CN104716373A - Flow battery with negative electrode of titanium pair - Google Patents
Flow battery with negative electrode of titanium pair Download PDFInfo
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- CN104716373A CN104716373A CN201310676839.2A CN201310676839A CN104716373A CN 104716373 A CN104716373 A CN 104716373A CN 201310676839 A CN201310676839 A CN 201310676839A CN 104716373 A CN104716373 A CN 104716373A
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- titanium
- tantalum
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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
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention belongs to the fields of chemical engineering and industries, and especially relates to the field of a flow battery with large scale energy storage ability. The negative electrode pair of the battery is a titanium pair, the positive electrode of the battery is Co (III)/Co (II), Mn (III)/Mn (II), Mn (IV)/Mn (II), I (VII)/I (V) or I (V)/I, the electrolyte solutions of the positive electrode and the negative electrode are separated through an ion exchange membrane, and the electrolyte solutions of the positive electrode and the negative electrode respectively flow between a solution storage tank and the battery under the promotion of a pump. The fluid battery has the advantages of high battery voltage, simple manufacturing process, low cost and high cycle life.
Description
Technical field
The present invention relates to a kind of structure of New galvanic battery system, particularly a kind of negative pole is the right flow battery of titanium electricity.
Technical background
Flow battery be a kind of with active material realize under flow regime charging, discharge for the large-scale energy storage device of feature, in recent years, along with the development of the regenerative resources such as wind and solar energy, flow battery shows good development prospect due to its extensive energy storage feature.Up to now, flow battery has developed multiple system, and from iron/pneumatic cell, to sodium polysulfide/bromine and all-vanadium flow battery, and new system is explored, but, still have many systems of good performance to fail to obtain enough attention.Particularly, 1979, the ferrotitanium battery that F Savinell etc. propose, anode was Fe
3+/ Fe
2+, negative pole is TiO
2+/ Ti
3+, the theoretical voltage of this battery is low, only has 0.77V (actual discharge only has 0.67V), and for this reason, ferrotitanium battery fails to be developed.In this battery, Fe
3+/ Fe
2+half-cell has good invertibity and dynamic characteristic faster, and follow-up developments have gone out siderochrome battery; And titanium half-cell reaction speed is relatively slow, easily form TiO
2precipitation, makes electrode passivation, and for this reason, titanium electricity obtains follow-up application to failing.But research shows, by the change of electrolyte ratio, under neutrality or acid condition, TiO
2+/ Ti
3+have that solubility is high, oxidation-reduction potential is low, good reversibility, advantage that stable chemical nature is good, with suitable positive pole electricity to pairing, the flow battery new system of a series of function admirable can be obtained.
Summary of the invention
The object of the present invention is to provide a series of electric to the New galvanic battery system for negative pole with titanium.Be different from existing flow battery system, thinking of the present invention is: under neutrality or acid condition, employing solubility is high, oxidation-reduction potential is low, good reversibility, the good titanium electricity of stable chemical nature is to as negative pole, employing solubility is high, oxidation-reduction potential is high, good reversibility, the cobalt (III) that stable chemical nature is good/cobalt (II), manganese (III)/manganese (II), manganese (IV)/manganese (II), iodine (VII)/iodine (V) or iodine (V)/iodine are as positive pole, construct a kind of flow battery system of Novel series, realize the demand of extensive energy storage.
