CN101615678A - A kind of ion-exchange membrane for liquid flow energy-storing batteries and liquid flow energy storage battery group - Google Patents
A kind of ion-exchange membrane for liquid flow energy-storing batteries and liquid flow energy storage battery group Download PDFInfo
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- CN101615678A CN101615678A CN200810012011A CN200810012011A CN101615678A CN 101615678 A CN101615678 A CN 101615678A CN 200810012011 A CN200810012011 A CN 200810012011A CN 200810012011 A CN200810012011 A CN 200810012011A CN 101615678 A CN101615678 A CN 101615678A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to liquid flow energy storage battery, specifically a kind of ion-exchange membrane for liquid flow energy-storing batteries and liquid flow energy storage battery group, described amberplex partly constitutes by two, some is a cation-exchange membrane, another partly is an anion-exchange membrane, and two parts engage or the compound amberplex that becomes an integral body by methods such as hot pressing, blade coating, impregnation dryings.Adopt the amberplex of the present invention can balance or stop the mutual migration of electroactive ion in anodal and the anolyte solution, the electroactive ion of maintenance battery both sides be in a basic balance; Adopt liquid flow energy storage battery group of the present invention can keep charge/discharge capacity unattenuated substantially, increase the battery set charge/discharge cycle-index, and do not need auxiliary equipment.
Description
Technical field
The present invention relates to liquid flow energy storage battery, specifically a kind of ion-exchange membrane for liquid flow energy-storing batteries and liquid flow energy storage battery group.
Background technology
Liquid flow energy storage battery is a kind of as secondary cell, carrying out oxidation and reduction reaction by electrolyte solution respectively at two half-cells charges and discharge process, thereby realize the conversion of energy, liquid flow energy storage battery has electrical power storage and efficient transformation function, characteristics such as long service life, environmental protection, safety, be easy to be complementary, for the utilization of regenerative resource provides technique guarantee with renewable energy systems such as solar energy, wind energies.
All-vanadium liquid flow energy storage battery is a kind of of liquid flow energy storage battery, vanadium ion by different valence state transforms storage and the release that realizes electric energy mutually, has a series of advantage: at first, its active material is present in the liquid, the solid phase that conventional batteries does not take place when discharging and recharging often to be had changes or form changes, and the active material life-span is long; Secondly, the amount of capacity of battery depends on the concentration and the volume (being the total content of cell active materials) of electrolyte, and watt level depends on the size of battery pack, thereby the user can adjust battery capacity or power as required easily; Once more, electrolyte is in flow regime when battery operated, and concentration polarization is littler than other batteries; At last, but battery deep discharge and battery is not caused damage.
Though all-vanadium liquid flow energy storage battery has series of advantages as mentioned above, but the weak point that also has it, be embodied in: because in charging and discharge process, the migratory direction of different valence state vanadium ion in amberplex is different with the migration amount, this just causes the vanadium ion total amount of battery one side constantly to reduce, and the vanadium ion total amount of opposite side constantly increases, and finally causes the continuous reduction of battery charging and discharging capacity.In addition, positive pole and negative pole electrolyte are in the battery plus-negative plate cyclic process, because positive pole and negative pole electrolyte at the caused water transport phenomena of the concentration difference of amberplex both sides, finally cause anodal and the negative pole electrolyte is long-pending unbalance.In the vanadium redox battery running, when amberplex adopted anion-exchange membrane, the water purification migratory direction was anodal to negative pole, and when amberplex adopted cation-exchange membrane, the water migratory direction was opposite.
Present disclosed patent documentation is decayed and the water migration problem because of electroactive material moves the charge/discharge capacity that causes at liquid flow energy storage battery, proposes following solution:
WO:02071522 has designed a kind of secondary cell, and this battery is made up of two electrode chambers and a cation-exchange membrane of separating, and when battery operated, anodal and negative pole electrolyte is respectively by separately electrolyte storage tank inflow electrode chambers separately; In order to move from the water of positive pole in the balancing battery running to negative pole, a kind of container has been used in this invention, this container is made up of two compartments and a reverse osmosis membrane of separating, the positive pole and the negative pole electrolyte that flow out from the battery plus-negative plate chamber enter this container respectively, the water that water moves to negative pole from positive pole to positive pole moves with balancing battery from negative pole by reverse osmosis membrane.
