CN103578793A - Active equalizing method for cells of module of super-capacitor - Google Patents
Active equalizing method for cells of module of super-capacitor Download PDFInfo
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- CN103578793A CN103578793A CN201210262763.4A CN201210262763A CN103578793A CN 103578793 A CN103578793 A CN 103578793A CN 201210262763 A CN201210262763 A CN 201210262763A CN 103578793 A CN103578793 A CN 103578793A
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Abstract
The invention discloses an active equalizing method for cells of a module of a super-capacitor. Shuttle molecules with oxidation reduction potential are added in an electrolyte solution of the cells of the module of the super capacitor, wherein the excitation voltage of the shuttle molecules is higher than the rated charging voltage of the super-capacitor and is lower than the critical damage voltage of the cells of the super-capacitor. According to the active equalizing method for the cells of the module of the super capacitor, the cells of the module are directly and evenly integrated in the manufacturing of the cells, an active equalizing strategy is executed, and an equalizing scheme is simple and easy to practice. A complex external integrated managing circuit is not needed in the equalization of the module, and thus cost is lowered greatly. Complex line connection related in an external equalizing scheme is avoided in the connection among modules, and thus the system management of the modules is simplified greatly.
Description
Technical field
The present invention relates to super capacitor battery core and module, relate in particular to a kind of active equalization method of super-capacitor module battery core.
Background technology
Ultracapacitor is again double electric layer capacitor, is a kind of Novel energy storage apparatus, and it has the features such as short, long service life of charging interval, good temp characteristic, energy savings and environmental protection, and tool has been widely used.The voltage of single super capacitor battery core is lower, and in super-capacitor module, energy-storage system connects to provide required higher voltage in application by a plurality of battery cores.Because capacity and the internal resistance of each battery core exists difference, therefore the voltage of each battery core in series connection will have wider distribution.Voltage difference between battery core mainly comes from the difference of the leakage current between battery core.The voltage of institute's load of the battery core that leakage current is large is little, and the voltage of the battery core institute load that leakage current is little is large.Under charged state, the voltage difference between battery core will make battery core that leakage current is little in overcharging state, causes the destruction of electrode structure and the decay of battery core performance.At present, the leakage current difference reducing between battery core has passive equilibrium and two kinds of strategies of active balancing.In passive equilibrium strategy, respectively with one external resistance parallel connection of each battery core, is wherein the more than 10 times of leakage current from the electric current of external resistance transmission.Active strategy is tandem tap circuit in parallel resistance, to realize the control to the switch of resistance in parallel.These two kinds of strategies have all increased the leakage current of battery core, cause the reduction of charge efficiency, and have greatly increased the complexity of the management circuit of super-capacitor module.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of this invention is to provide a kind of active equalization method of super-capacitor module battery core, to meet when charging, battery core is carried out to over-charge protective; When activating, reduce the fluctuation of leakage current between battery core; The maximum voltage bearing during unified battery core charging, the consistency of raising battery core capacity.
Technical scheme: in order to realize foregoing invention object, the technical solution used in the present invention is:
A kind of active equalization method of super-capacitor module battery core: add the molecule that shuttles back and forth with oxidation-reduction potential in the electrolyte of super-capacitor module battery core; The excitation voltage of the described molecule that shuttles back and forth is higher than the specified charging voltage of super capacitor, and lower than the critical infringement voltage of super capacitor battery core.
Described critical infringement voltage refers to: under this voltage, the performance of super capacitor battery core, in 10000 circulations, has performance obviously to decay, for example: obviously decay can be battery core volume lowering 10%, and performance index are not limited to this.
The described molecule that shuttles back and forth comprises derivative, metal porphyrins and the side chain substitutive derivative thereof of derivative, triazolium salt and side chain replacement thereof that ferrocene and derivative, ferrocene and derivative thereof, imidazole salts and side chain thereof replace.
