CN110224157B - Non-circulating flow battery - Google Patents
Non-circulating flow battery Download PDFInfo
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- CN110224157B CN110224157B CN201910363373.8A CN201910363373A CN110224157B CN 110224157 B CN110224157 B CN 110224157B CN 201910363373 A CN201910363373 A CN 201910363373A CN 110224157 B CN110224157 B CN 110224157B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
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- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 101710134784 Agnoprotein Proteins 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 3
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- 102000004310 Ion Channels Human genes 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000011572 manganese Substances 0.000 description 9
- 229910052720 vanadium Inorganic materials 0.000 description 8
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
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- 230000036647 reaction Effects 0.000 description 4
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- 150000003839 salts Chemical class 0.000 description 3
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- 229910000604 Ferrochrome Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- 229910004298 SiO 2 Inorganic materials 0.000 description 1
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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
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04276—Arrangements for managing the electrolyte stream, e.g. heat exchange
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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
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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
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
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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
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Abstract
The invention discloses a non-circulating flow battery, which comprises a battery monomer and is characterized in that: it is a plurality of the battery monomer passes through bipolar plate and establishes ties in proper order, be equipped with in the battery monomer with complete confined positive pole electrolyte chamber and negative pole electrolyte chamber, positive electrolyte and negative pole electrolyte among the battery monomer seal respectively in positive pole electrolyte chamber and negative pole electrolyte intracavity. The non-circulating flow battery structure provided by the invention omits an electrolyte storage tank, a circulating pump, a circulating pipeline and other structures, so that the occupied space of the whole flow battery is greatly reduced, and meanwhile, the volumetric specific energy density of the flow battery is increased on the basis of the volume of the whole flow battery. Meanwhile, electrolyte in different battery monomers is prevented from being mixed through a circulating pipeline, and leakage loss caused by formation of an ion channel is avoided.
Description
Technical Field
The invention relates to the technical field of flow battery energy storage, in particular to a non-circulating flow battery.
Background
In the conventional flow battery, positive and negative electrolytes respectively circulate through positive and negative circulation systems, and the circulation systems include an electrolyte storage tank, a circulation pump, a circulation pipeline and other components, and are generally used for peak shaving energy storage of a large-scale power station. Recently, more and more researchers begin to apply the flow battery to the field of electric vehicles, the flow battery as a power battery only needs to replace the electrolyte, but the flow battery occupies a large space, has a high manufacturing cost, and has a low volumetric energy and a low gravimetric energy of a battery system.
In addition, when the output power of the flow battery needs to be improved, the plurality of single batteries are connected in series through the bipolar plates to increase the output voltage, and the electrolyte among the plurality of single batteries must be communicated with the circulating pipeline through the plurality of parallel electrolyte branch pipes, so that the electrolyte of different single batteries is connected in series to form an ion channel, and the ion channel and the electron channel form a closed loop to generate leakage current, thereby influencing the efficiency of the whole electric pile. In the existing flow battery structure, the application of the flow battery is limited because the problems cannot be solved effectively.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a non-circulating flow battery which has a simple structure, large volume ratio energy and leakage avoidance.
In order to achieve the above object, the present invention provides a non-circulating flow battery, which includes a battery cell, and is characterized in that: the single batteries are sequentially connected in series through bipolar plates to form a galvanic pile, each single battery comprises a positive electrolyte cavity and a negative electrolyte cavity which are completely sealed at the periphery, a diaphragm is arranged between each positive electrolyte cavity and each negative electrolyte cavity, and two ends of the galvanic pile are respectively provided with a drainage plate.
Furthermore, the upper end and the lower end of the anode electrolyte cavity and the lower end of the cathode electrolyte cavity are respectively provided with an anode electrolyte frame and a cathode electrolyte frame.
Furthermore, the positive electrode electrolyte frame and the negative electrode electrolyte frame are provided with liquid injection holes, and the liquid injection holes are in sealing fit with the liquid injection hole covers.
Further, the electric pile is positioned in an insulating shell with an upper end opening, and the upper end opening of the shell is sealed by a cover plate.
Furthermore, one of a graphite felt, a carbon felt and foamed nickel is arranged in the positive electrolyte cavity and the negative electrolyte cavity.
Further, 3% -8% of gas-phase SiO is added into the anode electrolyte cavity and the cathode electrolyte cavity 2 Or glass fiber cotton with equal thickness is arranged.