US 6475661 has designed a kind of circulate electrolyte mode, anodal electrolyte enters from the anode chamber of battery pack one end, the anode chamber of next batteries of back inflow of coming out is so got back to anodal electrolysis liquid storage tank after the anode chamber by minor details flows out, negative pole electrolyte is also like this.This feed liquor mode makes the electrical potential difference of first segment and final section battery obviously reduce, and leakage current is eliminated substantially.And, in battery pack, adopt anion-exchange membrane and cation-exchange membrane cycle alternation to use, come compensation water to see through the transmission of film with this.
WO2007/040545 has designed a kind of all-vanadium liquid flow energy storage battery system, system comprises a battery pack, battery pack is made up of such multiple batteries: at least one batteries is made up of positive electrode and the catholyte that matches with positive electrode, negative electrode and the anolyte that matches with negative electrode, a cation-exchange membrane that is used for separating negative electrode and anolyte, and an other batteries adopts anion-exchange membrane to replace cation-exchange membrane.This battery pack structure that is used alternatingly by anion-exchange membrane and cation-exchange membrane is used for stoping water migration clean between negative electrode and the anolyte, clean vanadium migration and the concentration of proton and sulfate ion to change.
Above-mentioned patent documentation is mostly by increasing subsystem, introduce auxiliary equipment or improve the ion migration and the water migration situation of electrolyte solution by changing the electrolyte solution type of flow, but can bring simultaneously such as increasing equipment investment, reducing problems such as battery pack efficient; Though the net migration amount that the way of anion-exchange membrane and cation-exchange membrane can reduce water and vanadium ion is alternately installed in employing in battery pack, it is different with the net migration amount that sees through anion-exchange membrane that but vanadium ion sees through the net migration amount of cation-exchange membrane, therefore, the capacity unbalance problem of battery both sides solution still can appear in long-play, finally causes the decay of battery set charge/discharge capacity.
Summary of the invention
The objective of the invention is to design a kind of ion-exchange membrane for liquid flow energy-storing batteries and liquid flow energy storage battery group, adopt the liquid flow energy storage battery group of this amberplex can balance or stop the mutual migration of electroactive ion in anodal and the anolyte solution, thereby keep the charge/discharge capacity of battery pack unattenuated substantially, increase the battery set charge/discharge cycle-index, and do not need auxiliary equipment.
For achieving the above object, the technical solution used in the present invention is:
A kind of ion-exchange membrane for liquid flow energy-storing batteries, it partly constitutes by two, some is a cation-exchange membrane, and another partly is an anion-exchange membrane, and two parts engage or the compound amberplex that becomes an integral body by methods such as hot pressing, blade coating, impregnation dryings.
A kind of ion-exchange membrane for liquid flow energy-storing batteries, it partly engages by two and forms, and some is a cation-exchange membrane, and another partly is an anion-exchange membrane, and the effective area of two parts film calculates according to following ratio:
Wherein, S
CationThe effective area of-cation-exchange membrane;
S
AnionThe effective area of-anion-exchange membrane;
Flux
c-active ion sees through the net migration flux of unit are cation-exchange membrane;
Flux
a-active ion sees through the net migration flux of unit are anion-exchange membrane;
The effective area ratio of described two parts film is generally 10: 1～and 1: 10, and the effective area of amberplex is the effective area sum of two parts film, above-mentioned " effective area " is meant contacted area between amberplex and the electrode; Two parts film can have two kinds of junctures: first kind is cation-exchange membrane and the hot pressing of anion-exchange membrane joint by constituting this amberplex, and two film joints are bonded together, and forms the amberplex of an integral body; Second kind of the substrate frame by inboard edges and grooves, cation-exchange membrane, anion-exchange membrane, cation-exchange membrane fixed frame and anion-exchange membrane fixed frame are formed; Cation-exchange membrane and anion-exchange membrane are embedded in respectively in cation-exchange membrane fixed frame and the anion-exchange membrane fixed frame, cation-exchange membrane fixed frame and anion-exchange membrane fixed frame are embedded in the groove of substrate frame inner side edge, become as a whole by heat bonding or solvent welding between the substrate frame of amberplex, amberplex fixed frame and inboard edges and grooves.
