CN112786938A - Acid-base mixed high-voltage aqueous zinc battery and zinc flow battery with double dissolution deposition reaction - Google Patents

Acid-base mixed high-voltage aqueous zinc battery and zinc flow battery with double dissolution deposition reaction Download PDF

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CN112786938A
CN112786938A CN201911094650.6A CN201911094650A CN112786938A CN 112786938 A CN112786938 A CN 112786938A CN 201911094650 A CN201911094650 A CN 201911094650A CN 112786938 A CN112786938 A CN 112786938A
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electrolyte
negative electrode
zinc
reaction chamber
positive
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CN112786938B (en
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刘宇
刘常
迟晓伟
韩奇
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Shanghai Institute of Ceramics 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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H01M2300/0011—Sulfuric acid-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • 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

The present invention relates to an acid-base mixed high-voltage aqueous zinc battery and a zinc flow battery having a double dissolution deposition reaction, the acid-base mixed high-voltage aqueous zinc battery having a double dissolution deposition reaction including: the battery comprises a positive electrode, a negative electrode, a diaphragm, a positive electrolyte and a negative electrolyte, wherein the positive electrode and the negative electrode are separated by the diaphragm and are respectively in the positive electrolyte and the negative electrolyte which are independent from each other; the positive electrode is a carbon electrode without active substances; the negative electrode is a zinc negative electrode; the positive electrolyte is an acid electrolyte containing manganese salt; the negative electrode electrolyte is an alkaline electrolyte containing zinc salt; the diaphragm is a bipolar membrane compounded by a cation exchange membrane and an anion exchange membrane or a solid electrolyte diaphragm conducting specific ions.

Description

Acid-base mixed high-voltage aqueous zinc battery and zinc flow battery with double dissolution deposition reaction
Technical Field
The invention relates to an acid-base mixed high-voltage aqueous zinc battery and a zinc flow battery with double dissolution deposition reactions, belonging to the technical field of secondary batteries.
Background
At present, due to environmental pollution and exhaustion of fossil fuels, people begin to utilize new energy sources such as solar energy and wind energy, but most of the new energy sources are intermittent, so that the new energy sources can be more effectively utilized by developing an energy storage technology, and an electrochemical energy storage technology represented by a lithium ion battery has the characteristics of high energy density, mature technology, green environmental protection and the like and is widely concerned by people. However, the lithium ion battery adopts organic electrolyte, is easy to ignite, has certain potential safety hazard, and is not suitable for being applied to a large-scale power energy storage system.
The aqueous battery adopts aqueous solution as battery electrolyte, has high safety, greatly reduces the cost compared with organic electrolyte, and has wide application prospect in the fields of civil and industrial energy storage. The rechargeable water system zinc battery adopts metal zinc and a compound with high specific energy as a negative electrode, has higher specific capacity, is widely concerned by people in recent years due to the characteristics of environmental protection, safety, low cost and the like, but the working voltage window of the water system zinc ion battery is severely limited because the electrochemical stability window of water is only 1.23V, so that the battery has lower specific energy.
In order to increase the voltage of an aqueous battery, wang (Suo, L.; borodin, O.; gao, T.; olguin, M.; ho, J.; fan, X.; luo, C.; wang, C.; xu, K.; water-in-salt "electrochemical activities high-voltage aqueous alkali-chemistry. Science 2015,350 (6263), 938-43.) groups designed a high concentration salt electrolyte that significantly reduced the electrochemical activity of Water molecules as described in the above non-patent documents, thereby successfully broadening the electrochemical window of Water to 3V, but this approach greatly increased the cost of the battery due to the use of expensive high concentration salts, and in addition, only a small portion of the salts may have such a high solubility in Water (21 mol L.) -1 ) This greatly limits the options available for battery systems. The patent (Chinese publication No. CN 105140575A) proposes an aqueous battery of acid-base double electrolyte, but the positive electrode of the battery lacks manganese salt as a positive electrode reactant during charging, so that the coulomb efficiency of the battery is lower; whileIn the circulation process, hydrogen ions and hydroxyl can permeate each other, and the pH difference of the electrolytes on two sides cannot be maintained; furthermore, the cycling of the metal negative electrode in alkaline environment is prone to dendrite formation, which severely limits its cycling stability. In order to solve the above problems, the present invention provides an acid-base mixed high-voltage aqueous zinc battery having a double dissolution deposition reaction.