Preferably, the active component of the positive electrode in the discharge state is VOSO 4 The active component of the negative electrode is V 2 (SO4) 3 。
Preferably, the positive active ingredient is FeSO in the discharge state 4 The active component of the negative electrode is ZnSO 4 Adding 0.1-2 mol/L H into the electrolyte cavity of the anode 2 SO 4 (ii) a 0.1-2 mol/L (NH) is added into the negative electrode electrolyte cavity 4 ) 2 SO 4 Or Na 2 SO 4 。
Preferably, the active component of the positive electrode in the discharge state is MnSO 4 Adding 0.1-2 mol/L H into the electrolyte cavity of the anode 2 SO 4 And 0.005-0.5 mol/L AgNO 3 (ii) a The active component of the negative electrode is ZnSO 4 Adding into the negative electrode electrolyte cavity0.1-2 mol/L of (NH) 4 ) 2 SO 4 Or Na 2 SO 4 。
Preferably, the active component of the positive electrode in the discharge state is MnSO 4 Adding 0.1-2 mol/L H into the electrolyte cavity of the anode 2 SO 4 And 0.005-0.5 mol/L AgNO 3 (ii) a The active component of the negative electrode is MnSO 4 0.1-2 mol/L (NH 4) is added into the negative electrode electrolyte cavity 2 SO 4 Or Na 2 SO 4 And 0.001 to 0.2mol/L of SeO 2 Or Na 2 SeO 3 。
The invention has the beneficial effects that:
1. the occupied space is small, and the volumetric specific energy is improved. According to the non-circulating flow redox flow battery structure provided by the invention, the positive and negative electrolytes are completely sealed in the positive and negative electrolyte cavities, the positive and negative electrolytes can only flow in the respective cavities, and exchange ions through the diaphragms, so that the structures of an electrolyte storage tank, a circulating pump, a circulating pipeline and the like are omitted, and the occupied space of the whole redox flow battery is greatly reduced. Meanwhile, the graphite felt, the carbon felt and the foamed nickel are arranged in the positive and negative electrolyte cavities to increase the reaction area and the reaction rate, and the volumetric specific energy density of the flow battery is increased on the basis of the volume of the whole flow battery.
2. Completely avoiding leakage loss. The positive and negative electrolyte cavities are completely isolated from the periphery, so that the serial connection and communication of electrolytes in different battery monomers through a circulating pipeline are avoided, and the leakage loss caused by the formation of an ion channel is avoided.
Drawings
FIG. 1 is a schematic view of the structure of the present invention.
Fig. 2 is a charge-discharge curve diagram of the all-vanadium redox flow battery of the invention and the conventional one.
Fig. 3 is a charge-discharge curve diagram of the zinc-iron flow battery of the invention.
Fig. 4 is a charge-discharge curve diagram of the zinc-manganese flow battery and the full-manganese flow battery.
The components in the figures are numbered as follows: the device comprises a shell 1, a cover plate 2, a drainage plate 3, a bipolar plate 4, a positive electrolyte frame 5, a negative electrolyte frame 6, a diaphragm 7, an electrolyte injection hole 8, an electrolyte injection hole cover 9, a positive electrolyte cavity 10 and a negative electrolyte cavity 11.
Detailed Description
The invention will be described in more detail below with reference to the accompanying drawings, which are included to provide a more clear understanding of the invention, but are not intended to limit the invention.
As shown in figure 1, the non-circulating flow battery comprises single batteries, wherein the single batteries are sequentially connected in series through bipolar plates 4 to form a galvanic pile, the galvanic pile is integrally placed in an insulating shell 1 with an opening at the upper end, the opening at the upper end of the shell 1 is sealed through a cover plate 2, and one side of each single battery at two ends, which is close to the shell 1, is provided with a flow guide plate 3. Be equipped with complete sealed positive electrolyte chamber 10 and negative pole electrolyte chamber 11 in the battery monomer, separate through diaphragm 7 between positive electrolyte chamber 10 and the negative pole electrolyte chamber 11, both ends are equipped with positive electrolyte frame 5 and negative pole electrolyte frame 6 respectively about it, all open on positive electrolyte frame 5 and the negative pole electrolyte frame 6 and annotate liquid hole 8, annotate liquid hole 8 and annotate liquid hole lid 9 seal fit. The positive electrolyte and the negative electrolyte in the single battery are respectively sealed in the positive electrolyte cavity 10 and the negative electrolyte cavity 11. Therefore, structures such as an electrolyte storage tank, a circulating pump, a circulating pipeline and the like are omitted, the occupied space of the whole flow battery is greatly reduced, meanwhile, the reaction area and the reaction rate are increased by arranging the graphite felt, the carbon felt and the foamed nickel in the anode and cathode electrolyte cavities, and the volumetric specific energy density of the flow battery is increased on the basis of the volume of the whole flow battery. Meanwhile, due to the fact that a liquid inlet pipeline and a liquid outlet pipeline of the anode electrolyte cavity and the cathode electrolyte cavity are omitted, the situation that electrolytes in different battery monomers are communicated in series through a circulating pipeline is avoided, and electric leakage loss caused by formation of an ion channel is avoided.
