CN104143660B - Plumbic acid-all vanadium mixed energy storage battery - Google Patents

Plumbic acid-all vanadium mixed energy storage battery Download PDF

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CN104143660B
CN104143660B CN201310167808.4A CN201310167808A CN104143660B CN 104143660 B CN104143660 B CN 104143660B CN 201310167808 A CN201310167808 A CN 201310167808A CN 104143660 B CN104143660 B CN 104143660B
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vanadium
acid
electrolyte
battery
electrode
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CN104143660A (en
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赖勤志
张华民
程元徽
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a plumbic acid-all vanadium mixed energy storage battery which comprises a positive electrode, a positive electrolyte cavity, a diaphragm, a negative electrolyte cavity and a negative electrode. The positive electrode is a PbO2 electrode. The negative electrode is a lead electrode. The positive electrolyte cavity is filled with a tetravalent vanadium acidic solution which is used as a positive electrolyte. The negative electrolyte cavity is filled with a trivalent vanadium acidic solution which is used as a negative electrolyte. By the adoption of electrodes of a lead-acid cell and an electrolyte of an all-vanadium redox flow battery and with the combination of electrochemical current forming reactions of the lead-acid cell and the all-vanadium redox flow battery, the lead-acid cell and the all-vanadium redox flow battery are combined organically, thus raising battery capacity and energy density.