Disclosure of Invention
The invention aims to provide an acid-base mixed high-voltage aqueous zinc battery with double dissolution and deposition reactions, aiming at the problem of low energy density of the aqueous zinc battery, and the method can effectively improve the energy density and the cycling stability of the battery.
In a first aspect, the present invention provides an acid-base mixed high-voltage aqueous zinc battery having a double dissolution deposition reaction, including: the battery comprises a positive electrode, a negative electrode, a diaphragm, positive electrolyte and negative electrolyte, wherein the positive electrode and the negative electrode are separated by the diaphragm and are respectively in the positive electrolyte and the negative electrolyte which are independent from each other;
the positive electrode is a carbon electrode without active material;
the negative electrode is a zinc negative electrode;
the positive electrolyte is an acid electrolyte containing manganese salt;
the negative electrode electrolyte is an alkaline electrolyte containing zinc salt;
the diaphragm is a bipolar membrane compounded by a layer of cation exchange membrane and a layer of anion exchange membrane or a solid electrolyte diaphragm conducting specific ions.
The invention provides a method for improving the working voltage of a battery by using acid-base mixed electrolyte, which is different from the de-intercalation reaction of a conventional zinc battery, and the positive/negative electrodes are both dissolution-deposition reaction, so that the specific capacity of the battery is greatly improved, and the aim of improving the energy density of the battery is fulfilled. The principle is that the electrode reaction of zinc under neutral and acidic conditions is as follows: zn-2e - →Zn 2+ The standard electrode potential is-0.762V, and the electrode reaction of zinc under alkalinity is Zn-2e - +4OH - →Zn(OH) 4 - The standard electrode potential is-1.215V, thereforeIf the zinc cathode is allowed to operate under alkaline conditions, the voltage of the cell will increase by 0.453V. In addition, manganese salt is added into the electrolyte of the positive electrode, manganese ions can generate manganese dioxide deposition and dissolution reaction under the acidic condition, the two-electron transfer process is adopted, and compared with the zinc ion de-intercalation reaction (single-electron transfer process) of the traditional water-system zinc-manganese battery, the capacity is improved by one time (616 mAh/g).
Preferably, the positive electrode is carbon paper, carbon cloth or carbon felt; the zinc cathode is a metal zinc or composite zinc electrode.
Preferably, the manganese salt in the manganese salt-containing acidic electrolyte is at least one of manganese sulfate, manganese nitrate and manganese acetate; the acid in the manganese salt-containing acidic electrolyte is nitric acid or sulfuric acid.
Preferably, the concentration of the manganese salt in the manganese salt-containing acidic electrolyte is 0.5-2mol/L, and the concentration of the acid is 0.5-1mol/L.
Preferably, the zinc salt in the alkaline electrolyte containing the zinc salt is selected from at least one of zinc chloride, zinc acetate, zinc sulfate and zinc nitrate; the alkali in the zinc salt-containing alkaline electrolyte is at least one selected from potassium hydroxide, sodium hydroxide and lithium hydroxide.
Preferably, the concentration of the zinc salt in the zinc salt-containing alkaline electrolyte is 0.05-0.2mol/L, and the concentration of the alkali is 2-4mol/L.
In a second aspect, in addition to using a diaphragm to separate electrolytes on both sides, the cell structure also needs to ensure that the electrolytes on both sides do not cross, so the invention provides an acid-base mixed high-voltage aqueous zinc cell structure (a in fig. 1) with double dissolution deposition reaction, comprising:
a negative electrode sheet made of a negative electrode;
a negative electrode reaction chamber for accommodating a negative electrode electrolyte;
the positive electrode reaction chamber is used for accommodating positive electrode electrolyte;
the diaphragm is positioned between the positive electrode reaction chamber and the negative electrode reaction chamber and is used for separating the positive electrode electrolyte and the negative electrode electrolyte;
and a positive plate made of a positive electrode and positioned on one side of the positive electrode reaction chamber.
In the present disclosure, the main body of the cell structure is composed of two reaction chambers (anode chamber, cathode chamber), two baffles and three gaskets, and the structure is tightened by bolts, so that the tightness of the cell can be ensured.
