CN104094462B - Oxidation, reduction liquid secondary cell - Google Patents
Oxidation, reduction liquid secondary cell Download PDFInfo
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- CN104094462B CN104094462B CN201380008195.8A CN201380008195A CN104094462B CN 104094462 B CN104094462 B CN 104094462B CN 201380008195 A CN201380008195 A CN 201380008195A CN 104094462 B CN104094462 B CN 104094462B
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- oxidation
- secondary cell
- reduction liquid
- electrode
- liquid secondary
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- 239000007788 liquid Substances 0.000 title claims abstract description 67
- 230000003647 oxidation Effects 0.000 title claims abstract description 64
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 claims abstract description 49
- 239000002184 metal Substances 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 35
- 239000011248 coating agent Substances 0.000 claims abstract description 33
- 150000002739 metals Chemical class 0.000 claims abstract description 32
- 230000005611 electricity Effects 0.000 claims abstract description 18
- 239000000969 carrier Substances 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 238000005342 ion exchange Methods 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 238000006479 redox reaction Methods 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 238000010422 painting Methods 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims 2
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 20
- 239000011255 nonaqueous electrolyte Substances 0.000 description 8
- 150000002500 ions Chemical group 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 101710031899 moon Proteins 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- BFASWJXWTSCDRR-UHFFFAOYSA-M prop-2-enyl carbonate Chemical compound [O-]C(=O)OC[C]=C BFASWJXWTSCDRR-UHFFFAOYSA-M 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
Abstract
The present invention relates to oxidation, reduction liquid secondary cell.The oxidation, reduction liquid secondary cell of the present invention includes the element cell comprising the pair of electrodes being made up of porous metals, and the surface-coated of wherein said porous metals has carbon.According to the present invention, it is provided that use the oxidation, reduction liquid secondary electricity of the porous metal electrode being uniformly coated with carbon, thus improve the electrical conductivity of electrode, and described electrode has the surface being uniformly coated with the carbon-coating with wide specific surface area, thus improves reactivity.Accordingly, it is capable to improve oxidation, reduction liquid secondary cell capacity and can efficiency and the resistance of battery can be effectively reduced.Additionally, described electrode is uniformly coated with carbon-coating, the most also improve corrosion resistance.
Description
Technical field
The present invention relates to secondary cell, and more specifically it relates to use and be wherein coated with carbon
The oxidation, reduction liquid secondary cell of the electrode of porous metals.
Background technology
Electric power stores the important technology of the performance for effectively maximizing every field, described field
Electric power, the ability improving electric power system or reliability, introducing is the most effectively used wherein to depend on
The expansion of the regenerative resource of a series of great variety of time, the energy recovery etc. of mobile object,
And they meet the development probability of the demand of contribution to society and are gradually increased.
In order to adjust the equilibrium of supply and demand of half autonomous areas' electric power system of such as microgrid, suitably distribute
The uneven output of the Renewable Energy Development of such as wind-power electricity generation or solar electrical energy generation and control by
The voltage produced from the difference of conventional electric power system and the impact of frequency change, the most actively enter
The row research to secondary cell, and in these areas to using the expectation of secondary cell
It is continuously increased.
About for storing the feature needed for the secondary cell of high power capacity electric energy, secondary cell should have
Having high energy storage density, therefore oxidation, reduction liquid secondary cell receives much concern, this is because secondary
Battery has high power capacity and high efficiency, and it is best suited for a little feature.
Forming oxidation, reduction liquid secondary cell makes battery carrier form the profile of whole battery, electricity
The center in pond is ion exchanged layer separately, and anode and negative electrode are positioned at the both sides of ion exchange layer.
Additionally, form oxidation, reduction liquid secondary cell to include bipolar plates and from being provided
The current collector of each electrode exterior conduction, stores anode slot and cathode can, the Qi Zhong electricity of electrolyte
Solve the import that mass flow is entered and the outlet that wherein electrolyte flows out.
This kind of oxidation, reduction liquid secondary cell is carried out various research and with exploitation thus improves output
With energy both efficiency.Recently, main use non-aqueous electrolyte rather than aqueous electrolyte.