In the above technical solution, one of a graphite felt, a carbon felt and a foam nickel is provided in the positive electrolyte chamber 10 and the negative electrolyte chamber 11, wherein the foam nickel can only be used in the alkaline electrolyte. Therefore, the reaction area of the electrochemical reaction can be increased, the reaction is more uniform, and the concentration polarization and the resistance are reduced.
In the technical scheme, 3-8% of gas-phase SiO is added into the anode electrolyte cavity 10 and the cathode electrolyte cavity 11 2 Or glass fiber cotton with equal thickness is arranged. Adding 3-8% of gas phase SiO 2 The electrolyte can be formed into a gel shape, the glass fiber cotton with the same thickness can fix the electrolyte, the electrolyte cannot overflow, and the glass fiber cotton is suitable for mobile equipment.
The first embodiment is as follows: all-vanadium redox flow battery
The all-vanadium redox flow battery is one of the most mature redox flow batteries in the prior art, and the electrode reaction is as follows:
and (3) positive electrode:
negative electrode:
the cell reaction is as follows:
theoretical voltage V =1.259V
The drainage plate 3 adopts an impermeable graphite plate, the bipolar plate 4 adopts a carbon-plastic composite plate, the positive electrolyte frame 5 and the negative electrolyte frame 6 adopt plastics, and the diaphragm 7 adopts a proton exchange membrane. When preparing the electrolyte, firstly H 2 SO 4 Preparing VOSO in solution 4 The solution is then electrolyzed to make V in the solution 2 (SO4) 3 And VOSO 4 Respectively accounting for 50 percent, and respectively injected into the anode electrolyte cavity 10 and the cathode electrolyte cavity 11, and the battery can be charged and discharged. The electrolyte of the all-vanadium battery does not flow macroscopically, so the maximum capacity of the battery is limited in design and cannot be adjusted by changing the volume of the liquid storage tank, but the battery omits the liquid storage tank, a circulating pump, a pipeline and an electrolyte channel in the electric pile, and is not assembled in a compression mode by using a screw rod, and the specific energy of the battery as a system is greatly improved.
As shown in fig. 2, the solid line is the charging and discharging curve of the all-vanadium redox flow battery of the present invention, and the dotted line is the conventional all-vanadium redox flow batteryAnd (4) a flow battery charging and discharging curve. The positive and negative electrolytes are composed of: 2mol/L VOSO 4 And 1mol/L of H 2 SO 4 And the charge-discharge current density i =100mA/cm 2 . Although the charge-discharge efficiency of the all-vanadium redox flow battery is reduced, the specific energy of the all-vanadium redox flow battery is improved by more than 50% due to the fact that a large amount of weight and space are saved.
Example two: zinc-iron flow battery
The zinc-iron battery is an improved system for the ferrochrome battery. Ferrochromium batteries were the first flow battery system, but the redox reaction of chromium was difficult and required expensive catalysts; and a large amount of hydrogen is evolved in the charging reaction of the negative electrode. The two problems can be solved by replacing the chromium cathode with the zinc cathode, and the voltage of the battery is greatly increased, so the specific energy of the battery is increased, and the charge-discharge reaction is as follows:
and (3) positive electrode:
negative electrode:
the cell reaction is as follows:
E＝1.53V
in discharge state, the active component of the positive electrode is FeSO 4 The active component of the negative electrode is ZnSO 4 0.1-2 mol/L H is added into the anode electrolyte cavity 10 2 SO 4 (ii) a 0.1-2 mol/L (NH) is added into the negative electrode electrolyte cavity 11 4 ) 2 SO 4 Or Na 2 SO 4 . This can suppress Fe, which is an active material of the positive electrode 2 (SO4) 3 Hydrolysis occurs to avoid the formation of Fe (OH) 3 And (3) colloid.
The diaphragm 7 is an anion exchange membrane, and during charging, anion SO 4 2- From the negative electrolyte chamber 11, through the diaphragm 7, and to the positive electrolyte chamber 10, in the discharge state, the reverse. Therefore, the positive charge and discharge processes are carried out,The volume of the negative electrode electrolyte may vary.
Although the oxidation-reduction potential of the anode is not too high, in the working voltage range of the battery, a proper metal material is still difficult to be used as the bipolar plate 3, so that the drainage plate 3 and the bipolar plate 4 are made of impermeable graphite plates and carbon-plastic composite plates.
As shown in fig. 3, the solid line is the charging and discharging curve of the zinc-iron flow battery of the present invention. Wherein the positive electrolyte is 1mol/L FeSO 4 And 0.5mol/L of H 2 SO 4 (ii) a 1mol/L ZnSO as the electrolyte of the negative electrode 4 And 0.5mol/L of Na 2 SO 4 And the charge-discharge current density i =25mA/cm 2 Compared with the traditional zinc-iron flow battery, the zinc-iron flow battery has higher specific energy, and the anode electrolyte is less in air contact, so that the oxidation can be avoided, and the battery performance is more stable.