Preferably, one side of the negative electrode reaction chamber close to the negative electrode sheet is provided with a first groove for placing a first gasket; and the negative plate and the negative reaction chamber are sealed by a first gasket.
Preferably, one side of the negative electrode reaction chamber close to the diaphragm is provided with a second groove for placing the diaphragm.
Preferably, one side of the positive electrode reaction chamber, which is close to the diaphragm, is provided with a third groove for placing a second gasket; and the positive electrode reaction chamber and the negative electrode reaction chamber are sealed through a second gasket.
Preferably, one side of the positive electrode reaction chamber, which is close to the positive electrode plate, is provided with a fourth groove for placing a third gasket; and the positive plate and the positive reaction chamber are sealed through a third gasket.
Preferably, a first baffle is arranged on one side of the negative plate away from the negative reaction chamber; and a second baffle is arranged on one side of the positive plate far away from the positive reaction chamber.
In a third aspect, the invention provides a flow battery for improving the cycling stability of an acid-base hybrid battery. There are two problems with static batteries: zinc is easy to form dendrite after being circulated in alkalinity; although the bipolar membrane can theoretically block hydrogen ions and hydroxide ions from passing through, the inevitable existence of a small amount of hydrogen ions and hydroxide ions can pass through the membrane under the action of concentration difference and electric field, so that the pH difference on two sides cannot be maintained stably. In order to solve the problems, the invention provides a flow battery mode to relieve the dendrite problem and the change of the pH value of the electrolyte, and compared with the structure of the high-voltage water system battery, the positive and negative electrolyte storage tanks and two peristaltic pumps are added.
To this end, the present invention provides a high-voltage aqueous zinc flow battery having a structure (b in fig. 1) including:
a negative electrode sheet made of a negative electrode;
a negative electrode reaction chamber for accommodating a negative electrode electrolyte;
the positive electrode reaction chamber is used for accommodating positive electrode electrolyte;
the diaphragm is positioned between the positive electrode reaction chamber and the negative electrode reaction chamber and is used for separating the positive electrode electrolyte from the negative electrode electrolyte;
and a positive plate made of a positive electrode and located on one side of the positive electrode reaction chamber:
the anode liquid storage tank is used for storing anode electrolyte and is communicated with the anode reaction chamber through a pipeline;
the negative electrode liquid storage tank is used for storing negative electrode electrolyte and is communicated with the negative electrode reaction chamber through a pipeline;
the first peristaltic pump is used for driving the positive electrolyte to flow between the positive liquid storage tank and the positive reaction chamber;
and the second peristaltic pump is used for driving the cathode electrolyte to flow between the cathode liquid storage tank and the cathode reaction chamber.
Preferably, one side of the negative electrode reaction chamber, which is close to the negative electrode sheet, is provided with a first groove for placing a first gasket; and the negative plate and the negative reaction chamber are sealed through a first gasket.
Preferably, one side of the negative electrode reaction chamber close to the diaphragm is provided with a second groove for placing the diaphragm.
Preferably, one side of the positive electrode reaction chamber, which is close to the diaphragm, is provided with a third groove for placing a second gasket; and the positive electrode reaction chamber and the negative electrode reaction chamber are sealed by a second gasket.
Preferably, one side of the positive electrode reaction chamber, which is close to the positive electrode plate, is provided with a fourth groove for placing a third gasket; and the positive plate and the positive reaction chamber are sealed through a third gasket.
Preferably, a first baffle plate is arranged on one side of the negative electrode piece, which is far away from the negative electrode reaction chamber; and a second baffle is arranged on one side of the positive plate, which is far away from the positive reaction chamber.
Has the advantages that:
in the invention, the acid-base mixed high-voltage water system zinc battery with double dissolution deposition reactionCompared with the conventional water system zinc ion battery, the battery has higher cycle performance, extremely high discharge voltage platform (2.44V) and extremely high energy density (1503 Wh kg) -1 Based on the positive electrode material). Moreover, the obtained flow battery has longer cycle life, and the battery can still maintain 99.5 percent of initial discharge capacity after 6000 cycles.