In organic phase electrolyte, described in the shuttle back and forth oxidation-reduction potential maximum operating voltage of molecule be 2.3 ~ 4.5V.
The consumption of the described molecule that shuttles back and forth is the 1-5wt% of electrolyte.
The battery core voltage of described super-capacitor module is 1.5V ~ 3.6V.
The active equalization method of super-capacitor module battery core of the present invention directly adds the molecule that shuttles back and forth with suitable oxidation-reduction potential in the electrolyte of super-capacitor module battery core, thereby improves harmony and the consistency of battery core performance in energy-storage system.The function of oxidation-reduction pair comprises: while 1) charging, battery core is carried out to over-charge protective; 2), when activating, reduce the fluctuation of leakage current between battery core; 3) maximum voltage bearing while unifying battery core charging, the consistency of raising battery core capacity.
The electrochemical window of oxidation-reduction pair is a little more than specified (design) voltage of battery core, when battery core overcharges, the molecule that shuttles back and forth that overcharges or cross in the battery core of putting is excited, molecule is after positive pole is oxidized, through electrolyte, transferring to negative pole is reduced, thereby limited the voltage that battery core is born, balanced voltage that battery core is born.When charging voltage surpasses design load, the voltage that battery core is born is the redox potential restriction of oxidation-reduction pair molecule, has avoided the too high damage possible to battery core of charging voltage.After the molecule that shuttles back and forth is excited, mainly by molecule, the transfer between both positive and negative polarity completes the leakage current of battery core, thereby has improved consistency between battery core.
Beneficial effect: the active equalization method of super-capacitor module battery core of the present invention, directly the battery core equilibrium of module is integrated in the manufacture of battery core, be active equalization strategy, equalization scheme is simple; The equilibrium of module does not need complicated outside integrated management circuit, and cost reduces greatly; Complicated connection related in external Equilibrium scheme has been avoided in connection between module, and system management is greatly simplified; Avoid overcharged voltage to the impact of electrode and irreversibility infringement, thereby extended circulation and the useful life of battery core.
Accompanying drawing explanation
Fig. 1 is the structural representation of the super-capacitor module that is composed in series by more piece super capacitor battery core;
Fig. 2 utilizes the molecule that shuttles back and forth to carry out active balancing principle schematic to battery core;
Fig. 3 adds the super capacitor battery core charge-discharge performance comparison diagram shuttling back and forth after molecule.
Embodiment
Below in conjunction with accompanying drawing, the present invention will be further explained.
As shown in Figure 1, super-capacitor module is composed in series by more piece battery core, if every economize on electricity core provides voltage, is V, and the total voltage being provided by n economize on electricity core is nV.The total capacity of module is determined by the battery core of the capacity minimum in battery core of connecting.Voltage that battery core is born is determined by battery core internal resistance.When electric discharge, the battery core capacity of capacity minimum reaches electric discharge terminal at first.In when charging, the battery core of the capacity minimum state that reaches capacity at first.It is the highest that the battery core of internal resistance minimum is born voltage.Overcharge and all can produce irreversible infringement to the structure of battery core and performance with over-discharge can.In addition, the capacity between battery core does not mate the cut-off in advance that will cause charge or discharge, makes battery pack can use the reduction of capacity.At present, the equilibrium of super-capacitor module realizes by external circuit.The introducing of equalizing circuit increases considerably the administration module complexity of battery pack and super capacitor, has reduced the efficiency for charge-discharge of battery pack and module, and makes super capacitor cost high, expensive.