Technical scheme of the present invention is as follows: negative pole is that the right flow battery of titanium electricity is made up of battery cell 1, negative pole storage tank 8, positive pole storage tank 10, pump 12 and pipeline 13; Battery cell 1 is connected with negative pole storage tank 8 by pipeline 13, and negative pole storage tank 8 is connected and walks abreast into loop with pump 12, battery cell 1 by pipeline 13 successively; Battery cell 1 is connected with positive pole storage tank 10 by pipeline 13, and positive pole storage tank 10 is connected and walks abreast into loop with pump 12, battery cell 1 by pipeline 13 successively; The main body of electrolyte liquid 9 leaves in negative pole storage tank 8, and the main body of anode electrolyte 11 leaves in positive pole storage tank 10, is linked to be loop with pipeline 13 by pump 12 and battery cell 1; In charge and discharge process, electrolyte liquid 9 and anode electrolyte 11 are circulated at negative pole storage tank 8 and between positive pole storage tank 10 and battery cell 1 by pipeline 13 under pump 12 promotes; Wherein battery cell 1 is encapsulated in shell 7 by negative current collector 3, negative electrode 4, barrier film 2, anode electrode 6 and plus plate current-collecting body 5 and forms, and plus plate current-collecting body 5, anode electrode 6, barrier film 2, negative electrode 4, negative current collector 3 are connected successively; The electrolyte liquid 9 of barrier film 2 separate batteries monomer 1 and anode electrolyte 11; Electrolyte liquid 9 and the anode electrolyte 11 of this flow battery are the aqueous solution, negative electrode active material is that titanium IV/ titanium III electricity is right, positive active material electricity is to being cobalt III and cobalt II, manganese III/ manganese II, manganese IV/ manganese II, iodine VII/ iodine V or iodine V/ iodine, negative electrode active material is dissolved in electrolyte liquid 9, and positive active material is dissolved in anode electrolyte 11.
Anode electrode 6 of the present invention is material with carbon element, have the titanium or titanium alloy on conductive oxide film surface, have the titanium or titanium alloy on conductive nitride film surface, the tantalum with conductive oxide film surface and tantalum alloy, have the tantalum on conductive nitride film surface and tantalum alloy or have tantalum and the tantalum alloy on conductive carbide film surface, and form is the material of porous.
Negative electrode 4 of the present invention is material with carbon elements, have the titanium or titanium alloy on conductive oxide film surface, have the titanium or titanium alloy on conductive nitride film surface, the tantalum with conductive oxide film surface and tantalum alloy, have the tantalum on conductive nitride film surface and tantalum alloy or have tantalum and the tantalum alloy on conductive carbide film surface, and form is the material of porous.
Negative current collector 3 of the present invention is material with carbon element, titanium or titanium alloy, tantalum and tantalum alloy, stainless steel or plumbous and lead alloy.
Plus plate current-collecting body 5 of the present invention is material with carbon element, have the titanium or titanium alloy on conductive oxide film surface, have the titanium or titanium alloy on conductive nitride film surface, the tantalum with conductive oxide film surface and tantalum alloy, have the tantalum on conductive nitride film surface and tantalum alloy or have tantalum and the tantalum alloy on conductive carbide film surface.
The supporting electrolyte of electrolyte liquid 9 of the present invention and anode electrolyte 11 is sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, bromic acid, acid iodide, acetic acid, pyrovinic acid, sulfamic acid, flurosulphonic acid, more than one in sulfate, hydrochloride, hydrobromate, hydriodate, bromate, iodate, acetate, metilsulfate, sulfamate, fluorinated sulfonate.
The pH value of electrolyte liquid 9 of the present invention and anode electrolyte 11 is less than 8.
In electrolyte solution of the present invention, the concentration of titanium is 0.05 ~ 2.5 mole often liter; In electrolyte solution, the concentration of cobalt is 0.05 ~ 2.0 mole often liter; In electrolyte solution, the concentration of manganese is 0.05 ~ 2.0 mole often liter; In electrolyte solution, the concentration of iodine is 0.05 ~ 3.0 mole often liter.
Barrier film 2 of the present invention is cation-exchange membrane, anion-exchange membrane or selective penetrated property microporous barrier.
New galvanic battery system of the present invention has following features:
1, negative pole is under neutrality or acid condition, adopts high, that oxidation-reduction potential is low, good reversibility, stable chemical nature the are good titanium electricity of solubility right.
2, under just very neutral or acid condition, solubility is high, oxidation-reduction potential is high, good reversibility, stable chemical nature are good cobalt (III)/cobalt (II), manganese (III)/manganese (II), manganese (IV)/manganese (II), iodine (VII)/iodine (V) or iodine (V)/iodine is adopted.