Drawings
Fig. 1 is a schematic structural view of a high-voltage aqueous battery according to the present invention, in which (a) is a schematic structural view of an acid-base mixed high-voltage aqueous zinc battery having a double dissolution deposition reaction, and (b) is a schematic structural view of an acid-base mixed high-voltage aqueous zinc flow battery having a double dissolution deposition reaction;
FIG. 2 is a schematic diagram of the charging and discharging of an acid-base mixed high-voltage aqueous zinc flow battery with double dissolution deposition reaction obtained in example 1 of the present invention;
fig. 3 is a graph comparing the cycle performance of the acid-base mixed high-voltage aqueous zinc flow battery with double dissolution deposition reaction obtained in example 1 of the present invention with the cycle performance of a non-flow high-voltage aqueous zinc battery, wherein (a) is a flow battery cycle graph and (b) is a high-voltage aqueous zinc battery cycle graph;
fig. 4 is an electrochemical window of the electrolyte and cyclic voltammogram of two electrodes in the acid-base mixed high voltage aqueous zinc flow battery with double dissolution deposition reaction obtained in example 1 of the present invention;
fig. 5 is an XRD and SEM images of the positive electrode of the acid-base mixed high voltage aqueous zinc battery with double dissolution deposition reaction obtained in example 1 of the present invention in different states during cycling, wherein (a) is a voltage-time relationship of the battery in one cycle, (b) and (c) are XRD and SEM images of the positive electrode after discharging, (d) and (e) are XRD and SEM images of the positive electrode after charging, respectively, and (f) and (g) are XRD and SEM images of the positive electrode before charging, respectively;
fig. 6 is a SEM image of the zinc negative electrode of the high-voltage aqueous zinc flow battery and the high-voltage aqueous zinc battery after 300 cycles of the cycle, in which (a) is the zinc negative electrode of the high-voltage aqueous zinc flow battery and (b) is the zinc negative electrode of the non-flow high-voltage aqueous zinc battery;
FIG. 7 is a graph of discharge curve versus cycle performance for a cell obtained in example 2 of the present invention, wherein (a) is the discharge curve for the first turn of the cell and (b) is the cycle performance for the cell;
fig. 8 is a graph of discharge curve versus cycle performance for a cell obtained in example 3 of the present invention, wherein (a) is the discharge curve of the first turn of the cell and (b) is the cycle performance of the cell.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the present disclosure, an acid-base mixed high-voltage aqueous zinc battery having a double dissolution deposition reaction includes: the anode is a carbon electrode without active substances, the cathode is a zinc cathode, the anode electrolyte is an acidic electrolyte containing manganese salt, the cathode electrolyte is an alkaline electrolyte containing zinc salt, and the diaphragm is an organic film or a solid diaphragm capable of blocking hydrogen ions and hydroxyl ions from passing. The anode reaction of the high-voltage water-system zinc battery is different from the ion de-intercalation reaction of the anode of the conventional water-system zinc ion battery, namely the dissolution and deposition reaction of the electrode active substance, and the anode reaction and the cathode reaction occur in different pH environments.
In alternative embodiments, the zinc negative electrode may be one of a metallic zinc or a composite zinc electrode. The carbon electrode may be one of carbon paper, carbon cloth, and carbon felt.
In an alternative embodiment, the manganese salt of the acid electrolyte containing manganese salt may be one of manganese sulfate, manganese nitrate and manganese acetate, and the concentration of the manganese salt may be 0.5-2mol/L. The acid can be selected from nitric acid or sulfuric acid, and the concentration of the acid can be 0.5-1mol/L.
In an alternative embodiment, the zinc salt of the alkaline electrolyte containing zinc salt may be one of zinc chloride, zinc acetate, zinc sulfate, zinc nitrate, etc. The concentration of zinc salt can be 0.05-0.2mol/L. The alkali can be one of potassium hydroxide, sodium hydroxide and lithium hydroxide. The concentration of the base may be 2-4mol/L.
The battery system based on ion selective permeable membrane separation separates the electrolyte on two sides of the battery through the ion selective permeable membrane. Preferably, the separator is one of a bipolar membrane or a solid electrolyte separator that conducts specific ions.
