CN104716391A - Aqueous zinc ion single liquid flow battery - Google Patents
Aqueous zinc ion single liquid flow battery Download PDFInfo
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- CN104716391A CN104716391A CN201310696151.0A CN201310696151A CN104716391A CN 104716391 A CN104716391 A CN 104716391A CN 201310696151 A CN201310696151 A CN 201310696151A CN 104716391 A CN104716391 A CN 104716391A
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- ion
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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
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to an aqueous zinc ion single liquid flow battery system, which comprises a single battery or electric pile formed by over two single batteries in series connection, and an electrolyte solution equipped liquid storage tank. The single battery includes an anode and a cathode, the solute of the electrolyte solution is composed of a zinc ion-containing soluble salt and a soluble salt containing lithium ions and/or sodium ions, and the solvent is water. The anode active material is one of Li or/and Na ion embedded Mn oxide, Co oxide, Ni oxide and Fe oxide or a mixed oxide of more than two of the oxides, and the cathode is a sedimentary type electrode. The anode reaction of the battery adopts intercalation and deintercalation reaction of lithium ions or/and sodium ions, and has higher electrochemical reversibility than the zinc ion intercalation and deintercalation reaction of zinc ion liquid flow batteries. The cathode of the battery adopts zinc deposition dissolution, and compared with the lithium ion and/or sodium ion intercalation and deintercalation reaction of aqueous lithium ion battery cathodes, has higher reversibility, lower price and better cyclic stability.
Description
Technical field
The present invention relates to a kind of water system Zinc ion single-fluid battery system.
Background technology
In recent years, along with economic development and ambient pressure, the development of secondary cell is in the ascendant, and in traditional secondary cell, lithium ion battery has higher performance.Lithium ion battery utilizes Li
+carry out store electrical energy as energy-accumulating medium, utilize Li
+embedding and deintercalation realize the charge and discharge cycles of battery.But because lithium is comparatively active, cause the fail safe of lithium ion battery poor.
In conjunction with lithium ion battery and traditional zinc-manganese dioxide dry cell, it is positive pole with manganese dioxide that the Chinese patents such as CN101540417A make public for the first time a kind of, take zinc as negative pole, with the Rechargeable zinc ion battery that the solution containing zinc ion is electrolyte, when charging, zinc ion deviates from manganese dioxide through electrolyte then at cathode deposition, and during electric discharge, said process is contrary.Owing to utilizing zinc ion in the reversible deintercalation behavior of positive electrode, this battery has the advantage that capacity is high, the life-span is longer.
But above-mentioned patent is by the battery performance that improved of positive electrode and electrolyte, but the dendrite problems of zinc load is not fundamentally being improved, efficient, the long-life that constrain battery are run.For this problem, Chinese patent 201210260404.5 proposes the concept of Zinc ion single-fluid battery in conjunction with the advantage of Zinc ion battery and flow battery, improve the material Transfer process of electrode active material, improve battery performance, and improve zinc load dendrite problems greatly.
Zinc ion compares lithium ion radius to be increased, and embeds deintercalation reaction rate comparatively slow, and the positive electrode be applicable at present is limited, seriously constrains it and further develops.Review the anode material for lithium-ion batteries of lithium ion battery especially in water system and have years of researches history, but due to the negative material less stable of aquo-lithium ion battery, cycle life is lower limits development.
Summary of the invention
The pluses and minuses of the present invention in conjunction with Zinc ion battery, Zinc ion single-fluid battery, aquo-lithium ion battery and the restriction problem of existence.To achieve these goals, the concrete technical scheme of the present invention's employing is as follows:
A kind of water system Zinc ion single-fluid battery system, the solute of described electrolyte is by the soluble-salt containing zinc ion and contain lithium ion or/and the soluble-salt of sodium ion forms, and solvent is water;
Positive electrode active materials be embed Li or/and Na ion Mn, Co, Ni, Fe oxide in one or more mixed oxide; Negative pole is deposition type electrode.
Be filled with electrolyte in electrolyte storage tank, electrolyte storage tank is connected with the entrance and exit of monocell or pile by pipeline respectively through liquid delivery pump;
During charging, the lithium ion embedded in positive pole is or/and sodium ion deintercalation enters in electrolyte; Zinc ion deposits with zinc simple substance form at negative pole; During electric discharge, lithium ion is or/and sodium ion embeds in positive electrode; The zinc simple substance of cathode deposition is oxidized to zinc ion via being pumped back in fluid reservoir.