The present invention adds the molecule that shuttles back and forth with suitable oxidation-reduction potential in the electrolyte of super-capacitor module battery core, thereby improves harmony and the consistency of battery core performance in energy-storage system.As shown in Figure 2 and Figure 3, when batteries charging, reach the oxidation-reduction pair in battery core while overcharging state and be activated, the voltage that battery core is born by the molecule that shuttles back and forth redox reaction limit, therefore, the state that overcharges of electric capacity is limited, and has avoided the battery core performance degradation causing owing to overcharging.Wherein, oxidation-reduction pair includes but not limited to following material:
(1) ferrocene and derivative thereof, general structure is as follows:
In formula, X group includes but not limited to H, F, Cl, Br, C
xh
y, CN, OH, OC
xh
y; X=1 ~ 6, y=3 ~ 13.
(2) cobaltocene and derivative thereof, general structure is as follows:
In formula, X group includes but not limited to H, F, Cl, Br, C
xh
y, CN, OH, OC
xh
y; X=1 ~ 6, y=3 ~ 13.
(3) imidazole and its derivants, general structure is as follows:
In formula, R1, R2 group include but not limited to H, F, Cl, Br, C
xh
y, CN, OH, OC
xh
y; X=1 ~ 6, y=3 ~ 13.
(4) triazole and derivative compound thereof, general structure is as follows:
In formula, R1, R2 group include but not limited to H, F, Cl, Br, C
xh
y, CN, OH, OC
xh
y; X=1 ~ 6, y=3 ~ 13.
(5) metalloporphyrin and derivative thereof, general structure is as follows:
In formula, M includes but not limited to Fe, Co, Ni, Cu, Zn; R1, R2, R3, R4 group include but not limited to H, F, Cl, Br, C
xh
y, CN, OH, OC
xh
y; X=1 ~ 6, y=3 ~ 13.
Embodiment 1
After being uniformly mixed in NMP, high surface area activited carbon, conductive black and bonding agent form super capacitor electrode in aluminium foil surface coating.Through overbaking, dry after, positive pole, negative pole and porous septum material are carried out under anhydrous and oxygen-free condition, transferring in aluminum plastic film shell after lamination.Electrolyte is 1MLiPF
6at EC/DEC(1:1) mixed solvent, imidazoles or glyoxal ethyline add in electrode solution as additive, and the concentration of imidazoles is 1-5 wt%.0.5mL electrolyte is made a bet after super capacitor battery core at anhydrous and oxygen-free environment, standing in a vacuum.After aluminum plastic film shell being sealed after 30min, super capacitor battery core is migrated out to glove box and carry out flanging sizing.
The performance test of super capacitor battery core is carried out discharging and recharging on instrument.Specified (design) charging voltage of super capacitor battery core is 2.4V.In actual test, critical infringement voltage is 2.8V.When voltage reaches 2.6V, imidazole molecule is excited.The charging voltage of super capacitor is defined in 2.6V.Charging current significantly improves, and charging circuit current value increases with the concentration rising of added imidazole molecule.During electric discharge, when lower voltage arrives 2.5V, in charging circuit, electric current significantly reduces, and the leak resistance of current value and super capacitor is directly proportional.
At maximum charging voltage, reaching 2.6V(overcharges) in the situation that, the performance of super capacitor battery core decays without obvious in >10000 circulation.
Embodiment 2
After being uniformly mixed in NMP, high surface area activited carbon, conductive black and bonding agent form super capacitor electrode in aluminium foil surface coating.Through overbaking, dry after, positive pole, negative pole and porous septum material are carried out under anhydrous and oxygen-free condition, transferring in aluminum plastic film shell after lamination.Electrolyte is 1MLiPF
6at EC/DEC(1:1) mixed solvent.0.5mL electrolyte is made a bet after super capacitor battery core at anhydrous and oxygen-free environment, standing in a vacuum.After aluminum plastic film shell being sealed after 30min, super capacitor battery core is migrated out to glove box and carry out flanging sizing.
The performance test of super capacitor battery core is carried out discharging and recharging on instrument.Specified (design) charging voltage of super capacitor battery core is 2.4V.In actual test, critical infringement voltage is 3.0V, and when voltage surpasses 2.7V, charging current obviously improves.At maximum charging voltage, reaching 3.0V(overcharges) in the situation that, the performance of super capacitor battery core is decay >30% after >10000 circulation, as shown in Figure 3.