In the present invention, a high-voltage aqueous zinc battery having an acid-base isolation electrode reaction has a specific structure (a in fig. 1) including, from left to right: the structure comprises a first baffle 1, a negative plate 2, a first gasket 3, a negative reaction chamber 4, a diaphragm 5, a second gasket 6, a positive reaction chamber 7, a third gasket 8, a positive plate 9 and a second baffle 10. It should be noted that "left" and "right" in the present invention are only descriptions applied to the positions of the respective components in fig. 1, and there is no specific directional characterization in the actual manufacturing process. Preferably, an inlet (or an outlet) for pouring in (or pouring out) the respective electrolytes is further provided on the positive electrode reaction chamber and the negative electrode reaction chamber.
In an alternative embodiment, the present invention mainly uses a gasket to ensure the sealing performance of the reaction chamber, and further uses a packaging method such as a bolt tightening method to ensure the sealing performance of the whole battery.
There are two problems with static high voltage aqueous zinc cells: zinc is easy to form dendrite after being circulated in alkalinity; although the bipolar membrane can theoretically block hydrogen ions and hydroxide ions from passing through, the inevitable small amount of hydrogen ions and hydroxide ions can pass through the membrane under the action of a concentration difference and an electric field, so that the pH difference on two sides cannot be maintained stably. In view of the above problems, the present invention proposes a flow battery to alleviate the dendrite problem and the slow change of the pH of the electrolyte. On the basis of the above-described high-voltage aqueous zinc battery structure, peristaltic pumps (a first peristaltic pump 12 and a second peristaltic pump 14) for driving the flow of the electrolyte, a negative reservoir tank 11 for storing the negative electrolyte, and a positive reservoir tank 13 for storing the positive electrolyte are added, as shown in b in fig. 1. And the anode liquid storage tank is used for storing the anode electrolyte and is circularly communicated with the anode reaction chamber through a pipeline. And the negative electrode liquid storage tank is used for storing the negative electrode electrolyte and is circularly communicated with the negative electrode reaction chamber through a pipeline. And the first peristaltic pump is used for driving the cathode electrolyte to circularly flow between the cathode liquid storage tank and the cathode reaction chamber. And the second peristaltic pump is used for driving the anode electrolyte to circularly flow between the anode liquid storage tank and the anode reaction chamber. It should be noted that "left" and "right" in the present invention are only descriptions applied to the positions of the components in fig. 1, and there is no specific directional characterization in the actual manufacturing process.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also merely one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
Preparing 100mL of positive electrolyte containing 1mol/L manganese sulfate and 0.5mol/L sulfuric acid;
100mL of negative electrode electrolyte containing 2.4mol/L potassium hydroxide and 0.1mol/L zinc acetate was prepared.
The metal zinc is used as a negative electrode, the carbon cloth is used as a positive electrode, and the bipolar membrane is used as a battery diaphragm (Fumasep FBM). A flow battery (see b in fig. 1) and a non-flow battery (see a in fig. 1) are assembled according to the battery structure shown in fig. 1, wherein the bipolar membrane is an ion permselective membrane and is composed of a cation exchange membrane (anode side) and an anion exchange membrane (cathode side), when the battery is assembled, the anode side faces to the cathode, and the cathode side faces to the anode, so that the hydrogen ions and hydroxide ions of the electrolytes on both sides can be ensured not to permeate each other.
Electrochemical testing of the assembled cell was carried out by constant voltage charging (2.65V) and constant current discharging (2 mA cm) -2 ). Fig. 2 is a charge-discharge curve of the high-voltage aqueous zinc flow battery with acid-base isolation electrode reaction obtained in example 1, and it can be found that the discharge voltage plateau of the battery is 2.44V, which is much higher than the voltage of the existing aqueous zinc ion battery.
The cycle performance of the high-voltage aqueous zinc battery with acid-base isolated electrode reaction is shown in fig. 3 (b). The cycle performance of the high-voltage aqueous zinc flow battery is shown in fig. 3 (a). The flow battery has excellent cycle performance, and after 6000 cycles, the discharge capacity of the battery can still be maintained at 99.5%, which is obviously superior to the cycle performance of a non-flow battery (1500 cycles, the discharge capacity retention rate is 94%).
From fig. 4, it can be found that the electrochemical stability window of the high-voltage aqueous zinc ion flow battery with acid-base isolation electrode reaction obtained in this example 1 is greatly widened (3V), which is much higher than the stability window of the electrolyte of the conventional aqueous battery (1.23V).
