CN103137986B - A kind of zinc bromine single flow battery - Google Patents
A kind of zinc bromine single flow battery Download PDFInfo
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- CN103137986B CN103137986B CN201110400161.6A CN201110400161A CN103137986B CN 103137986 B CN103137986 B CN 103137986B CN 201110400161 A CN201110400161 A CN 201110400161A CN 103137986 B CN103137986 B CN 103137986B
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- zinc
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- bromine
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- 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
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- 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
- Y02E60/30—Hydrogen technology
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Abstract
A kind of zinc bromine single flow battery, is made up of battery module, electrolyte liquid, negative pole fluid reservoir, circulating pump, circulation line; Side of the positive electrode adopts static encapsulating structure, without the need to being furnished with positive pole bromine electrolyte circulation system.This system adopts single liquid stream to arrange, compared with the zinc-bromine flow battery of tradition positive and negative pair of circulate electrolyte, decrease a set of circulating pump and circulation line, side of the positive electrode adopts hermetically-sealed construction, solve corrosion and the leakage problem of bromine, reduce the system energy consumption of battery, reduce cost, simplify battery structure; Compared with the zinc bromine storage battery without the circulatory system, because negative side still adopts flowable state electrolyte form, improve zinc depositional fabric, improve energy content of battery efficiency and life-span.
Description
Technical field
The present invention relates to single liquid flow energy storage battery, be specifically related to a kind of zinc bromine single flow battery.
Background technology
Zinc bromine liquid flow energy storage battery (Zinc-bromine redox flow battery, ZBB) be a kind of low cost, high efficiency, environmentally friendly liquid flow energy storage battery, there is energy density and current efficiency is high, device is simple and easy to manipulation, long service life, the advantage such as with low cost, be mainly used in the fields such as renewable energy power generation, electric automobile such as peak load regulation network, wind energy and solar energy.
Traditional zinc-bromine flow battery adopts the design of double pump, dual circuit, in charge and discharge process, drives electrolyte at battery internal circulation flow with circulating pump.When battery does not work, electrolyte is extracted out from cell cavity, is stored in hopper, makes to realize electrolyte open circuit between inside battery both positive and negative polarity, positive pole Charging state bromine can be prevented to be diffused into negative pole and directly chemical reaction occur and cause self discharge.When circular electrolyte can also prevent from charging simultaneously, zinc dendrite growth makes both positive and negative polarity short circuit through barrier film.
But because zinc-bromine flow battery needs the electrolyte circulation system such as circulating pump, hopper, the energy efficiency that result in zinc-bromine flow battery reduces due to the impact of system loss, these battery auxiliary equipment make zinc-bromine flow battery system configuration complicated on the other hand, be unfavorable for miniaturization, reduce the energy density of battery.
Patent CN99245261.9 describes a kind of zinc bromine storage battery for this reason, which eliminates the circulatory system such as circulating pump and positive and negative electrolyte reservoir of zinc-bromine flow battery, makes battery structure simple and compact, reduce system energy consumption.But because positive and negative electrode both sides are all without circulating pump design, the actual energy density that result in battery is lower, cannot high current charge-discharge.
Summary of the invention
The present invention is directed to the problems referred to above, in conjunction with the advantage of zinc-bromine flow battery and zinc bromine storage battery, evade the shortcoming of the two, propose a kind of zinc bromine single flow battery, and Curve guide impeller has been carried out to anode electrode.
For achieving the above object, the technical solution used in the present invention is as follows,
A kind of zinc bromine single flow battery, is made up of battery module, electrolyte liquid, negative pole fluid reservoir, circulating pump, circulation line;
Cathode electrolyte storage tank is connected with the electrolyte liquid entrance and exit of battery module respectively by two circulation lines, and the connecting line between the electrolyte liquid entrance and cathode electrolyte storage tank of battery module is provided with circulating pump;
Battery module is formed by a joint or the above monocell connection of two joints, and electrolyte liquid flows through monocell negative pole;
The positive pole of monocell is made up of matrix and the lotion containing positive active material zinc bromide that adheres to thereon.
Described positive pole is made up of matrix and the positive pole pole cream that adheres to thereon, and matrix is the porous, electrically conductive material with carbon element of carbon felt, graphite felt, carbon paper or carbon cloth;
Count by weight, described positive pole pole cream is made up of 10-100 part zinc bromide, 1-10 part carbon dust, 0.5-5 part complexing agent and 3-5 part deionized water.
Described complexing agent is quaternary ammonium salt compound.Described quaternary ammonium salt compound is ethanaminium, N-methvl ethyl pyrrolidine.
The described positive pole pole carrying capacity of cream on matrix is 1-20mg/cm
2.