The described soluble-salt containing zinc ion is one or more in zinc sulfate, zinc nitrate, zinc chloride or zinc bromide; In electrolyte, zinc ion concentration is 0.5-1.0mol/L;
Soluble salt solutions containing lithium ion is one or more in lithium sulfate, lithium nitrate, lithium chloride or lithium bromide; Soluble salt solutions containing sodium ion is one or more in sodium sulphate, sodium nitrate, sodium chloride or sodium bromide; In electrolyte, lithium ion and/or Na ion concentration are 1.0-2.0mol/L.
The pH value of electrolyte is greater than 2.0.
Positive pole is made up of the positive electrode on matrix and its, and positive electrode is made up of positive electrode active materials, conductive agent, binding agent; Embed Li or/and Na ion Mn, Co, Ni, Fe oxide in one or more mixed oxide, conductive agent is material with carbon element, binding agent is PTFE or PVDF, the mass ratio 60%-80% of positive electrode active materials in positive pole, conductive agent is mass ratio 5%-30% in positive pole, and binding agent is mass ratio 10%-35% in positive pole.
Described negative pole is deposition type electrode, and described deposition type electrode is tabular or cavernous metal or material with carbon element.
Beneficial effect of the present invention:
The present invention proposes the embedding deintercalation reaction of anode material of lithium or sodium ion, negative pole adopts the cells concepts of deposition solubilizing reaction of zinc, and by electrolyte solution, positive electrode preferred, improve the performance of this battery.The shortcoming of above-mentioned battery evaded by this battery, and because positive pole reaction adopts embedding and the deintercalation reaction of lithium ion or sodium ion, the zinc ion comparing zinc ion flow battery positive pole embeds deintercalation reaction and has higher electrochemical reversibility; This battery adopts the deposition of zinc to dissolve due to negative pole, compares the lithium of aquo-lithium ion battery negative pole or sodium ion and embeds deintercalation reaction and have higher invertibity and lower price and better cyclical stability.
Figure of description
Fig. 1 is the monocell schematic diagram that embodiment 1 is assembled; Wherein 1-positive end plate; 2-negative end plate; 3-positive pole; 4-negative pole; 5-pump; 6-electrolyte storage tank;
Fig. 2 is the cycle performance of battery figure of the monocell that embodiment 1 is assembled;
Fig. 3 is the cycle performance of battery figure of the monocell that embodiment 2 is assembled.
Embodiment
Embodiment 1
The preparation of positive electrode: (for Mn oxide)
The MnSO of preparation 1L0.05mol/L
4, 0.05mol/L LiNO
3with 0.05mol/L K
2s
2o
2mixed solution, adds the dense H of 5mL98% (w)
2s0
4, after fully stirring with glass bar, obtain the mixed solution of an achromaticity and clarification.By gained colourless solution isothermal reaction 36h in 40 DEG C of water-baths.After having reacted, collected by suction black precipitate, be neutral with deionized water cyclic washing to solution, well obtains positive electrode in 100 DEG C of vacuumize 12h in an oven.
The preparation of positive pole:
By prepared positive electrode and acetylene black, PTFE (5% (w)) in mass ratio 75:15:10 mix, fully grind evenly with agate mortar.Add ethanol in proper amount, with blade equably blade coating at 3x3cm
2nickel foam on, put into 120 DEG C of vacuum drying chambers and be dried to constant weight, at 10MPa pressure flakiness, positive active material carrying capacity is 5mg/cm
2.
Electrolyte configuration and battery assembling:
The 0.5mol/L ZnSO of electrolyte: 40ml
4+ 1.0mol/L LiNO
3solution, electrolyte PH value is 3.0; Monocell is positive end plate, positive pole 3x3cm successively
2, negative pole 3x3cm
2graphite cake, negative positive end plate, single-cell structure and system are shown in Fig. 1.
Battery testing:
Electrolyte flow rate: 5ml/min; Charging and discharging currents density 20mA/cm
2; Charging capacity 20mAh/cm
2.
Battery performance is shown in Fig. 2, and long-life experimental result is shown in Fig. 3.Known at charging and discharging currents density 20mA/cm by Fig. 2, Fig. 3
2; Charging capacity 20mAh/cm
2under condition, the energy efficiency of battery reaches about 95%, and 400 times cycle performance has no obvious decay.Compare the 5-10 percentage point of the performance boost under Zinc ion single-fluid battery the same terms.And 400 times cycle performance is undamped, and cyclical stability is compared aquo-lithium ion battery and obtained very big improvement.