From fig. 5, it can be seen that a layer of charged product was deposited on the carbon fiber in the SEM picture after charging, and the product was manganese dioxide by XRD analysis, indicating that deposition of manganese dioxide occurred in the positive electrode during charging, and that the layer of manganese dioxide disappeared after discharging, and both SEM and XRD pictures are consistent with those before charging, indicating that the battery has good reversibility.
Fig. 6 shows that after 300 cycles, the surface of the zinc cathode of the flow battery has no obvious dendrite generation, and is smoother and smoother than the zinc cathode of the non-flow high-voltage water-based zinc battery.
Example 2
Preparing a positive electrolyte containing 1mol/L sulfuric acid, 0.1mol/L potassium permanganate and 0.5mol/L sodium sulfate;
preparing a negative electrode electrolyte containing 2.4mol/L of potassium hydroxide and 0.1mol/L of zinc acetate.
A performance test of the non-liquid flow high-voltage aqueous zinc battery assembled according to a in figure 1 shows that the battery has extremely low efficiency (< 25%) in a subsequent charging process because the battery has low efficiency and poor cycle performance due to oxygen evolution reaction of electrolyte caused by overhigh voltage in the charging process because the battery is assembled according to a figure 7.
Example 3
Preparing a positive electrolyte containing 1mol/L sulfuric acid and 0.5mol/L sodium sulfate;
preparing a negative electrode electrolyte containing 2.4mol/L of potassium hydroxide and 0.1mol/L of zinc acetate.
The method is characterized in that metal zinc is used as a negative electrode, a positive electrode is carbon paper coated with manganese dioxide (manganese dioxide: acetylene black: PVDF =7: 1), a bipolar membrane is used as a battery diaphragm, and a non-flow battery is assembled according to a mode in a in figure 1, a performance test of the battery is shown in figure 8, the efficiency of the battery in a subsequent charging process is low (< 50%), because bivalent manganese ions are lacked in electrolyte, although the manganese ions are generated in a discharging process, manganese loaded on an electrode is less, and the manganese ions are greatly diluted in the solution, so that the manganese ion concentration is extremely low, manganese dioxide cannot be formed in the charging process, the coulombic efficiency of the battery is low, and the good cycle performance of the battery can be ensured only by adding the manganese ions into the electrolyte of the positive electrode.
Example 4
100mL of anode electrolyte containing 1mol/L manganese sulfate and 0.5mol/L sulfuric acid is prepared;
100mL of negative electrode electrolyte containing 2.4mol/L of sodium hydroxide and 0.1mol/L of zinc acetate was prepared.
The battery was assembled in accordance with the battery structure shown in fig. 1, with metallic zinc as the negative electrode, carbon felt as the positive electrode, and NASICON-type solid electrolyte as the battery separator.

Claims (11)

1. An acid-base mixed high voltage aqueous zinc battery having a double dissolution deposition reaction, comprising: the battery comprises a positive electrode, a negative electrode, a diaphragm, a positive electrolyte and a negative electrolyte, wherein the positive electrode and the negative electrode are separated by the diaphragm and are respectively in the positive electrolyte and the negative electrolyte which are independent from each other;
the positive electrode is a carbon electrode without active substances;
the negative electrode is a zinc negative electrode;
the positive electrolyte is an acid electrolyte containing manganese salt;
the negative electrode electrolyte is an alkaline electrolyte containing zinc salt;
the diaphragm is a bipolar membrane compounded by a cation exchange membrane and an anion exchange membrane or a solid electrolyte diaphragm conducting specific ions.
2. The high-voltage aqueous zinc battery according to claim 1, wherein the positive electrode is carbon paper, carbon cloth, or carbon felt; the zinc cathode is a metal zinc or composite zinc electrode.
3. The high-voltage aqueous zinc battery according to claim 1 or 2, wherein the manganese salt in the manganese salt-containing acidic electrolyte is one or more of manganese sulfate, manganese nitrate, and manganese acetate; the acid in the manganese salt-containing acidic electrolyte is one or more of nitric acid or sulfuric acid; preferably, the concentration of the manganese salt in the manganese salt-containing acidic electrolyte is 0.5-2mol/L, and the concentration of the acid is 0.5-1mol/L.