Embodiment 3
After being uniformly mixed in NMP, high surface area activited carbon, conductive black and bonding agent (85:10:5) form the super capacitor negative pole utmost point in aluminium foil surface coating.The electrode utmost point through overbaking, dry after, positive pole, negative pole and porous septum material are carried out under anhydrous and oxygen-free condition, transferring in aluminum plastic film shell after lamination.Electrolyte is 1M N (C
2h
5)
4bF
4in second cyanogen solvent, 2-5 wt% 1,1 dimethyl ferrocene adds in electrode solution as additive.0.5mL electrolyte is made a bet after super capacitor battery core at anhydrous and oxygen-free environment, standing in a vacuum.After aluminum plastic film shell being sealed after 30min, super capacitor battery core is migrated out to glove box and carry out flanging sizing.
The performance test of super capacitor battery core is carried out discharging and recharging on instrument.The design charging voltage of super capacitor battery core is 2.4V.In actual test, critical infringement voltage is 3.4V.When voltage reaches 2.4V, ferrocene molecule is excited.The charging voltage of super capacitor is defined in 2.4V.Charging current significantly improves, and charging circuit current value increases with the concentration rising of added ferrocene molecule.During electric discharge, when lower voltage arrives 2.4V, in charging circuit, electric current significantly reduces, and the leak resistance of current value and super capacitor is directly proportional.
At maximum charging voltage, reaching 2.9V(overcharges) in the situation that, the performance of super capacitor battery core decays without obvious in >10000 circulation.
Embodiment 4
After being uniformly mixed in NMP, high surface area activited carbon, conductive black and bonding agent (85:10:5) form the super capacitor negative pole utmost point in aluminium foil surface coating.The electrode utmost point through overbaking, dry after, positive pole, negative pole and porous septum material are carried out under anhydrous and oxygen-free condition, transferring in aluminum plastic film shell after lamination.Electrolyte is 1M N (C
2h
5)
4bF
4in second cyanogen solvent.0.5mL electrolyte is made a bet after super capacitor battery core at anhydrous and oxygen-free environment, standing in a vacuum.After aluminum plastic film shell being sealed after 30min, super capacitor battery core is migrated out to glove box and carry out flanging sizing.
The performance test of super capacitor battery core is carried out discharging and recharging on instrument.The design charging voltage of super capacitor battery core is 2.7V.In actual test, critical infringement voltage is 3.4V, and when voltage surpasses 2.9V, charging current obviously improves.At maximum charging voltage, reaching 3.4V(overcharges) in the situation that, the performance of super capacitor battery core is decay >30% after >10000 circulation.
Claims (10)
1. an active equalization method for super-capacitor module battery core, is characterized in that: in the electrolyte of super-capacitor module battery core, add the molecule that shuttles back and forth with oxidation-reduction potential; The excitation voltage of the described molecule that shuttles back and forth is higher than the specified charging voltage of super capacitor, and lower than the critical infringement voltage of super capacitor battery core.
2. the active equalization method of super-capacitor module battery core according to claim 1, is characterized in that: described in derivative, metal porphyrins and the side chain substitutive derivative thereof that derivative, triazolium salt and side chain thereof that molecule comprises that ferrocene and derivative, cobaltocene and derivative thereof, imidazole salts and side chain thereof replace replace that shuttle back and forth.
3. the active equalization method of super-capacitor module battery core according to claim 2, is characterized in that: the general structure of described ferrocene and derivative thereof is as follows:
In formula, X group includes but not limited to H, F, Cl, Br, C
xh
y, CN, OH, OC
xh
y; X=1 ~ 6, y=3 ~ 13.