As it has been described above, for the oxidation, reduction liquid secondary cell developing application non-aqueous electrolyte,
Need use the high-affinity of non-aqueous electrolyte and there is the electrode of excellent electric conductivity, therefore
Need the research and development of the electrode meeting these requirements badly.
The feelings of the energy electrode material of commercial oxidation reduction liquid stream secondary cell it are used at carbon-based material
Under condition, owing to the affinity of non-aqueous electrolyte is the lowest and electrical conductivity compared with metal electrode
Significantly reduce, therefore can the carrying of efficiency when being applied to non-aqueous oxidation, reduction liquid secondary cell
Height is limited.
Carrying out the every research for development of metallic electrode to improve non-aqueous redox flow
The electrochemical characteristic of stream secondary cell.But, increase the ratio table of metal electrode in the fabrication process
Area is conditional, and therefore these researchs do not propose to improve non-aqueous oxidation, reduction liquid two
The essence solution of the energy efficiency of primary cell.
Disclosure
Technical problem
The present invention relates to provide to use the porous metals with excellent electric conductivity to guarantee electrode
The oxidation, reduction liquid secondary cell of electrical conductivity.
The present invention relates to provide and use the carbon being uniformly coated with bigger serface to improve energy efficiency
The oxidation, reduction liquid secondary cell of porous metal electrode.
The carbon that the present invention relates to provide wherein porous metal electrode to be coated with bigger serface therefore
The reactive oxidation, reduction liquid secondary cell improved.
Technical scheme
One aspect of the present invention provides and includes element cell, a pair current collector and a pair battery
The oxidation, reduction liquid secondary cell of frame.This element cell comprises pair of electrodes, described electrode by
Porous metals are formed and the surface-coated of described porous metals has carbon.This pair current collector and list
Two outer surfaces of unit's battery connect.This pair battery carrier is connected with each outer surface of current collector.
In the oxidation, reduction liquid secondary cell of the present invention, compared with the weight of porous metals,
On the surface of porous metals, the amount of the carbon of coating can be 50wt% or lower.
In the oxidation, reduction liquid secondary cell of the present invention, porous metals can be selected from nickel (Ni),
Any one in copper (Cu), ferrum (Fe), molybdenum (Mo), titanium (Ti), platinum (Pt) and iridium (Ir).
In the oxidation, reduction liquid secondary cell of the present invention, can use selected from dip coating method
It is coated with any one in spraying method.
In the oxidation, reduction liquid secondary cell of the present invention, for the carbon of the coating serosity of coating
Content can be 50wt% or higher.
In the oxidation, reduction liquid secondary cell of the present invention, element cell includes ion exchange layer,
Each it is connected and includes the pair of electrodes of anode and negative electrode with two surfaces of ion exchange layer,
And one of them surface is connected and another surface with the outer surface of each electrode of this electrode pair
A pair plate being connected with current collector.
In the oxidation, reduction liquid secondary cell of the present invention, element cell is anti-according to oxidoreduction
Electricity should be produced by the ion exchange layer between electrode.
The oxidation, reduction liquid secondary cell of the present invention may also include anode slot and cathode can, pump,
Inlet and outlet.This anode and cathode can are separately positioned on left side and the right side of battery carrier, and
Configured to store electrolyte so that electrolyte flow.This pump each with anode slot and negative electrode
Groove connects and provides electrolyte.This import pump is connected with battery carrier in case this electrolyte via
Battery carrier flows into element cell.This outlet is connected with battery carrier so that from the electricity of element cell outflow
Solve mass flow and enter anode slot and cathode can.
Another aspect provides oxidation, reduction liquid secondary cell and include that at least one has
There is the element cell of at least one pair of electrode formed by the porous metals being coated with carbon.
Another aspect provides oxidation, reduction liquid secondary cell, it includes relative shape
A pair battery carrier become and be spaced, be each connected with the inner surface of a pair battery carrier
The element cell that current collector and at least two are formed between a pair current collector, wherein said
Element cell includes at least one pair of electrode formed by the porous metals being coated with carbon.