4. The high-voltage aqueous zinc battery according to any one of claims 1 to 3, wherein the zinc salt in the alkaline electrolyte containing a zinc salt is at least one selected from the group consisting of zinc chloride, zinc acetate, zinc sulfate, and zinc nitrate; the alkali in the zinc salt-containing alkaline electrolyte is at least one selected from potassium hydroxide, sodium hydroxide and lithium hydroxide; preferably, the concentration of the zinc salt in the zinc salt-containing alkaline electrolyte is 0.05-0.2mol/L, and the concentration of the alkali is 2-4mol/L.
5. An acid-base mixed high-voltage aqueous zinc battery having a double dissolution deposition reaction, characterized in that the structure of the high-voltage aqueous zinc battery comprises:
a negative electrode sheet made of a negative electrode;
a negative electrode reaction chamber for accommodating a negative electrode electrolyte;
the positive electrode reaction chamber is used for accommodating positive electrode electrolyte;
the diaphragm is positioned between the positive electrode reaction chamber and the negative electrode reaction chamber and is used for separating the positive electrode electrolyte from the negative electrode electrolyte;
and a positive electrode plate made of a positive electrode positioned at one side of the positive electrode reaction chamber.
6. The high-voltage aqueous zinc battery according to claim 5, wherein a side of the negative electrode reaction chamber adjacent to the negative electrode sheet has a first groove for placing a first gasket; and the negative plate and the negative reaction chamber are sealed through a first gasket.
7. The high-voltage aqueous zinc battery according to claim 5 or 6, wherein a side of the negative electrode reaction chamber adjacent to the separator has a second groove for placing the separator.
8. The high-voltage aqueous zinc battery according to any one of claims 5 to 7, wherein a side of the positive electrode reaction chamber adjacent to the separator has a third groove for placing a second gasket; and the positive electrode reaction chamber and the negative electrode reaction chamber are sealed by a second gasket.
9. The high-voltage aqueous zinc battery according to any one of claims 5 to 8, wherein the positive electrode reaction chamber has a fourth groove for placing a third gasket on a side thereof adjacent to the positive electrode tab; and the positive plate and the positive reaction chamber are sealed through a third gasket.
10. The high-voltage aqueous zinc battery according to any one of claims 5 to 9, wherein a first baffle plate is provided on a side of the negative electrode sheet away from the negative electrode reaction chamber; and a second baffle is arranged on one side of the positive plate far away from the positive reaction chamber.
11. A high-voltage aqueous zinc flow battery characterized by a structure comprising:
a negative electrode sheet made of a negative electrode;
a negative electrode reaction chamber for accommodating a negative electrode electrolyte;
the positive electrode reaction chamber is used for accommodating a positive electrode electrolyte;
the diaphragm is positioned between the positive electrode reaction chamber and the negative electrode reaction chamber and is used for separating the positive electrode electrolyte and the negative electrode electrolyte;
and a positive electrode plate made of a positive electrode on one side of the positive electrode reaction chamber:
the positive electrode liquid storage tank is used for storing positive electrode electrolyte and is communicated with the positive electrode reaction chamber through a pipeline;
the negative electrode liquid storage tank is used for storing negative electrode electrolyte and is communicated with the negative electrode reaction chamber through a pipeline;
the first peristaltic pump is used for driving the positive electrolyte to flow between the positive liquid storage tank and the positive reaction chamber;
and the second peristaltic pump is used for driving the cathode electrolyte to flow between the cathode liquid storage tank and the cathode reaction chamber.
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CN114784331A (en) * 2022-05-18 2022-07-22 西安交通大学 Acid-base regulation system of zinc-bromine flow battery and working method thereof
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CN113782841A (en) * 2021-06-30 2021-12-10 浙江长兴绿色电池科技有限公司 Zinc battery electrolyte and preparation method thereof
CN114927658A (en) * 2022-05-06 2022-08-19 中国科学院上海硅酸盐研究所 Device and method for modifying surface of anode material based on ion exchange membrane
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CN115548471A (en) * 2022-11-10 2022-12-30 吉林大学 Water system zinc-carbon double-ion battery with wide potential window

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