
Claims (6)
1. the complete plumbous flow battery of perchloric acid system sedimentation type, comprise positive electrode substrate, negative pole matrix and perchloric acid composite electrolyte, obtained the perchloric acid electrolyte of electro-deposition brown lead oxide positive pole, the plumbous negative pole of electro-deposition and regeneration by charging process, realize the storage process of electric energy.
2. a complete plumbous flow battery as claimed in claim 1, it is characterized in that positive electrode substrate is in anode floor area load conductive intermediate layer, wherein, anode floor can be titanium plate or titanium alloy sheet, also can be easy and PbO
2form the conducting metal oxide SnO of solid solution
2plate, can by a small amount of Sb of doping
2o
3, Sb
2o
5, Bi
2o
3, Bi
2o
5other metal oxides carry out modification to it; The conductive intermediate layer of load can be Pt metal or Pt alloy, also can be metal oxide SnO
2, Sb
2o
3, Sb
2o
5, Bi
2o
3and Bi
2o
5.
3. a complete plumbous flow battery as claimed in claim 1, is characterized in that negative pole matrix can be the copper, silver or the lead metal that conduct electricity, can be also inactive, conductive material, or in inactive, conductive material, be electroplate with copper, silver or lead metal layer.
4. a complete plumbous single flow battery as claimed in claim 1, it is characterized in that perchloric acid composite electrolyte is the mixed solution of lead perchlorate and perchloric acid, wherein lead perchlorate concentration is 0.1-2 mol/L, perchloric acid concentration is 0.5-3 mol/L, containing the additive increasing positive pole and negative pole face amount in electrolyte.
5. the complete plumbous flow battery as described in claim 1 or 4, is characterized in that the additive increasing positive pole face amount in electrolyte is La
3+, Eu
3+, Pm
3+, Th
3+, Yb
3+, Sm
3+, Gd
3+and Ce
3+have in the rare earth element ion of 4f electronic structure one or more, its addition is the 0.01-10% of electrolyte weight degree.
6. the complete plumbous flow battery as described in claim 1 or 4, the additive that it is characterized in that increasing in electrolyte negative pole face amount is one or more in gelatine, sodium lignosulfonate, naphthols and DPE-3, and its addition is the 0.01-10% of electrolyte weight degree.
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| CN109638329A (en) * | 2018-12-19 | 2019-04-16 | 中国科学技术大学 | A kind of water system flow battery |
| CN112397756A (en) * | 2020-11-13 | 2021-02-23 | 旭派电源有限公司 | Lead-acid flow battery |
| WO2024120530A1 (en) * | 2022-12-09 | 2024-06-13 | 中国科学院大连化学物理研究所 | Naphthalene-type compound and preparation method therefor and use thereof |
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