Advantageous effects
According to the present invention, it is provided that use the oxidation of the porous metal electrode being uniformly coated with carbon also
Stock solution stream secondary cell, therefore improves the electrical conductivity of electrode.
Additionally, the surface of porous metal electrode is uniformly coated with the carbon-coating with bigger serface,
Therefore reactivity can be improved.
Accordingly, it is capable to improve oxidation, reduction liquid secondary cell capacity and can efficiency and can be effective
Reduce the resistance of battery.Additionally, electrode is uniformly coated with carbon-coating, therefore can also improve corrosion-resistant
Property.
Accompanying drawing describes
Fig. 1 and 2 is the view of the oxidation, reduction liquid secondary cell describing embodiment of the present invention.
Fig. 3 is the form figure with comparative example of the electrode for comparing the present invention.
Figure 4 and 5 are the circulations for the embodiment Yu comparative example comparing electrode of the present invention
The chart of voltammetry (CV) feature.
Fig. 6 is the energy efficiency for comparing the embodiment of electrode of the present invention and comparative example
Chart.
Fig. 7 and 8 is for describing the oxidation, reduction liquid secondary of another embodiment of the present invention electricity
The view in pond.
Invention mode
Before the detailed description of embodiment of the present invention, specification and claims make
Term and word be not necessarily to be construed as the limit to the implication in normally used implication or dictionary
System and the principle of the concept of term that suitably should define based on inventor use and the technology of the present invention
Implication and concept explanation that scope is consistent thus the present invention is described in the best way.Accordingly, because
The configuration illustrated in the embodiment described in this manual and accompanying drawing is merely illustrative embodiment party
Case and do not represent whole technical scopes of the present invention, carries it is therefore to be understood that present invention resides in
Hand over each equivalent, amendment and substitute during the application.
Below, the exemplary of the present invention is described in detail by referring to the drawings.Throughout this
Description uses identical reference number to refer to same or analogous part.But, following
Illustrate and appended accompanying drawing in by omit unnecessarily obscure the present invention main points well-known functions or
The detailed description of configuration.Based on same cause, some assemblies amplify in the accompanying drawings, omit or show
Meaning property illustrates, and the size of various piece not exclusively reflect actual size.
Below, with reference to appended accompanying drawing, the exemplary of concept of the present invention is carried out
Describe in detail.
First, the oxidation, reduction liquid secondary cell of embodiment of the present invention is described.Fig. 1 and 2
It it is the view of oxidation, reduction liquid secondary cell for describing embodiment of the present invention.Herein,
Fig. 1 is the assembly of the dismounting of the oxidation, reduction liquid secondary cell showing embodiment of the present invention
Exploded view, and Fig. 2 is the horizontal stroke of the oxidation, reduction liquid secondary cell showing embodiment of the present invention
The sectional view in cross section.
With reference to Fig. 1 and 2, the oxidation, reduction liquid secondary cell of embodiment of the present invention is to use
The wherein redox reaction of the metal ion that quantivalence changes and the secondary of charge or discharge
Battery.Additionally, the oxygen of embodiment of the present invention can be driven in the voltage range of 0 to 3.0V
Change reduction liquid stream secondary cell.
The oxidation, reduction liquid secondary cell of embodiment of the present invention can be formed to have in template
Two outer surfaces of the element cell 100 and element cell 100 with multiple structure are connected also
A pair current collector 40 of being formed in template and respectively outer surface with current collector 40 be connected and
The battery carrier 50 formed in template.
Herein, element cell 100 include ion exchange layer 10, electrode 20 and its each have
The bipolar plates 30 (below, be abbreviated as " plate ") of template, and in its structure being had,
Anode in electrode 20 is positioned at into anticathode opposite, and each electrode 20 exchanges based on ion
The layer center of 10 is connected with two surfaces of ion exchange layer 10, and described plate 30 is respective and
The anode of electrode 20 and the outer surface of negative electrode connect.Meanwhile, although not shown, can at electrode
It is selectively inserted as liner between 20 and ion exchange layer 10.