A kind of ion-exchange membrane for liquid flow energy-storing batteries, it is the multilayer complex films that is composited by cation-exchange membrane and anion-exchange membrane, i.e. the moon/positive double-layered compound film, or sun/the moon/three layers of composite membrane of sun, or the moon/sun/three layers of composite membrane of the moon; Complex method between cation-exchange membrane and the anion-exchange membrane has: pressure sintering, blade coating or spraying process, impregnation drying method etc., and wherein, pressure sintering is by being obtained composite membrane two kinds of films hot pressing regular hour under certain temperature and pressure; Knife coating is to make composite membrane by oven dry behind the another kind of amberplex of a kind of amberplex surface casting one deck; Spraying process is to make composite membrane by oven dry spray the another kind of ion-exchange coating solution of one deck equably on a kind of amberplex surface after; The impregnation drying method is by a kind of amberplex being immersed in certain hour in the another kind of ion-exchange coating solution, repeating to soak back oven dry for several times and make composite membrane.
A kind of liquid flow energy storage battery group, by bipolar plates, positive pole, amberplex, negative pole and another bipolar plates repeat successively stackedly constitute, each electrode places electrode frame separately, the battery pack two ends are opposite polarity termination electrode, termination electrode is made of collector plate and end plate, whole battery group is according to filter-press arrangement sealing assembling, and described amberplex is aforesaid maqting type or compound amberplex; The input of battery pack can be taked constant current mode or constant voltage mode, and the output of battery pack can be taked constant current mode, constant voltage mode, permanent power mode or varying load pattern etc.; The anodal electrolyte solution of battery contains V in the described battery pack
4+/ V
5+Oxidation-reduction pair, and anolyte solution contains V
2+/ V
3+Oxidation-reduction pair; Initial composition before the electrolyte solution charging is: anodal electrolyte is V
4+Solution, negative pole electrolyte are V
3+Solution; Anodal identical with the anolyte liquor capacity, and the concentration of contained electroactive material equates; Concentration range anodal and the contained electroactive material of anolyte solution is: 1～2.5 mol, supporting electrolyte are the sulfuric acid solution of 2～3 mol; Battery pack when adopting the constant current mode input and output, limits on the charging voltage and is limited to single battery voltage 1.7V in charging and discharge cycles process, limits under the discharge voltage and is limited to single battery voltage 0.8V.
The present invention has following advantage:
1, adopt amberplex of the present invention, because this amberplex is formed than engaging according to certain effective area by two kinds of dissimilar amberplexes (being cation-exchange membrane and anion-exchange membrane), therefore effective area that can be by regulating the cation-exchange membrane that constitutes this amberplex and the anion-exchange membrane recently electroactive ion of balance sees through cation-exchange membrane and the net migration amount that sees through anion-exchange membrane, keeps the electroactive total ion concentration of battery both sides in a basic balance;
2. owing to the net migration amount of electroactive ion through dissimilar cation-exchange membranes all is not quite similar with the net migration amount that sees through dissimilar anion-exchange membranes, therefore above-mentioned amberplex can adopt any matched combined of dissimilar cation-exchange membranes and dissimilar anion-exchange membrane, and this is significant aspect useful life at the whole cost that reduces amberplex and raising amberplex;
3. can also be composited by two kinds of dissimilar amberplexes owing to amberplex of the present invention, therefore can effectively stop the mutual migration of electroactive ion in anodal and the anolyte solution, electroactive total ion concentration is constant in the electrolyte of maintenance battery both sides;
4. adopt liquid flow energy storage battery group of the present invention, because single battery all adopts amberplex of the present invention in the battery pack, therefore battery pack of the present invention can keep charge/discharge capacity unattenuated substantially, increases the charge and discharge cycles number of times, and does not need auxiliary equipment.