Monocell side of the positive electrode in battery module adopts static encapsulating structure, without the need to being furnished with positive pole bromine electrolyte circulation system;
In charge and discharge process, the active material zinc ion in electrolyte liquid and the metallic zinc in negative pole are changed mutually.
Described negative pole is carbon felt, graphite felt, carbon paper, carbon cloth or foam metal.
Described electrolyte liquid is zinc ion acid solution, and concentration is 1-5mol/L.
Described barrier film is amberplex or microporous barrier.
Battery module is formed by a joint or the above cells in series of two joints, parallel connection or also series-parallel connection of going here and there,
Monocell is formed by stacking by positive end plate, collector, positive pole, barrier film, negative pole, collector, negative end plate successively;
During the two above cells in series of joint, its by positive end plate and collector, with collector and negative end plate, and positive pole, barrier film, negative pole that collector more than two groups is arranged in order are formed by stacking.
During charging, electrolyte is delivered to negative pole via pump from fluid reservoir, and the free zinc ion in electrolyte is directly deposited on electrode with zinc simple substance form, and bromide ion forms bromo-complex with complexing agent after positive pole internal oxidation is bromine simple substance.During electric discharge, zinc simple substance is oxidized to zinc ion via being pumped back in fluid reservoir, and bromo-complex is reduced to bromide ion.
Beneficial effect of the present invention:
1. this system adopts single liquid stream to arrange, compared with the zinc-bromine flow battery of tradition positive and negative pair of circulate electrolyte, decrease a set of circulating pump and circulation line, side of the positive electrode adopts static encapsulating structure, solve corrosion and the leakage problem of bromine, reduce the system energy consumption of battery, reduce cost, simplify battery structure;
2., compared with the zinc bromine storage battery without the circulatory system, because negative side still adopts flowable state electrolyte form, improve zinc depositional fabric, improve energy content of battery efficiency and life-span;
3. this battery system positive pole adopts the method for matrix collocation pole cream, has been mixed into the cell active materials of high concentration in the cream of pole, solves the problem that energy density that positive pole causes because electrolyte cannot flow is lower.
Figure of description
Fig. 1 is zinc bromine single flow battery structural representation of the present invention;
Wherein: 1-positive end plate, 2-negative end plate, 3-plus plate current-collecting body, 4-positive pole, 5-barrier film, 6-negative pole, 7-cathode electrolyte storage tank, 8-circulating pump;
Fig. 2 is the zinc bromine single flow battery systematic function figure that embodiment 1 is assembled;
Fig. 3 is the zinc bromine single flow battery systematic function figure that embodiment 2 is assembled;
Fig. 4 is that the zinc bromine single flow battery of traditional zinc-bromine flow battery, zinc bromine storage battery and embodiment 1 is at 20mA/cm
2under charging and discharging curve comparison diagram.
Embodiment
Embodiment 1
The preparation of positive pole pole cream:
1) pole cream slurry configuration: count by weight, by carbon dust 5 parts, ethanaminium, N-methvl, it is for subsequent use that ethyl pyrrolidine 2 parts, zinc bromide 40 parts, 3 parts of deionized water machinery are mixed into pasty state;
2) method of spraying is adopted pole cream slurry to be coated in equably a side surface of carbon paper, carrying capacity: 5mg/cm
2;
3) bromide solutions configuration: the bromide solutions of preparation 4mol/L, assembles battery after the positive pole prepared is immersed in solution 10min, and is assembled towards barrier film the side being coated with pole cream.
Prepared by electrolyte liquid:
The bromide solutions of preparation 2mol/L is stand-by.
Battery assembles:
Monocell comprises positive end plate, plus plate current-collecting body, positive pole, film, negative pole, negative end plate in order successively.
Battery electrode area 36cm
2, charging and discharging currents density: 20mA/cm
2, battery coulombic efficiency: 99%, voltage efficiency: 82%, energy efficiency: 81%, is shown in Fig. 2.
Embodiment 2
The preparation of positive pole pole cream:
1) pole cream slurry configuration: count by weight, by carbon dust 1 part, trimethylammonium bromide 1 part, zinc bromide 10 parts, that 3 parts of deionized water machinery is mixed into pasty state is for subsequent use;
2) method of blade coating is adopted pole cream slurry to be coated in equably a side surface of carbon felt; Carrying capacity: 20mg/cm
2.
3) bromide solutions configuration: the bromide solutions of preparation 4mol/L, assembles battery after the positive pole prepared is immersed in solution 20min, and is assembled towards barrier film the side being coated with pole cream.
Prepared by electrolyte liquid:
The bromide solutions of preparation 2mol/L is stand-by.
Battery assembles:
Monocell comprises positive end plate, plus plate current-collecting body, positive pole, film, negative pole negative end plate in order successively.