As it has been described above, ion exchange layer 10, electrode 20 and its each there is plate 30 shape of template
Become the element cell 100 of multiple structure form.
The oxidation of the wherein metal ion that quantivalence changes is there is also in element cell 100
Former reaction.In this case, by ion exchange layer 10 the anode of electrode 20 and negative electrode it
Between occur redox reaction, therefore by redox reaction produce electricity.
When producing electricity at the anode and negative electrode of the electrode 20 at element cell 100, plate 30 He
The electricity produced collected by current collector 40.Battery carrier 50 keep and support above-mentioned ion exchange layer 10,
Pair of electrodes 20, plate are to 30 and the shape of a pair current collector 40.
Additionally, the oxidation, reduction liquid secondary cell of embodiment of the present invention may also include anode slot
60, cathode can 70, pump 61 and 71, import 63 and 73 and outlet 65 and 75.
Anode slot 60 and cathode can 70 store anodolyte and catholyte respectively with when needing
Will time flow.Preferably, anode slot 60 and cathode can 70 use non-aqueous electrolyte to make respectively
For anodolyte and catholyte, but, it be also possible to use aqueous electrolyte.So, sun
Pole groove 60 and cathode can 70 are individually placed upon the electrode 20 corresponding to said units battery 100
Anode and negative electrode element cell 100 two outer surfaces on.
Additionally, anode slot 60 and cathode can 70 are respectively by import 63 and 73 and outlet 65
It is connected with battery carrier 50 with 75.Import 63 and 73 is the electricity of anode slot 60 and cathode can 70
Solve mass flow and enter the passage that element cell 100 is passed through, and to export 65 and 75 be electrolysis mass flow
Go out the passage that element cell 100 passes through.Further it is provided that pump 61 and 71 is so that electrolyte flows out
Anode slot 60 and cathode can 70 and supply electrolyte, and pump 61 to element cell 100
With 71 be respectively arranged between anode slot 60 and import 63 and cathode can 70 and import 73
Between.
Therefore, pump 61 and 71, import 63 and 73, battery carrier 50 and collection can be passed through respectively
The electrolyte flowed out from anode slot 60 and cathode can 70 is supplied to element cell 100 by electrical equipment 40
And with reverse order, flow into and be stored in anode slot 60 and cathode can 70.
In the oxidation, reduction liquid secondary cell configured according to the embodiment above, ion exchanges
Layer 10 can be formed by perfluorinated sulfonic acid (Nafion).Additionally, plate 30 can be formed by graphite.
As it has been described above, electrode 20 inner surface with plate 30 respectively is connected.So, electrode 20
The surface each with porous metals is uniformly coated with the feature of carbon-coating.According to embodiment party of the present invention
The oxidation, reduction liquid secondary cell of case, electrode 20 is uniformly coated with shape at carbon at its porous metals
Become.
Herein, porous metals can be selected from nickel (Ni), copper (Cu), ferrum (Fe), molybdenum (Mo), titanium (Ti),
Any one in platinum (Pt) and iridium (Ir).
Moreover it is preferred that compared with the weight of porous metals, coating porous metals make porous
On metal surface, the amount of the carbon of coating is 50wt% or lower.Moreover it is preferred that immersion coating
Method or spraying method can be used as painting method.When preparation is for the carbon coating serosity of coating,
Preparation coating serosity is to have the carbon content of 50wt% or higher.
As it has been described above, at aqueous or non-aqueous oxidation, reduction liquid secondary cell and hereafter will retouch
The porous metal electrode being uniformly coated with carbon is used, therefore on the surface of the stacking type cell stated
Can improve non-aqueous oxidation, reduction liquid secondary cell capacity and can efficiency and corrosion can be improved
Characteristic.
Then, the electrode shape of electrode embodiments of the present invention can be compared with comparative example.
Fig. 3 is the field emission scanning electron microscope of form and the comparative example comparing electrode of the present invention
(FESEM) image illustrates and discloses the embodiment of electrode of the present invention.
With reference to Fig. 3, it may be determined that the surface of porous metals is uniformly coated with the embodiment of carbon
Electrode 20.The details of comparative example and embodiment is the most following [table 1].