4. the active equalization method of super-capacitor module battery core according to claim 2, is characterized in that: the general structure of described cobaltocene and derivative thereof is as follows:
In formula, X group includes but not limited to H, F, Cl, Br, C
xh
y, CN, OH, OC
xh
y; X=1 ~ 6, y=3 ~ 13.
5. the active equalization method of super-capacitor module battery core according to claim 2, is characterized in that: the general structure of described imidazole and its derivants is as follows:
In formula, R1, R2 group include but not limited to H, F, Cl, Br, C
xh
y, CN, OH, OC
xh
y; X=1 ~ 6, y=3 ~ 13.
6. the active equalization method of super-capacitor module battery core according to claim 2, is characterized in that: the general structure of described triazole and derivative compound thereof is as follows:
In formula, R1, R2 group include but not limited to H, F, Cl, Br, C
xh
y, CN, OH, OC
xh
y; X=1 ~ 6, y=3 ~ 13.
7. the active equalization method of super-capacitor module battery core according to claim 2, is characterized in that: the general structure of described metalloporphyrin and derivative thereof is as follows:
In formula, M includes but not limited to Fe, Co, Ni, Cu, Zn; R1, R2, R3, R4 group include but not limited to H, F, Cl, Br, C
xh
y, CN, OH, O C
xh
y; X=1 ~ 6, y=3 ~ 13.
8. the active equalization method of super-capacitor module battery core according to claim 1, is characterized in that: in organic phase electrolyte, described in the shuttle back and forth oxidation-reduction potential maximum operating voltage of molecule be 2.3 ~ 4.5V.
9. the active equalization method of super-capacitor module battery core according to claim 1, is characterized in that: described in the 1 ~ 5wt% that the consumption of molecule is electrolyte that shuttles back and forth.
10. the active equalization method of super-capacitor module battery core according to claim 1, is characterized in that: the battery core voltage of described super-capacitor module is 1.5V ~ 3.6V.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6004698A (en) * | 1997-08-21 | 1999-12-21 | The United States Of America As Represented By The United States Department Of Energy | Solid polymer electrolyte electrochemical storage cell containing a redox shuttle additive for overcharge protection |
| CN1284208A (en) * | 1998-01-28 | 2001-02-14 | 凯米科有限责任公司 | Rebox flow battery system and cell stack |
| US20070178370A1 (en) * | 2006-02-02 | 2007-08-02 | The University Of Chicago | Lithium-ion batteries with intrinsic pulse overcharge protection |
| CN102280266A (en) * | 2011-05-30 | 2011-12-14 | 大连交通大学 | Super capacitor with superposed liquid-flow pseudocapacitance |
| CN102509650A (en) * | 2011-09-28 | 2012-06-20 | 江苏富朗特新能源有限公司 | Grouping method of organic super-capacitor modules |
-
2012
- 2012-07-27 CN CN201210262763.4A patent/CN103578793A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6004698A (en) * | 1997-08-21 | 1999-12-21 | The United States Of America As Represented By The United States Department Of Energy | Solid polymer electrolyte electrochemical storage cell containing a redox shuttle additive for overcharge protection |
| CN1284208A (en) * | 1998-01-28 | 2001-02-14 | 凯米科有限责任公司 | Rebox flow battery system and cell stack |
| US20070178370A1 (en) * | 2006-02-02 | 2007-08-02 | The University Of Chicago | Lithium-ion batteries with intrinsic pulse overcharge protection |
| CN102280266A (en) * | 2011-05-30 | 2011-12-14 | 大连交通大学 | Super capacitor with superposed liquid-flow pseudocapacitance |
| CN102509650A (en) * | 2011-09-28 | 2012-06-20 | 江苏富朗特新能源有限公司 | Grouping method of organic super-capacitor modules |
Non-Patent Citations (1)
| Title |
|---|
| 杨德才: "《锂离子电池安全性-原理、设计与测试》", 31 May 2012, 电子科技大学出版社 * |
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Application publication date: 20140212 |