Description of drawings
Fig. 1 is according to the described amberplex split of claim 4 structural representation;
Fig. 2 is according to the described overall structure amberplex of claim 3 schematic diagram;
Fig. 3 is according to the described three layers of composite membrane section structure schematic diagram of claim 5;
Fig. 4 is a single-cell structure sketch in the liquid flow energy storage battery group;
Fig. 5 is a liquid flow energy storage battery group overall appearance schematic diagram.
Embodiment
Details are as follows for battery pack general structure of the present invention:
Fig. 1 is the amberplex structural representation according to described minute body structure of claim 4, amberplex is made up of substrate frame 1, cation-exchange membrane 2, anion-exchange membrane 3, cation-exchange membrane fixed frame 4 and the anion-exchange membrane fixed frame 5 of inboard edges and grooves, in order to guarantee the sealing of amberplex, make substrate frame, film and fixed frame form an integral body, can adopt two kinds of methods: a kind of is to adopt heat bonding, and a kind of is to adopt solvent welding.When adopting heat bonding, because the melt temperature difference of dissimilar films, this just requires the thermoplasticity of substrate frame and fixed frame to get well, and because the swellability of film, when requiring heat bonding, amberplex will be in dry state; When adopting solvent welding, will make it bonding with bonding agent between substrate frame and the film and between fixed frame and the film, but stop up runner owing to bonding agent may come off, therefore preferably use the method for heat bonding.
Fig. 2 is according to the described integrally-built amberplex schematic diagram of claim 3, by with cation-exchange membrane 2 and anion-exchange membrane 3 joints (retiform part among the figure) hot pressing, make the bonding part hot melt together, form the amberplex of an integral body.
Fig. 3 is the section structure schematic diagram according to the described three layers of composite membrane of claim 5, and this composite membrane is composited by cation-exchange membrane 2, anion-exchange membrane 3 and cation-exchange membrane 2 (perhaps by anion-exchange membrane 3, cation-exchange membrane 2 and anion-exchange membrane 3).
Fig. 4 is the structure diagram of each batteries in the liquid flow energy storage battery group of assembling according to typical press filtration mode, every batteries is by bipolar plates 6, positive electrode battery frame 7, positive electrode 8, amberplex 9, negative electrode 10 and negative electrode battery frame 11 constitute, wherein, amberplex 9 has as Fig. 1 or structure as shown in Figure 2, the liquid flow energy storage battery group repeats stacked by each batteries according to electric series model and constitutes, positive end plate 12 plays self-contained battery group and the effect that is connected external circuit with negative end plate 13, screw rod 14 plays the effect of fastening battery pack, and the overall appearance of battery pack as shown in Figure 5.
Assembling out rated power according to the monocell of structure shown in Figure 4 is 1.1 kilowatts battery pack, this battery pack is made up of according to electric series system 15 joint monocells, wherein, amberplex is the amberplex with shown in Figure 1 minute body structure, their effective area ratio is 6: 1, adopts the method for heat bonding to be combined as a whole between amberplex and substrate frame and the fixed frame.The battery set charge/discharge mode adopts constant current mode, the input and output electric current is 52 amperes, the battery pack output voltage range: 0-25 volt, electrolyte adopt the vanadium ion solution of 1.5 mol, supporting electrolyte is the sulfuric acid solution of 3 mol, and both positive and negative polarity electrolyte volume is 20 liters.
Battery pack power efficient 83%, entire cell system effectiveness 71%, battery pack initiation of charge capacity is 48 ampere-hours, the total concentration that records vanadium ion in anodal and the negative pole electrolyte is respectively: 1.4935 mol and 1.4977 mol.Battery pack is when carrying out the 500th charge and discharge cycles, its charging capacity is 46 ampere-hours, the charging capacity attenuation rate is lower than 5%, recording this moment anodal and negative pole electrolyte amasss and is respectively 20.3 liters and 19.7 liters, the total concentration of vanadium ion is respectively in the both positive and negative polarity electrolyte: 1.4882 mol and 1.5012 mol, battery pack power efficient is 82%, and the entire cell system effectiveness is 70%.