[table 1]
| Metal types | Aperture | The amount of carbon coating | |
| Comparative example 1 | Ni | 800 | 0wt% |
| Comparative example 2 | Cu | 800 | 0wt% |
| Embodiment 1 | Ni | 800 | 5wt% |
| Embodiment 2 | Cu | 800 | 5wt% |
Use spraying method coating embodiment of the present invention 1 and the electrode 20 of embodiment 2,
Prepare and there is conductive black (Super-P): binding agent: N-Methyl pyrrolidone (NMP)=2.5:2.5:95
Compositions serosity after, when the surface-coated of porous metals has carbon.With coating before and
Detect the amount of the carbon (amount of carbon coating) of coating with weight ratio after coating.
The circulation of electrode of the present invention is compared by the embodiment of electrode of the present invention and comparative example
Voltammetry (CV) feature.Fig. 4 and Fig. 5 is the CV of the embodiment for comparing electrode of the present invention
The diagram of the CV feature of feature and comparative example.Herein, the contrast to above-mentioned [table 1] is implemented
Example 1 and comparative example 2 and use the spray of organic bath based on Allyl carbonate (PC)
Coating method is coated with the embodiment of the porous metal electrode of carbon and carries out CV characteristic evaluating.
In figures 4 and 5, special in order to evaluate the electrochemistry of the porous metal electrode being coated with carbon
Levy, various non-aqueous electrolytes carry out CV detection.In this case, with Ag/Ag+
-1.8 compared are examined to the potential range of 0.0V under the conditions of the sweep speed of 1mV/s
Survey.Fig. 4 is to show Co (bpy)+Comparative example in PC electrolyte and the CV of embodiment
The chart of feature, and Fig. 5 is to show Ni (bpy)+Comparative example in PC electrolyte and reality
Execute the chart of the CV feature of scheme.
As shown in Figure 4 and Figure 5, reference comparative example and the CV result of embodiment, when
In the non-aqueous electrolyte of each Based PC, application is coated with copper (Cu) and nickel (Ni) the porous gold of carbon
When belonging to electrode, it may be determined that compared with comparative example, the reactivity of embodiment dramatically increases.
Special that is, it is possible to determine that the current value for ionic oxide formation improves.The raising of current value be by
In the lifting of the electrode conductivity using porous metals, and also because on porous metals surface
The carbon of coating effectively provides redox reaction site.
Then, electrode of the present invention is compared by electrode embodiments of the present invention and comparative example
Can efficiency characteristics.Fig. 6 is for comparing the embodiment of electrode of the present invention and comparative example
The chart of energy efficiency.Herein, the efficiency of the battery of comparative example 1 and comparative example 2
Rate is used as anode and negative electrode, and compares the embodiment 1 as anode and negative electrode and embodiment party
The energy efficiency of the battery of case 2.
With reference to Fig. 6, it may be determined that be coated with according to the application of embodiment 1 and embodiment 2
The coulombic efficiency that the battery display of carbon strengthens and energy efficiency.In the case of the embodiment of application,
Can efficiency be initially 82%, it be that the energy efficiency of comparative example of application than 77% is more preferable
Feature.Additionally, by the carbon coating coulombic efficiency on the surface of porous metal electrode from 93%
Improve to 95%.
Fig. 7 and Fig. 8 is the oxidation, reduction liquid secondary for describing another embodiment of the present invention
The view of battery.Herein, Fig. 7 is the oxidation, reduction liquid showing another embodiment of the present invention
The exploded view splitting assembly of secondary cell.Fig. 8 is the oxygen showing another embodiment of the present invention
Change the cross-sectional view in the cross section of reduction liquid stream secondary cell.
With reference to Fig. 7 and Fig. 8, the oxidation, reduction liquid secondary cell of another embodiment of the present invention
It it is the secondary electricity of the redox reaction charge or discharge of the metal ion using quantivalence change
Pond.Additionally, another embodiment of the present invention can be driven in the voltage range of 1.5 to 3.0V
Oxidation, reduction liquid secondary cell.