Embodiment 2
The preparation of positive electrode: (for Ni, Mn mixed oxide)
Be the nickel acetate of 3:3:6:1 by mol ratio, manganese sulfate, potassium permanganate, lithium sulfate be placed in agate mortar and grind about 0.5h, to be ground when no longer deepening to system color, solid mixture is transferred in small beaker, be placed in (80 ± 5) DEG C water-bath and heat about 10h, porphyrize, porphyrize after 300 DEG C of high-temperature calcination 3h in Muffle furnace.
The preparation of positive pole:
By prepared positive electrode and acetylene black, PTFE (5% (w)) in mass ratio 75:15:10 mix, fully grind evenly with agate mortar.Add ethanol in proper amount, with blade equably blade coating at 3x3cm
2nickel foam on, put into 120 DEG C of vacuum drying chambers and be dried to constant weight, at 10MPa pressure flakiness, positive active material carrying capacity is 10mg/cm
2.
Electrolyte configuration and battery assembling:
The 0.5mol/L Zn(NO of electrolyte: 40ml
3)
2+ 1.0mol/L Li
2sO
4solution, with potassium hydroxide regulation and control electrolyte PH value for 8.0; Monocell is positive end plate, positive pole 3x3cm successively
2, negative pole 3x3cm
2graphite cake, negative positive end plate.Single-cell structure and system are shown in Fig. 1.
Battery testing:
Electrolyte flow rate: 5ml/min; Charging and discharging currents density 20mA/cm
2; Charging capacity 20mAh/cm
2.
Battery performance is shown in Fig. 3.As shown in Figure 3 at charging and discharging currents density 20mA/cm
2; Charging capacity 20mAh/cm
2under condition, the energy efficiency of battery reaches about 90%, compares the 5-10 percentage point of the performance boost under Zinc ion single-fluid battery the same terms.And 320 times cycle performance is undamped, and cyclical stability is compared aquo-lithium ion battery and obtained very big improvement.
This battery adopts embedding and the deintercalation reaction of lithium ion due to positive pole reaction, and the zinc ion comparing zinc ion flow battery positive pole embeds deintercalation reaction and has higher electrochemical reversibility; This battery adopts the deposition of zinc to dissolve due to negative pole, and the Lithium-ion embeding deintercalation reaction comparing aquo-lithium ion battery negative pole has higher invertibity and lower price and better cyclical stability.
Claims (6)
1. a water system zinc ion flow battery, comprises the pile of a joint monocell or the above cells in series of two joints, the fluid reservoir of electrolyte is housed; Monocell comprises positive pole, negative pole, it is characterized in that: the solute of described electrolyte is by the soluble-salt containing zinc ion and contain lithium ion or/and the soluble-salt of sodium ion forms, and solvent is water;
Positive electrode active materials be embed Li or/and Na ion Mn, Co, Ni, Fe oxide in one or more mixed oxide; Negative pole is deposition type electrode.
2. water system Zinc ion single-fluid battery according to claim 1, is characterized in that:
Be filled with electrolyte in electrolyte storage tank, electrolyte storage tank is connected with the entrance and exit of monocell or pile by pipeline respectively through liquid delivery pump;
During charging, the lithium ion embedded in positive pole is or/and sodium ion deintercalation enters in electrolyte; Zinc ion deposits with zinc simple substance form at negative pole; During electric discharge, lithium ion is or/and sodium ion embeds in positive electrode; The zinc simple substance of cathode deposition is oxidized to zinc ion via being pumped back in fluid reservoir.
3. water system Zinc ion single-fluid battery according to claim 1, is characterized in that: the described soluble-salt containing zinc ion is one or more in zinc sulfate, zinc nitrate, zinc chloride or zinc bromide; In electrolyte, zinc ion concentration is 0.5-1.0mol/L;
Soluble salt solutions containing lithium ion is one or more in lithium sulfate, lithium nitrate, lithium chloride or lithium bromide; Soluble salt solutions containing sodium ion is one or more in sodium sulphate, sodium nitrate, sodium chloride or sodium bromide; In electrolyte, lithium ion and/or Na ion concentration are 1.0-2.0mol/L.
4. water system Zinc ion single-fluid battery according to claim 1, is characterized in that: the pH value of electrolyte is greater than 2.0.
5. water system Zinc ion single-fluid battery according to claim 1, is characterized in that: positive pole is made up of the positive electrode on matrix and its, and positive electrode is made up of positive electrode active materials, conductive agent, binding agent; Embed Li or/and Na ion Mn, Co, Ni, Fe oxide in one or more mixed oxide, conductive agent is material with carbon element, binding agent is PTFE or PVDF, the mass ratio 60%-80% of positive electrode active materials in positive pole, conductive agent is mass ratio 5%-30% in positive pole, and binding agent is mass ratio 10%-35% in positive pole.