This New galvanic battery system has that cell voltage is high, manufacturing process is simple, cost is low, cycle life advantages of higher, can be widely used in the industries such as electric power, traffic, electronics.
Accompanying drawing explanation
Fig. 1. a kind of negative pole is the flow battery structure chart of Ti electrode
1 battery cell, 2 barrier films, 3 negative current collectors, 4 negative electrodes, 5 plus plate current-collecting bodies, 6 anode electrodes, 7 shells, 8 negative pole storage tanks, 9 electrolyte liquid, 10 positive pole storage tanks, 11 anode electrolytes, 12 pumps, 13 pipelines.
Embodiment
Example 1
Adopt graphite felt as anode electrode, impermeable graphite plate as plus plate current-collecting body, graphite felt as negative current collector, adopts 1.0M TiOSO as negative electrode, impermeable graphite plate
4+ 3M H
2sO
4as electrolyte liquid, using Nafion117 cation-exchange membrane as barrier film, adopt 1.0M CoSO
4+ 3M H
2sO
4as anode electrolyte, in the shell that positive and negative electrode and membrane encapsulates are formed at polymethyl methacrylate, composition titanium cobalt flow battery monomer; Electrolyte liquid and magnetic drive pump, negative pole storage tank connect into electrolyte loop, and anode electrolyte connects into electrolyte loop with magnetic drive pump, positive pole storage tank too.When the solution flow rate on positive and negative electrode surface is about 10cm/s, with 5mA/cm
2current density discharge and recharge, this titanium cobalt flow battery average discharge volt is at more than 1.8V, and energy efficiency reaches more than 80%, and the water between anode electrolyte and electrolyte liquid shifts low, and hundreds of primary cell performance that circulates does not decay.
Example 2
Adopt graphite felt as anode electrode, impermeable graphite plate as plus plate current-collecting body, graphite felt as negative current collector, adopts 0.2M TiOSO as negative electrode, impermeable graphite plate
4+ 5M H
2sO
4as electrolyte liquid, using Nafion117 cation-exchange membrane as barrier film, adopt 0.2M MnSO
4+ 0.2M Na
2h
2p
2o
7+ 5M H
2sO
4as anode electrolyte, in the shell that positive and negative electrode and membrane encapsulates are formed at polymethyl methacrylate, composition titanium manganese flow battery monomer; Electrolyte liquid and magnetic drive pump, negative pole storage tank connect into electrolyte loop, and anode electrolyte connects into electrolyte loop with magnetic drive pump, positive pole storage tank too.When the solution flow rate on positive and negative electrode surface is about 5cm/s, with 5mA/cm
2current density discharge and recharge, this titanium manganese flow battery average discharge volt is at more than 1.0V, and energy efficiency reaches more than 70%, and the water between anode electrolyte and electrolyte liquid shifts low, and hundreds of primary cell performance that circulates does not decay.
Example 3
Adopt brown lead oxide as the lead alloy be repeatedly oxidized in anode electrode, sulfuric acid as plus plate current-collecting body, graphite felt as negative current collector, adopts 1.0M TiOSO as negative electrode, impermeable graphite plate
4+ 3M H
2sO
4as electrolyte liquid, using Nafion117 cation-exchange membrane as barrier film, adopt 0.5M HIO
3+ 3M H
2sO
4as anode electrolyte, in the shell that positive and negative electrode and membrane encapsulates are formed at polymethyl methacrylate, composition titanium iodine flow battery monomer; Electrolyte liquid and magnetic drive pump, negative pole storage tank connect into electrolyte loop, and anode electrolyte connects into electrolyte loop with magnetic drive pump, positive pole storage tank too.When the solution flow rate on positive and negative electrode surface is about 5cm/s, with 5mA/cm
2current density discharge and recharge, this titanium iodine flow battery average discharge volt is at more than 1.6V, and energy efficiency reaches more than 75%, and the water between anode electrolyte and electrolyte liquid shifts low, and hundreds of primary cell performance that circulates does not decay.