Description

A kind of plumbic acid-full vanadium hybrid energy-storing battery
Technical field
The present invention relates to energy-storage battery, specifically a kind of plumbic acid-full vanadium hybrid energy-storing battery.
Background technology
A few days ago increasingly short with world energy supplies, people start the exploitation to regenerative resources such as wind energy, solar energy With utilize extensive concern, but the stable power-supplying of the renewable energy system such as solar energy to be ensured, wind energy, be necessary for reference to high Effect, cheap, safe and reliable energy storage technology are coordinated with it, make a general survey of various energy storage technologies, and the wherein liquor stream of chemical energy storage mode is stored up Battery one of battery of the extensive energy storage of current optimum can be become with its unique advantage.
All-vanadium liquid flow energy storage battery is a kind of low energy consumption, high efficiency, environmentally friendly liquid flow energy storage battery, has energy Density and current efficiency are high, device is simply steerable, long service life, with low cost the advantages of, be mainly used in peak load regulation network, The fields such as the renewable energy power generation such as wind energy and solar energy, electric automobile.
But current all-vanadium liquid flow energy storage battery haves the shortcomings that price height, energy density are low, limits it extensive Use.
Lead-acid battery technology maturation, existing century-old developing history, at present automobile-used, rise and the field such as employ and have widely Application.But lead-acid battery limits application in extensive energy storage field due to its relatively low capacity.
The present invention passes through using the electrode of lead-acid battery and the electrolyte of all-vanadium flow battery, in conjunction with lead-acid battery and full vanadium The electrification of flow battery studies stream reaction, the two is organically combined, improves battery capacity and the energy density of battery.
Content of the invention
It is an object of the invention to by using the electrode of lead-acid battery and the electrolyte of all-vanadium flow battery, in conjunction with plumbic acid Battery studies stream reaction with the electrification of all-vanadium flow battery, the two is organically combined, improves battery capacity and energy density.
For achieving the above object, the technical solution used in the present invention is as follows：
A kind of plumbic acid-full vanadium hybrid energy-storing battery, including the positive pole setting gradually, anolyte sap cavity, barrier film, negative electricity Solution sap cavity, negative pole, just extremely PbO2Electrode, negative pole is lead electrode, and the acid solution being filled with tetravalence vanadium in anolyte sap cavity is made For anode electrolyte, the acid solution being filled with trivalent vanadium in electrolyte sap cavity is as electrolyte liquid.
When battery charges, there is tetravalence vanadium first to the oxidation reaction of pentavalent vanadium in positive pole, with the consumption of tetravalence vanadium, PbSO4 progressively participates in electrification and studies stream reaction, generates PbO2；There is trivalent vanadium first to the reduction reaction of bivalent vanadium in negative pole, with The consumption of trivalent vanadium, PbSO4 progressively participates in electrification and studies stream reaction, generates Pb；
During electric discharge, there is the reduction reaction of PbO2 to PbSO4 in positive pole first, and with the consumption of PbO2, pentavalent vanadium is progressively joined Study stream reaction with electrification, generate tetravalence vanadium；There is the oxidation reaction of Pb to PbSO4 first in negative pole, with the consumption of PbSO4, Bivalent vanadium progressively participates in electrification and studies stream reaction, generates trivalent vanadium.
Anode electrolyte is the acid solution of concentration 0.1-4mol/L tetravalent vanadium ion, and electrolyte liquid is concentration 0.1- The acid solution of 4mol/L trivalent vanadium ion, described acid solutions are 0.5-5mol/L.
The described sour mixed system for hydrochloric acid, sulfuric acid, phosphoric acid or above-mentioned acid；Described barrier film includes cationic membrane, anion The dense film such as film or perforated membrane.
Beneficial effects of the present invention：
1st, pass through using the electrode of lead-acid battery and the electrolyte of all-vanadium flow battery, in conjunction with lead-acid battery and all-vanadium flow The electrification of battery studies stream reaction, and the two is organically combined, and improves battery capacity and energy density.
2nd, plumbic acid-full vanadium hybrid energy-storing battery actual energy density reaches 30Wh/kg, higher than all-vanadium liquid flow energy storage battery 15Wh/kg.
Brief description
Fig. 1 is plumbic acid-full vanadium energy-storage battery structural representation；Wherein 1- anolyte sap cavity, 2- electrolyte sap cavity, 3- Pump, 4- end plate, 5- barrier film, 6-PbO2Positive pole, 7- lead electrode
Fig. 2 is the electric curve comparison of battery charging of comparative example and embodiment 1；
Fig. 3 is the electric curve comparison of battery charging of comparative example and embodiment 2；
Fig. 4 is the electric curve comparison of battery charging of comparative example and embodiment 3.
Specific embodiment
The following examples are that the present invention is further illustrated, rather than limit the scope of the present invention.
Comparative example
All-vanadium liquid flow energy storage battery：
1) both positive and negative polarity adopts 5*5*0.3cm carbon felt；
2) anode electrolyte adopts the 3mol/L sulfuric acid solution of the 1.5mol mol/L tetravalence vanadium of 30mL；
3) electrolyte liquid adopts the 3mol/L sulfuric acid solution of the 1.5mol mol/L trivalent vanadium of 30mL；
4) barrier film adopts cationic membrane Nafion115；
5) battery charging and discharging system：80m A/cm2, charge cutoff voltage：1.55V, discharge cut-off voltage：1.0V.
Embodiment 1
Plumbic acid full vanadium energy-storage battery：
1) positive pole adopts 5*5cm PbO2Electrode；
2) negative pole adopts 5*5cm Pb electrode；
3) anode electrolyte adopts the 3mol/L sulfuric acid solution of the 1.5mol mol/L tetravalence vanadium of 30mL；
4) electrolyte liquid adopts the 3mol/L hydrochloric acid solution of the 1.5mol mol/L trivalent vanadium of 30mL；
5) barrier film adopts cationic membrane Nafion115；
6) battery charging and discharging system：80m A/cm2, charge cutoff voltage：2.2V, discharge cut-off voltage：1.0V.
Charging and discharging curve according to Fig. 2 calculates and understands：Plumbic acid-full vanadium energy-storage battery when battery volume is identical, during charging Between extend one times, discharge time also accordingly extends, and has higher capacity.Meanwhile, plumbic acid-full vanadium energy-storage battery is in 80m A/ cm2Lower operation, energy efficiency is 80.5%.
Embodiment 2
Plumbic acid full vanadium energy-storage battery：
7) positive pole adopts 5*5cm PbO2Electrode；
8) negative pole adopts 5*5cm Pb electrode；
9) anode electrolyte adopts the 3mol/L phosphoric acid solution of the 1.5mol mol/L tetravalence vanadium of 30mL；
10) electrolyte liquid adopts the 3mol/L sulfuric acid solution of the 1.5mol mol/L trivalent vanadium of 30mL；
11) barrier film adopts cationic membrane Nafion115；
12) battery charging and discharging system：80m A/cm2, charge cutoff voltage：2.2V, discharge cut-off voltage：1.0V.
Charging and discharging curve according to Fig. 3 calculates and understands：Plumbic acid-full vanadium energy-storage battery is in 80m A/cm2Lower operation, can dose-effect Rate is 80.7%.
Embodiment 3
Plumbic acid full vanadium energy-storage battery：
13) positive pole adopts 5*5cm PbO2Electrode；
14) negative pole adopts 5*5cm Pb electrode；
15) anode electrolyte adopts the 3mol/L hydrochloric acid solution of the 1.5mol mol/L tetravalence vanadium of 30mL；
16) electrolyte liquid adopts the 3mol/L phosphoric acid solution of the 1.5mol mol/L trivalent vanadium of 30mL；
17) barrier film adopts cationic membrane Nafion115；
18) battery charging and discharging system：80m A/cm2, charge cutoff voltage：2.2V, discharge cut-off voltage：1.0V.
Charging and discharging curve according to Fig. 4 calculates and understands：Plumbic acid-full vanadium energy-storage battery is in 80m A/cm2Lower operation, can dose-effect Rate is 81.7%.