6. water system Zinc ion single-fluid battery according to claim 1, is characterized in that: described negative pole is deposition type electrode, and described deposition type electrode is tabular or cavernous metal or material with carbon element.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070901A (en) * | 2015-07-16 | 2015-11-18 | 张家港智电芳华蓄电研究所有限公司 | Method for preparing secondary battery of zinc-lithium-manganese water system |
| CN105336952A (en) * | 2015-10-15 | 2016-02-17 | 中国科学院青岛生物能源与过程研究所 | Sodium zinc double-ion chargeable cell |
| CN105336971A (en) * | 2015-09-25 | 2016-02-17 | 中国人民解放军63971部队 | Water-system zinc-manganese single flow battery |
| CN106549188A (en) * | 2015-09-18 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of zinc sulfur single flow battery system |
| WO2017084372A1 (en) * | 2015-11-19 | 2017-05-26 | 广州道动新能源有限公司 | New-generation dual-electrolyte zinc secondary battery |
| CN107591531A (en) * | 2017-09-25 | 2018-01-16 | 华南师范大学 | A kind of lithium/sodium double ion manganese-base oxide positive electrode and preparation method and application |
| CN108365246A (en) * | 2018-01-12 | 2018-08-03 | 复旦大学 | A kind of half flow battery with ion embedded type solid cathode |
| CN109755560A (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 double flow battery |
| CN111244561A (en) * | 2020-03-08 | 2020-06-05 | 南开大学 | Preparation method of high-energy-density and high-voltage graphite-zinc-based ion battery based on aqueous electrolyte |
| CN114976294A (en) * | 2022-06-07 | 2022-08-30 | 辽宁大学 | Stacked water system high-voltage button battery and preparation method thereof |
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| CN101677135B (en) * | 2008-09-18 | 2012-10-31 | 中国人民解放军63971部队 | Zinc-manganese flow battery |
| CN102201590B (en) * | 2011-04-22 | 2013-10-16 | 北京化工大学 | Acidic zinc single liquid flow energy storage battery |
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Non-Patent Citations (1)
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| M.SKYLLAS-KAZACOS ET AL.: "Progress in flow battery research and development", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070901A (en) * | 2015-07-16 | 2015-11-18 | 张家港智电芳华蓄电研究所有限公司 | Method for preparing secondary battery of zinc-lithium-manganese water system |
| CN105070901B (en) * | 2015-07-16 | 2019-01-25 | 张家港智电芳华蓄电研究所有限公司 | A kind of preparation method of zinc lithium manganese aqueous systems secondary cell |
| 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 |
| CN106549188A (en) * | 2015-09-18 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of zinc sulfur single flow battery system |
| CN105336971B (en) * | 2015-09-25 | 2018-08-17 | 中国人民解放军63971部队 | Water-system zinc-manganese single flow battery |
| CN105336971A (en) * | 2015-09-25 | 2016-02-17 | 中国人民解放军63971部队 | Water-system zinc-manganese single flow battery |
| CN105336952B (en) * | 2015-10-15 | 2018-10-02 | 中国科学院青岛生物能源与过程研究所 | A kind of sodium zinc double ion rechargeable battery |
| CN105336952A (en) * | 2015-10-15 | 2016-02-17 | 中国科学院青岛生物能源与过程研究所 | Sodium zinc double-ion chargeable cell |
| WO2017084372A1 (en) * | 2015-11-19 | 2017-05-26 | 广州道动新能源有限公司 | New-generation dual-electrolyte zinc secondary battery |
| CN107591531A (en) * | 2017-09-25 | 2018-01-16 | 华南师范大学 | A kind of lithium/sodium double ion manganese-base oxide positive electrode and preparation method and application |
| CN109755560A (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 double flow battery |
| CN108365246A (en) * | 2018-01-12 | 2018-08-03 | 复旦大学 | A kind of half flow battery with ion embedded type solid cathode |
| CN111244561A (en) * | 2020-03-08 | 2020-06-05 | 南开大学 | Preparation method of high-energy-density and high-voltage graphite-zinc-based ion battery based on aqueous electrolyte |
| CN111244561B (en) * | 2020-03-08 | 2023-01-13 | 南开大学 | Preparation method of high-energy-density and high-voltage graphite-zinc-based ion battery based on aqueous electrolyte |
| CN114976294A (en) * | 2022-06-07 | 2022-08-30 | 辽宁大学 | Stacked water system high-voltage button battery and preparation method thereof |
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| CN104716391B (en) | 2017-06-06 |
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