Adopt the battery pack identical with embodiment 1, different is, adopt the method for solvent welding to be combined as a whole between amberplex and substrate frame and the fixed frame, battery pack power efficient 82.5%, entire cell system effectiveness 71%, battery pack is after 500 charge and discharge cycles of operation, its charging capacity decays to 45.6 ampere-hours by 48 ampere-hours, attenuation rate is lower than 5%, anodal and negative pole electrolyte long-pending by original separately 20 liters become 20.4 liters at positive pole, 19.6 liters at negative pole, the total concentration of vanadium ion becomes 1.4885 mol and 1.5026 mol by 1.4997 original mol and 1.4964 mol respectively in the both positive and negative polarity electrolyte, this moment, battery pack power efficient was 80%, and the entire cell system effectiveness is 70%.
Adopt the battery pack identical with embodiment 1, different is, respectively save the amberplex employing frame mode as shown in Figure 2 of monocell in the battery pack, promptly by constituting two kinds of film joint hot pressing of amberplex, make the bonding part hot melt together, form the amberplex of an integral body, battery pack power efficient 82%, entire cell system effectiveness 72%, battery pack is after 500 charge and discharge cycles of operation, its charging capacity decays to 46 ampere-hours by 47.8 ampere-hours, attenuation rate is lower than 5%, anodal and negative pole electrolyte long-pending by original separately 20 liters become 20.2 liters at positive pole, 19.8 liters at negative pole, the total concentration of vanadium ion becomes 1.4894 mol and 1.5103 mol by 1.5013 original mol and 1.4989 mol respectively in the both positive and negative polarity electrolyte, and this moment, battery pack power efficient was 81%, and the entire cell system effectiveness is 71%.
Embodiment 4
Adopt the battery pack identical with embodiment 1, different is, constituting the anion-exchange membrane of amberplex and the effective area ratio of cation-exchange membrane is 4: 1, battery pack power efficient 81%, entire cell system effectiveness 70%, battery pack initiation of charge capacity is 48.2 ampere-hours, and the total concentration that records vanadium ion in anodal and the negative pole electrolyte is respectively: 1.4987 mol and 1.4973 mol.Battery pack is when carrying out the 500th charge and discharge cycles, its charging capacity is 45.5 ampere-hours, the charging capacity attenuation rate is lower than 5%, recording this moment anodal and negative pole electrolyte amasss and is respectively 20.5 liters and 19.5 liters, the total concentration of vanadium ion is respectively in the both positive and negative polarity electrolyte: 1.4878 mol and 1.5023 mol, battery pack power efficient is 80%, and the entire cell system effectiveness is 69%.
Adopt the battery pack identical with embodiment 1, different is, amberplex is three layers of composite membrane as shown in Figure 3, composite membrane prepares with pressure sintering, battery pack power efficient 82%, entire cell system effectiveness 71%, battery pack initiation of charge capacity is 48 ampere-hours, the total concentration that records vanadium ion in anodal and the negative pole electrolyte is respectively: 1.4977 mol and 1.5013 mol.Battery pack is when carrying out the 500th charge and discharge cycles, its charging capacity is 46.2 ampere-hours, the charging capacity attenuation rate is lower than 5%, recording this moment anodal and negative pole electrolyte amasss and is respectively 20.3 liters and 19.7 liters, the total concentration of vanadium ion is respectively in the both positive and negative polarity electrolyte: 1.4942 mol and 1.5034 mol, battery pack power efficient is 81%, and the entire cell system effectiveness is 70%.
Adopt the battery pack identical with embodiment 5, different is, composite membrane prepares with knife coating, battery pack power efficient 83%, entire cell system effectiveness 71%, battery pack initiation of charge capacity is 47.9 ampere-hours, and the total concentration that records vanadium ion in anodal and the negative pole electrolyte is respectively: 1.5007 mol and 1.4993 mol.Battery pack is when carrying out the 500th charge and discharge cycles, its charging capacity is 45.8 ampere-hours, the charging capacity attenuation rate is lower than 5%, recording this moment anodal and negative pole electrolyte amasss and is respectively 20.2 liters and 19.8 liters, the total concentration of vanadium ion is respectively in the both positive and negative polarity electrolyte: 1.4988 mol and 1.5105 mol, battery pack power efficient is 81%, and the entire cell system effectiveness is 70%.