Battery electrode area 36cm
2, charging and discharging currents density: 40mA/cm
2, battery coulombic efficiency: 95%, voltage efficiency: 80%, energy efficiency: 76%, is shown in Fig. 3.
Embodiment 3
The assembling of zinc-bromine flow battery
1) just very 36cm
2, thickness is the charcoal felt of 4mm
2) negative pole is 36cm
2, graphite cake
3) negative pole prepared by electrolyte: the zinc bromide 80ml solution for later use of preparation 2mol/L, both positive and negative polarity electrolyte is respectively 40ml.
Battery assembles:
Monocell comprises positive end plate, plus plate current-collecting body, positive pole, film, negative pole negative end plate in order successively.
The assembling of zinc bromine storage battery
The preparation of both positive and negative polarity pole cream:
1) pole cream slurry configuration: count by weight, by carbon dust 1 part, trimethylammonium bromide 1 part, zinc bromide 10 parts, that 3 parts of deionized water machinery is mixed into pasty state is for subsequent use;
2) method of blade coating is adopted pole cream slurry to be coated in equably a side surface of carbon felt; Carrying capacity: 20mg/cm
2.
3) bromide solutions configuration: the bromide solutions of preparation 4mol/L, assembles battery after the both positive and negative polarity prepared is immersed in solution 20min, and is assembled towards barrier film the side being coated with pole cream.
Battery assembles:
Monocell comprises positive end plate, plus plate current-collecting body, positive pole, film, negative pole, negative end plate in order successively.
Zinc bromine single flow battery 20mA/cm in zinc-bromine flow battery, zinc bromine storage battery, embodiment 1
2fig. 4 is shown in charging and discharging curve contrast.Zinc bromine single flow battery is compared zinc bromine storage battery and is had lower charging voltage and higher discharge voltage as seen from the figure, and the voltage efficiency of battery significantly improves; Although compare zinc-bromine flow battery voltage efficiency slightly to decline, because single flow battery eliminates positive pole circulating device, system effectiveness still has larger advantage.
Claims (8)
1. a zinc bromine single flow battery, is characterized in that: be made up of battery module, electrolyte liquid, cathode electrolyte storage tank, circulating pump, circulation line;
Cathode electrolyte storage tank is connected with the electrolyte liquid entrance and exit of battery module respectively by two circulation lines, and the connecting line between the electrolyte liquid entrance and cathode electrolyte storage tank of battery module is provided with circulating pump;
Battery module is formed by the above monocell connection of two joints, and electrolyte liquid flows through monocell negative pole;
The positive pole of monocell is made up of matrix and the lotion containing positive active material zinc bromide that adheres to thereon;
Described positive pole is made up of matrix and the positive pole pole cream that adheres to thereon, and matrix is the porous, electrically conductive material with carbon element of carbon felt, graphite felt, carbon paper or carbon cloth;
Count by weight, described positive pole pole cream is made up of 10-100 part zinc bromide, 1-10 part carbon dust, 0.5-5 part complexing agent and 3-5 part deionized water.
2. zinc bromine single flow battery according to claim 1, is characterized in that: described complexing agent is quaternary ammonium salt compound.
3. zinc bromine single flow battery according to claim 2, is characterized in that: described quaternary ammonium salt compound is ethanaminium, N-methvl ethyl pyrrolidine.
4. zinc bromine single flow battery according to claim 1, is characterized in that, the described positive pole pole carrying capacity of cream on matrix is 1-20mg/cm
2.
5. zinc bromine single flow battery according to claim 1: it is characterized in that:
Monocell side of the positive electrode in battery module adopts static encapsulating structure, without the need to being furnished with positive pole bromine electrolyte circulation system;
In charge and discharge process, the active material zinc ion in electrolyte liquid and the metallic zinc in negative pole are changed mutually.
6. zinc bromine single flow battery according to claim 1, is characterized in that: described negative pole is carbon felt, graphite felt, carbon paper, carbon cloth or foam metal.
7. zinc bromine single flow battery according to claim 1, it is characterized in that: described electrolyte liquid is zinc ion acid solution, concentration is 1-5mol/L.