The oxidation, reduction liquid secondary cell of another embodiment of the present invention includes a pair battery carrier
50, a pair current collector 40 and multiple element cell 100.
A pair battery carrier 50 is spaced preset distance and toward each other.As it has been described above, a pair
Current collector 40 inner surface with a pair battery carrier 50 relative to each other respectively is connected.Multiple unit
Battery 100 is embedded between this pair current collector 40.As it has been described above, multiple element cells 100
Each include ion exchange layer 10, the electrode 20 including anode and negative electrode and plate 30.Shown as
, multiple element cells 100 are connected to each other in a continuous manner and share the plate 30 connected each other.
Such as, wherein formed the oxidation, reduction liquid secondary cell of three element cells 100 at Fig. 7 and
Shown in Fig. 8.As shown, owing to two plates 30 connected shared by three element cells 100,
Therefore there are four plates 30.So, the oxidation, reduction liquid secondary electricity of another embodiment of the present invention
Pond is the stacking type cell that wherein three element cells 100 stack in a continuous manner.
As it has been described above, the structure that the most multiple element cells 100 are connected to each other in a continuous manner
In, as disclosed in figure 3, electrode 20 each has the feature that its porous metals surface
Uniformly it is coated with carbon-coating.Owing to each electrode 20 has the oxidoreduction with embodiment of the present invention
The configuration that the electrode of liquid stream secondary cell is identical, therefore omits detailed description.
Although additionally, the most not shown, but the oxygen of another embodiment of the present invention
Change reduction liquid stream secondary cell and also include the oxidation, reduction liquid secondary electricity with embodiment of the present invention
The identical anode slot 60 in pond, cathode can 70, pump 61 and 71, import 63 and 73 and outlet
65 and 75.
Anode slot 60 and cathode can 70 store the anodolyte and the moon flowed when needed respectively
Pole electrolyte and use non-aqueous electrolyte as anodolyte and catholyte.So,
Anode slot 60 and cathode can 70 are individually placed upon the electrode 20 corresponding to said units battery 100
Anode and the left side of element cell 100 of negative electrode and right side.Additionally, anode slot 60 and negative electrode
Groove 70 respectively by import 63 and 73 and outlet 65 and 75 be connected with battery carrier 50.This
Outward, it is provided that pump 61 and 71 is to make electrolyte flow and to incite somebody to action from anode slot 60 and cathode can 70
Electrolyte supplies to element cell 100, and be respectively implanted in anode slot 60 and import 63 it
Between and cathode can 70 and import 73 between.It is to say, can pass through respectively pump 61 and 71,
Import 63 and 73, battery carrier 50 and current collector 40 will flow from anode slot 60 and cathode can 70
The electrolyte supply gone out to element cell 100 and is flowed in reverse order and is stored in anode
In groove 60 and cathode can 70.
Meanwhile, in the above-described embodiment, describe and only use dip coating method or spraying side
Method coats on porous metals.But, embodiment of the present invention are not limited except as.Namely
Say, if it is desired, optionally or compoundly use such as CVD method, sputtering side
Each method of method, chemical gaseous phase depositing process etc..
Additionally, in the above-described embodiment, describe in one embodiment wherein electrode by
The situation that porous metals are formed.But, embodiment of the present invention are not limited except as, and can
Form metal in a grid formation.Additionally, when using carbon suitable when coated, such as general type
The type of writing board shape is also possible.
Additionally, in the above-described embodiment, describe in one embodiment wherein non-aqueous
The situation of coat is formed on the electrode of oxidation, reduction liquid secondary cell.But, the present invention's
Embodiment is not limited except as, and also can be applicable to aqueous oxidation, reduction liquid secondary cell
Electrode.
Additionally, in the above-described embodiment, describe and carry in oxidation, reduction liquid secondary cell
The example of the electrode of confession.But, embodiment of the present invention are not limited except as；Electrode can be extensive
It is applied to include the battery of the electrode being positioned in electrolyte and be particularly applied to stack type electricity
Pond.