Adopt the battery pack identical with embodiment 5, different is, composite membrane prepares with the impregnation drying method, battery pack power efficient 82%, entire cell system effectiveness 70%, battery pack initiation of charge capacity is 48.1 ampere-hours, and the total concentration that records vanadium ion in anodal and the negative pole electrolyte is respectively: 1.4995 mol and 1.4863 mol.Battery pack is when carrying out the 500th charge and discharge cycles, its charging capacity is 46 ampere-hours, the charging capacity attenuation rate is lower than 5%, recording this moment anodal and negative pole electrolyte amasss and is respectively 20.3 liters and 19.7 liters, the total concentration of vanadium ion is respectively in the both positive and negative polarity electrolyte: 1.5027 mol and 1.4843 mol, battery pack power efficient is 81%, and the entire cell system effectiveness is 69%.
Different with embodiment 1～7, when amberplex adopts the single ionic exchange membrane fully, during as the Nafion115 cation-exchange membrane, battery pack is after 500 charge and discharge cycles of operation, its charging capacity decays to 40 ampere-hours by 48 ampere-hours, attenuation rate is greater than 10%, anodal and negative pole electrolyte long-pending by original separately 20 liters become 22 liters at positive pole, 18 liters at negative pole, the total concentration of vanadium ion becomes 1.3548 mol and 1.6497 mol by 1.5043 original mol and 1.4993 mol respectively in the both positive and negative polarity electrolyte, battery pack power efficient is 80%, and the entire cell system effectiveness is 69%.
Claims (8)
1. ion-exchange membrane for liquid flow energy-storing batteries is characterized in that: described amberplex partly constitutes by two, and some is a cation-exchange membrane, and another partly is an anion-exchange membrane, and the effective area of two parts film calculates according to following ratio:
Wherein, S
CationThe effective area of-cation-exchange membrane;
S
AnionThe effective area of-anion-exchange membrane;
Flux
c-electroactive ion sees through the net migration flux of unit are cation-exchange membrane;
Flux
a-electroactive ion sees through the net migration flux of unit are anion-exchange membrane;
And the effective area of amberplex is the effective area sum of two parts film.
2. according to the described amberplex of claim 1, it is characterized in that: constitute the cation-exchange membrane of this amberplex and the effective area ratio of anion-exchange membrane and be generally S
Cation: S
Anion=10: 1～1: 10.
3. according to the described amberplex of claim 1, it is characterized in that: by the cation-exchange membrane and the hot pressing of anion-exchange membrane joint that will constitute this amberplex, two film joints are bonded together, form the amberplex of an integral body.
4. according to the described amberplex of claim 1, it is characterized in that: its substrate frame by inboard edges and grooves, cation-exchange membrane, anion-exchange membrane, cation-exchange membrane fixed frame and anion-exchange membrane fixed frame are formed; Cation-exchange membrane and anion-exchange membrane are embedded in respectively in cation-exchange membrane fixed frame and the anion-exchange membrane fixed frame, cation-exchange membrane fixed frame and anion-exchange membrane fixed frame are embedded in the groove of substrate frame inner side edge, become as a whole by heat bonding or solvent welding between the substrate frame of amberplex, amberplex fixed frame and inboard edges and grooves.
5. ion-exchange membrane for liquid flow energy-storing batteries, it is characterized in that: it is the multilayer complex films that is composited by cation-exchange membrane and anion-exchange membrane, i.e. the moon/positive double-layered compound film, or sun/the moon/three layers of composite membrane of sun, or the moon/sun/three layers of composite membrane of the moon.
6. according to the described amberplex of claim 5, it is characterized in that: constituting the cation-exchange membrane of this composite membrane and the complex method between the anion-exchange membrane has: pressure sintering, blade coating, spraying process or impregnation drying method.