Part negative pole is that the electrode potential of the right flow battery of titanium electricity and cell voltage are listed in table 1.
Table 1 part negative pole is the right flow battery list of titanium electricity
| Flow battery title | Titanium cobalt battery | Titanium-manganese battery | Titanium-manganese battery | Titanium iodine battery | Titanium iodine battery |
| Positive pole | Ti 3+/TiO 2+ | Ti 3+/TiO 2+ | Ti 3+/TiO 2+ | Ti 3+/TiO 2+ | Ti 3+/TiO 2+ |
| Anodic potentials | -0.04V | -0.04V | -0.04V | -0.04V | -0.04V |
| Negative pole | Cobalt (III)/cobalt (II) | Manganese (III)/manganese (II) | Manganese (IV)/manganese (II) | Iodine (VII)/iodine (V) | Iodine (V)/iodine |
| Negative pole current potential | 1.82V | 1.51V | 1.23V | 1.6V | 1.4V |
| Cell voltage | 1.86V | 1.55V | 1.27V | 1.64V | 1.44V |
Claims (9)
1. negative pole is the right flow battery of titanium electricity, it is characterized in that this flow battery is made up of battery cell (1), negative pole storage tank (8), positive pole storage tank (10), pump (12) and pipeline (13); Battery cell (1) is connected with negative pole storage tank (8) by pipeline (13), and negative pole storage tank (8) is connected and walks abreast into loop with pump (12), battery cell (1) by pipeline (13) successively; Battery cell (1) is connected with positive pole storage tank (10) by pipeline (13), and positive pole storage tank (10) is connected and walks abreast into loop with pump (12), battery cell (1) by pipeline (13) successively; The main body of electrolyte liquid (9) leaves in negative pole storage tank (8), the main body of anode electrolyte (11) leaves in positive pole storage tank (10), is linked to be loop with pipeline (13) by pump (12) and battery cell (1); In charge and discharge process, electrolyte liquid (9) and anode electrolyte (11) are circulated at negative pole storage tank (8) and between positive pole storage tank (10) and battery cell (1) by pipeline (13) under pump (12) promotes; Wherein battery cell (1) is encapsulated in shell (7) by negative current collector (3), negative electrode (4), barrier film (2), anode electrode (6) and plus plate current-collecting body (5) and forms, and plus plate current-collecting body (5), anode electrode (6), barrier film (2), negative electrode (4), negative current collector (3) are connected successively; The electrolyte liquid (9) of barrier film (2) separate batteries monomer (1) and anode electrolyte (11); Electrolyte liquid (9) and the anode electrolyte (11) of this flow battery are the aqueous solution, negative electrode active material is that titanium IV/ titanium III electricity is right, positive active material electricity is to being cobalt III and cobalt II, manganese III/ manganese II, manganese IV/ manganese II, iodine VII/ iodine V or iodine V/ iodine, negative electrode active material is dissolved in electrolyte liquid (9), and positive active material is dissolved in anode electrolyte (11).
2. a kind of negative pole according to claim 1 is the right flow battery of titanium electricity, it is characterized in that anode electrode (6) is material with carbon element, has the titanium or titanium alloy on conductive oxide film surface, has the titanium or titanium alloy on conductive nitride film surface, the tantalum with conductive oxide film surface and tantalum alloy, has the tantalum on conductive nitride film surface and tantalum alloy or have tantalum and the tantalum alloy on conductive carbide film surface, form is the material of porous.
3. a kind of negative pole according to claim 1 is the right flow battery of titanium electricity, it is characterized in that negative electrode (4) is material with carbon element, has the titanium or titanium alloy on conductive oxide film surface, has the titanium or titanium alloy on conductive nitride film surface, the tantalum with conductive oxide film surface and tantalum alloy, has the tantalum on conductive nitride film surface and tantalum alloy or have tantalum and the tantalum alloy on conductive carbide film surface, form is the material of porous.