Although by reference to the particularly described present invention of exemplary, but art technology
Personnel understand can carry out various forms without departing from the spirit and scope of the present invention with thin
The change of joint.Therefore, only consider exemplary with descriptive sense and be not used in limit
Purpose processed.The scope of the present invention not by the present invention detailed description but by appended right
Require to define, and all repairing of being included in scope of the scope of the present invention
Change and equivalent.
Claims (10)
1. oxidation, reduction liquid secondary cell, comprising:
Element cell, it comprises pair of electrodes, and described electrode is formed by porous metals and described
The surface-coated of porous metals has carbon；
A pair current collector, it is connected with two outer surfaces of described element cell；And
A pair battery carrier, it is connected with each outer surface of described current collector；
Wherein coating on the surface of described porous metals compared with the weight of described porous metals
The amount of carbon is 50wt% or lower, and the carbon content of the coating serosity for coating is 50wt%
Or it is higher.
2. oxidation, reduction liquid secondary cell as claimed in claim 1, wherein said porous gold
Belong to in nickel (Ni), copper (Cu), ferrum (Fe), molybdenum (Mo), titanium (Ti), platinum (Pt) and iridium (Ir)
Any one.
3. oxidation, reduction liquid secondary cell as claimed in claim 1, wherein uses selected from leaching
Any one in stain painting method and spraying method carries out described coating.
4. oxidation, reduction liquid secondary cell as claimed in claim 1, wherein said unit electricity
Pond includes:
Ion exchange layer；
Pair of electrodes, is each connected with two surfaces of described ion exchange layer and includes anode
And negative electrode；And
A pair plate, one of them surface is connected also with the outer surface of each electrode of described electrode pair
And another surface is connected with described current collector.
5. oxidation, reduction liquid secondary cell as claimed in claim 4, wherein said unit electricity
Pond produces electricity according to redox reaction by the ion exchange layer between described electrode.
6. oxidation, reduction liquid secondary cell as claimed in claim 1, it also includes:
Anode slot and cathode can, its left side being separately positioned on described battery carrier and right side and its
It is configured to store electrolyte so that described electrolyte flow；
Pump, it is connected with described anode slot and cathode can and it is configurable to provide described electrolysis
Matter；
Import, it is configured to be connected described pump with described battery carrier so that described electrolyte warp
Described element cell is flowed into by described battery carrier；And
Outlet, it is connected with described battery carrier so that the electrolysis mass flow flowed out from described element cell
Enter described anode slot and cathode can.
7. oxidation, reduction liquid secondary cell, comprising:
At least one element cell, described element cell has a pair by the porous gold being coated with carbon
Belong to the electrode formed；
Wherein coating on the surface of described porous metals compared with the weight of described porous metals
The amount of carbon is 50wt% or lower, and the carbon content of the coating serosity for coating is 50wt%
Or it is higher.
8. oxidation, reduction liquid secondary cell as claimed in claim 7, wherein said porous gold
Belong to in nickel (Ni), copper (Cu), ferrum (Fe), molybdenum (Mo), titanium (Ti), platinum (Pt) and iridium (Ir)
Any one.
9. oxidation, reduction liquid secondary cell as claimed in claim 7, wherein uses selected from leaching
Any one in stain painting method and spraying method carries out described coating.
10. oxidation, reduction liquid secondary cell, comprising:
A pair battery carrier, it is relatively formed and is spaced；
A pair current collector, its each inner surface with the pair of battery carrier be connected；And
At least two element cell, it forms between the pair of current collector,
Wherein said element cell includes a pair electrode formed by the porous metals being coated with carbon；
Wherein coating on the surface of described porous metals compared with the weight of described porous metals
The amount of carbon is 50wt% or lower, and the carbon content of the coating serosity for coating is 50wt%
Or it is higher.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120013470A KR101443680B1 (en) | 2012-02-09 | 2012-02-09 | Redox flow secondary cell |
| KR10-2012-0013470 | 2012-02-09 | ||
| PCT/KR2013/000781 WO2013118998A1 (en) | 2012-02-09 | 2013-01-31 | Redox flow secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104094462A CN104094462A (en) | 2014-10-08 |
| CN104094462B true CN104094462B (en) | 2016-11-30 |
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ID=
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