Claims (4)

1. a kind of plumbic acid-full vanadium hybrid energy-storing battery, including the positive pole setting gradually, anolyte sap cavity, barrier film, electrolyte Sap cavity, negative pole it is characterised in that：Just extremely PbO2Electrode, negative pole is lead electrode, is filled with tetravalence vanadium in anolyte sap cavity , as anode electrolyte, the acid solution being filled with trivalent vanadium in electrolyte sap cavity is as electrolyte liquid for acid solution；
Acid in the described acid solution of tetravalence vanadium or the acid solution of trivalent vanadium be one of hydrochloric acid, sulfuric acid, phosphoric acid or two kinds with The mixed system of upper above-mentioned acid.
2. plumbic acid as claimed in claim 1-full vanadium hybrid energy-storing battery it is characterised in that：Electricity
When charging in pond, there is tetravalence vanadium first to the oxidation reaction of pentavalent vanadium in positive pole, with the consumption of tetravalence vanadium, PbSO4Progressively join Study stream reaction with electrification, generate PbO2；There is trivalent vanadium first to the reduction reaction of bivalent vanadium, disappearing with trivalent vanadium in negative pole Consumption, PbSO4Progressively participate in electrification and study stream reaction, generate Pb；
During electric discharge, there is PbO in positive pole first2To PbSO4Reduction reaction, with PbO2Consumption, pentavalent vanadium progressively participates in electrification Study stream reaction, generate tetravalence vanadium；There is Pb to PbSO first in negative pole4Oxidation reaction, with PbSO4Consumption, bivalent vanadium by Step participates in electrification and studies stream reaction, generates trivalent vanadium.
3. plumbic acid as claimed in claim 1-full vanadium hybrid energy-storing battery it is characterised in that：Anode electrolyte is concentration 0.1- The acid solution of 4mol/L tetravalent vanadium ion, electrolyte liquid is concentration 0.1-4mol/L trivalent vanadium ion, described acid solutions For 0.5-5mol/L.
4. plumbic acid as claimed in claim 1-full vanadium hybrid energy-storing battery it is characterised in that：Described barrier film include dense film or Perforated membrane, described dense film is cationic membrane or anionic membrane.
CN201310167808.4A 2013-05-09 2013-05-09 Plumbic acid-all vanadium mixed energy storage battery Active CN104143660B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114267862A (en) * 2021-12-27 2022-04-01 华秦储能技术有限公司 All-vanadium redox flow battery hybrid energy storage system and galvanic pile formed by same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2149524A1 (en) * 1971-10-04 1973-04-12 Bosch Gmbh Robert Lead battery - contg vanadium for minimal capacity loss
WO1989005526A1 (en) * 1987-12-10 1989-06-15 Unisearch Limited All-vanadium redox battery and additives
CN1598063A (en) * 2003-09-18 2005-03-23 攀枝花钢铁有限责任公司钢铁研究院 Process for electrolyzing preparing electrolyte of full vanadium ion flow battery
CN101853956A (en) * 2010-06-12 2010-10-06 江苏华富控股集团有限公司 Lead-acid flow battery
CN102652377A (en) * 2010-04-27 2012-08-29 住友电气工业株式会社 Redox flow battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2149524A1 (en) * 1971-10-04 1973-04-12 Bosch Gmbh Robert Lead battery - contg vanadium for minimal capacity loss
WO1989005526A1 (en) * 1987-12-10 1989-06-15 Unisearch Limited All-vanadium redox battery and additives
CN1598063A (en) * 2003-09-18 2005-03-23 攀枝花钢铁有限责任公司钢铁研究院 Process for electrolyzing preparing electrolyte of full vanadium ion flow battery
CN102652377A (en) * 2010-04-27 2012-08-29 住友电气工业株式会社 Redox flow battery
CN101853956A (en) * 2010-06-12 2010-10-06 江苏华富控股集团有限公司 Lead-acid flow battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114267862A (en) * 2021-12-27 2022-04-01 华秦储能技术有限公司 All-vanadium redox flow battery hybrid energy storage system and galvanic pile formed by same

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