4. a kind of negative pole according to claim 1 is the right flow battery of titanium electricity, it is characterized in that negative current collector (3) is material with carbon element, titanium or titanium alloy, tantalum and tantalum alloy, stainless steel or plumbous and lead alloy.
5. a kind of negative pole according to claim 1 is the right flow battery of titanium electricity, it is characterized in that plus plate current-collecting body (5) is material with carbon element, has the titanium or titanium alloy on conductive oxide film surface, has the titanium or titanium alloy on conductive nitride film surface, the tantalum with conductive oxide film surface and tantalum alloy, has the tantalum on conductive nitride film surface and tantalum alloy or have tantalum and the tantalum alloy on conductive carbide film surface.
6. a kind of negative pole according to claim 1 is the right flow battery of titanium electricity, it is characterized in that the supporting electrolyte of electrolyte liquid (9) and anode electrolyte (11) is sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, bromic acid, acid iodide, acetic acid, pyrovinic acid, sulfamic acid, flurosulphonic acid, more than one in sulfate, hydrochloride, hydrobromate, hydriodate, bromate, iodate, acetate, metilsulfate, sulfamate, fluorinated sulfonate.
7. a kind of negative pole according to claim 1 is the right flow battery of titanium electricity, it is characterized in that the pH value of electrolyte liquid (9) and anode electrolyte (11) is less than 8.
8. a kind of negative pole according to claim 1 is the right flow battery of titanium electricity, it is characterized in that the concentration of titanium in electrolyte solution is 0.05 ~ 2.5 mole often liter; In electrolyte solution, the concentration of cobalt is 0.05 ~ 2.0 mole often liter; In electrolyte solution, the concentration of manganese is 0.05 ~ 2.0 mole often liter; In electrolyte solution, the concentration of iodine is 0.05 ~ 3.0 mole often liter.
9. a kind of negative pole according to claim 1 is the right flow battery of titanium electricity, it is characterized in that barrier film (2) is cation-exchange membrane, anion-exchange membrane or selective penetrated property microporous barrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310676839.2A CN104716373A (en) | 2013-12-13 | 2013-12-13 | Flow battery with negative electrode of titanium pair |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310676839.2A CN104716373A (en) | 2013-12-13 | 2013-12-13 | Flow battery with negative electrode of titanium pair |
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| Publication Number | Publication Date |
|---|---|
| CN104716373A true CN104716373A (en) | 2015-06-17 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110444800A (en) * | 2019-08-28 | 2019-11-12 | 山东瑞克环境科技有限公司 | Accumulator plant |
| CN113178608A (en) * | 2021-03-15 | 2021-07-27 | 大连海事大学 | Slurry type titanium manganese flow battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102315473A (en) * | 2011-06-28 | 2012-01-11 | 北京好风光储能技术有限公司 | Lithium ion flow redox battery |
| CN102723518A (en) * | 2011-03-30 | 2012-10-10 | 中国人民解放军63971部队 | All-lead liquid flow battery |
| WO2013131838A1 (en) * | 2012-03-05 | 2013-09-12 | Eos Holding Sa | Redox flow battery for hydrogen generation |
-
2013
- 2013-12-13 CN CN201310676839.2A patent/CN104716373A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102723518A (en) * | 2011-03-30 | 2012-10-10 | 中国人民解放军63971部队 | All-lead liquid flow battery |
| CN102315473A (en) * | 2011-06-28 | 2012-01-11 | 北京好风光储能技术有限公司 | Lithium ion flow redox battery |
| WO2013131838A1 (en) * | 2012-03-05 | 2013-09-12 | Eos Holding Sa | Redox flow battery for hydrogen generation |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110444800A (en) * | 2019-08-28 | 2019-11-12 | 山东瑞克环境科技有限公司 | Accumulator plant |
| CN113178608A (en) * | 2021-03-15 | 2021-07-27 | 大连海事大学 | Slurry type titanium manganese flow battery |
| CN113178608B (en) * | 2021-03-15 | 2024-06-04 | 大连海事大学 | Slurry type titanium-manganese flow battery |
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Application publication date: 20150617 |