8. zinc bromine single flow battery according to claim 1, is characterized in that: battery module is formed by the above cells in series of two joints, parallel connection or also series-parallel connection of going here and there,
Monocell is formed by stacking by positive end plate, plus plate current-collecting body, positive pole, barrier film, negative pole, negative end plate successively;
During the two above cells in series of joint, it is by positive end plate and plus plate current-collecting body, negative current collector and negative end plate, and adopts the positive pole be arranged in order of bipolar plates separation, barrier film, negative pole to be formed by stacking in the middle of collector more than two groups;
Described barrier film is amberplex or microporous barrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110400161.6A CN103137986B (en) | 2011-12-05 | 2011-12-05 | A kind of zinc bromine single flow battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110400161.6A CN103137986B (en) | 2011-12-05 | 2011-12-05 | A kind of zinc bromine single flow battery |
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| Publication Number | Publication Date |
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| CN103137986A CN103137986A (en) | 2013-06-05 |
| CN103137986B true CN103137986B (en) | 2015-08-12 |
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| CN201110400161.6A Expired - Fee Related CN103137986B (en) | 2011-12-05 | 2011-12-05 | A kind of zinc bromine single flow battery |
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| CN105680082A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Long-lifetime zinc-bromine flow battery structure and electrolyte |
| CN104600376B (en) * | 2014-12-22 | 2016-09-14 | 江苏新鹏重型机电制造有限公司 | Surge storage battery |
| CN106549188B (en) * | 2015-09-18 | 2019-01-22 | 中国科学院大连化学物理研究所 | A kind of zinc sulphur single flow battery system |
| CN107845826B (en) * | 2016-09-21 | 2023-08-11 | 中国科学院大连化学物理研究所 | Zinc bromine single flow battery |
| CN107871880A (en) * | 2016-09-22 | 2018-04-03 | 中国科学院大连化学物理研究所 | A kind of integrated zinc-bromine flow battery and its assemble method |
| CN108134141B (en) * | 2016-12-01 | 2020-05-05 | 中国科学院大连化学物理研究所 | Static zinc-bromine battery without diaphragm |
| CN109755621A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院大连化学物理研究所 | A kind of zinc-nickel single flow battery |
| CN109755604B (en) * | 2017-11-08 | 2021-09-17 | 中国科学院大连化学物理研究所 | Neutral zinc-iodine flow battery |
| CN109841852B (en) * | 2017-11-28 | 2021-07-06 | 中国科学院大连化学物理研究所 | Positive electrode active material for zinc-bromine single flow battery, and preparation and application thereof |
| CN108365247A (en) * | 2018-01-19 | 2018-08-03 | 复旦大学 | A kind of bromo- half flow battery with ion embedded type solid cathode |
| CN108400365B (en) * | 2018-03-01 | 2021-11-12 | 南京瑞贻电子科技有限公司 | Zinc-bromine flow battery |
| CN111106397B (en) * | 2018-10-25 | 2021-04-30 | 中国科学院大连化学物理研究所 | Zinc-nickel accumulator |
| CN111180777A (en) * | 2018-11-13 | 2020-05-19 | 陕西华银科技股份有限公司 | Positive electrode electrolyte for zinc-bromine single flow battery |
| CN111193033B (en) * | 2018-11-15 | 2021-06-08 | 中国科学院大连化学物理研究所 | Alkaline zinc-iron single flow battery |
| CN111244489B (en) * | 2018-11-28 | 2020-12-15 | 中国科学院大连化学物理研究所 | Application of electrode material in zinc-bromine single flow battery |
| CN111326778B (en) * | 2018-12-14 | 2021-06-25 | 中国科学院大连化学物理研究所 | Neutral lithium-bromine flow battery |
| CN110745003B (en) * | 2019-10-29 | 2020-07-21 | 长沙理工大学 | Electrical system of hybrid electric vehicle and working method thereof |
| CN112928282B (en) * | 2019-12-05 | 2022-05-20 | 中国科学院大连化学物理研究所 | Negative electrode for zinc-based flow battery, battery and application of negative electrode |
| CN112928319B (en) * | 2019-12-06 | 2022-12-27 | 中国科学院大连化学物理研究所 | High-capacity zinc-bromine single flow battery structure |
| CN112928298B (en) * | 2019-12-06 | 2022-05-17 | 中国科学院大连化学物理研究所 | Zinc-bromine single flow battery structure |
| WO2021172607A1 (en) * | 2020-02-25 | 2021-09-02 | 전자부품연구원 | Zinc-bromine flow battery including conductive intermediate layer |
| CN114497644B (en) * | 2020-11-12 | 2023-09-15 | 中国科学院大连化学物理研究所 | Zinc-based single flow battery operation method |
| CN114497660B (en) * | 2020-11-12 | 2023-12-19 | 中国科学院大连化学物理研究所 | Application of complexing agent in zinc-bromine storage battery electrolyte |
| CN114597455A (en) * | 2020-12-03 | 2022-06-07 | 中国科学院大连化学物理研究所 | Discharging operation method of zinc-bromine single flow battery and intermittent discharging zinc-bromine single flow battery |
| CN112599828B (en) * | 2020-12-15 | 2022-05-31 | 大连海事大学 | Novel titanium-manganese single flow battery |
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