7. liquid flow energy storage battery group, repeat stacked formation successively by bipolar plates, positive pole, amberplex, negative pole and another bipolar plates, each electrode places electrode frame separately, the battery pack two ends are opposite polarity termination electrode, termination electrode is made of collector plate and end plate, whole battery group is according to filter-press arrangement sealing assembling, and it is characterized in that: described amberplex is claim 1 or the described amberplex of claim 5.
8. according to the described battery pack of claim 7, it is characterized in that: the anodal electrolyte solution of battery contains V in the battery pack
4+/ V
5+Oxidation-reduction pair, and anolyte solution contains V
2+/ V
3+Oxidation-reduction pair; Initial composition before the electrolyte solution charging is: anodal electrolyte is V
4+Solution, negative pole electrolyte are V
3+Solution; Anodal identical with the volume of anolyte solution, and the concentration of contained electroactive material equates; Concentration range anodal and the contained electroactive material of anolyte solution is: 1～2.5 mol, supporting electrolyte are the sulfuric acid solution of 2～3 mol.
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| CN102011135A (en) * | 2010-12-06 | 2011-04-13 | 上海林洋储能科技有限公司 | Cyclic electrolysis reaction device and method for preparing vanadium battery electrolyte |
| CN102324535A (en) * | 2011-09-09 | 2012-01-18 | 深圳市金钒能源科技有限公司 | Vanadium redox flow battery integrated frame board and preparation method thereof and electric pile prepared by the frame board |
| CN102468494A (en) * | 2010-10-29 | 2012-05-23 | 新奥科技发展有限公司 | All-vanadium redox flow battery electrode and preparation method thereof, and all-vanadium redox flow battery |
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| CN100495780C (en) * | 2007-06-20 | 2009-06-03 | 天津大学 | Production of film electrode for fuel cell or electrolysis |
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| CN102468494A (en) * | 2010-10-29 | 2012-05-23 | 新奥科技发展有限公司 | All-vanadium redox flow battery electrode and preparation method thereof, and all-vanadium redox flow battery |
| CN102468494B (en) * | 2010-10-29 | 2016-02-10 | 新奥科技发展有限公司 | A kind of vanadium redox flow battery electrode and preparation method thereof, and all-vanadium flow battery |
| CN102011135A (en) * | 2010-12-06 | 2011-04-13 | 上海林洋储能科技有限公司 | Cyclic electrolysis reaction device and method for preparing vanadium battery electrolyte |
| CN102324535A (en) * | 2011-09-09 | 2012-01-18 | 深圳市金钒能源科技有限公司 | Vanadium redox flow battery integrated frame board and preparation method thereof and electric pile prepared by the frame board |
| CN104300101A (en) * | 2013-07-18 | 2015-01-21 | 中国科学院大连化学物理研究所 | Difunctional composite porous membrane and preparation and application thereof |
| CN104300101B (en) * | 2013-07-18 | 2017-05-03 | 中国科学院大连化学物理研究所 | Difunctional composite porous membrane and preparation and application thereof |
| CN103456977A (en) * | 2013-08-28 | 2013-12-18 | 广东电网公司电力科学研究院 | Method for improving operation efficiency of all-vanadium redox flow battery |
| CN104282923A (en) * | 2014-10-09 | 2015-01-14 | 中国科学院金属研究所 | Anode/enhanced/cathode amphoteric composite membrane for all-vanadium redox flow battery and preparation method of composite membrane |
| CN114744253A (en) * | 2022-04-01 | 2022-07-12 | 香港科技大学 | Method for inhibiting capacity attenuation and online capacity recovery of all-vanadium redox flow battery |
| CN114744253B (en) * | 2022-04-01 | 2023-09-29 | 香港科技大学 | Method for inhibiting capacity attenuation and online capacity recovery of all-vanadium redox flow battery |
| CN116190694A (en) * | 2022-09-07 | 2023-05-30 | 南京航空航天大学 | Calcium ion group thermoelectric conversion and energy storage system |
| CN116190694B (en) * | 2022-09-07 | 2024-02-13 | 南京航空航天大学 | Calcium ion group thermoelectric conversion and energy storage system |
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