This embodiment can also be used with a hydrochloric acid system, i.e. the electrolyte is formulated with chloride.
Example three: zinc-manganese flow battery
The zinc-manganese battery is one of the earliest invented and most widely applied batteries, and is generally applied to the field of dry batteries or storage batteries before. Due to MnO as a positive electrode active material 2 Mn whose reduction product is inert under alkaline to weakly acidic conditions 2 O 3 And thus may not be chargeable or may be difficult to charge. In addition, the potential of the reaction is low, the number of transferred electrons is also low, and the specific energy of the battery is limited. The invention adopts strong acid sulfuric acid as electrolyte, and the discharge product is completely dissolved in water, so that the charging operation can be carried out. The electrode reaction is as follows:
and (3) positive electrode:
negative electrode:
the cell reaction is as follows:
the theoretical voltage V =1.993V of the battery is basically equivalent to that of a lead-acid storage battery.
Compared with the traditional zinc-manganese battery, mn 2+ /MnO 2 The balance potential of the electricity pair is higher, the number of electrons transferred by unit reaction is doubled, and therefore the zinc-manganese flow battery has higher specific energy. In order to make up for the insufficient conductivity of the negative electrolyte after the full charge, 0.1-2 mol/L (NH) is added into the negative electrolyte cavity 11 4 ) 2 SO 4 Or Na 2 SO 4 As a conductive salt.
At H 2 SO 4 In the electrolyte system, mn is electro-oxidized 2+ Formation of MnO from salt 2 The activation energy of the catalyst is up to 69.8kJ/mol, and the charging reaction can be carried out under the high-temperature condition of 60-98 ℃ generally. For this purpose, 0.005-0.5 mol/L AgNO is added into the positive electrode electrolyte cavity 10 3 ，Mn 2+ Oxidation to MnO 2 The reaction can be carried out at normal temperature, and a graphite blanket or a carbon felt is arranged in the positive electrolyte chamber 10 to generate MnO during charging 2 The particles adhere to the surface of the fibers rather than settling to the bottom of the positive electrolyte chamber 10, and in the discharged state conduct current through the carbon fibers to the bipolar plate 4. The drainage plate 3 and the bipolar plate 4 adopt metal bipolar plates such as titanium, titanium-manganese alloy, titanium-nickel alloy and the like, so that the specific energy and specific power of the battery can be improved, and the reliability of the battery can also be improved; the diaphragm adopts an anion exchange membrane.
Example four: full manganese flow battery
As a more preferred embodiment of the third embodiment, the corresponding cell reaction is as follows:
E θ ＝1.23+1.18＝2.41V
when in discharge state, the active ingredients of the anode and the cathode are MnSO 4 The trace manganese ions penetrate through the anion exchange membrane, so that the battery is not influenced. At this time electricity is suppliedThe cell has a higher voltage and specific energy. However, when the manganese negative electrode is charged, the hydrogen evolution amount is too large, and 0.001-0.2 mol/L SeO is added into the positive electrode electrolyte cavity 10 2 Or Na 2 SeO 3 To be inhibited.
0.1-2 mol/L (NH 4) is added into the negative electrode electrolyte cavity 11 2 SO 4 Or Na 2 SO 4 As the conductive salt, the diaphragm 7 adopts an anion exchange membrane, so that the concentration balance of the positive and negative active substances is ensured. In addition, a certain amount of ZnSO can be added into the cathode electrolyte 4 Thus, zn is co-precipitated with Mn during charging, and H can be suppressed because Zn has a high hydrogen evolution overpotential 2 And (4) precipitating.
As shown in fig. 4, the solid line is the charging and discharging curve of the zinc-manganese redox flow battery of the present invention, and the dotted line is the charging and discharging curve of the full-manganese redox flow battery of the present invention. The charging current and the discharging current of the two batteries are both i =50mA/cm2, but the negative pole compositions of the two batteries are different. Wherein the positive electrolyte of the zinc-manganese flow battery is 1.5mol/L MnSO 4 Solution and 0.01mol/L AgNO 3 Solution, negative electrode electrolyte is 1.5mol/L ZnSO 4 And 0.2mol/L of NaSO 4 (ii) a The negative electrode electrolyte of the full manganese liquid flow also comprises 0.01mol/L of Na 2 SeO 3 。
This example is a new battery system. Compared with the traditional aqueous solution battery, the battery has higher voltage, can fully utilize active substances and has longer cycle life. Of the two, the full manganese cell has a higher voltage, but the side reaction is also large.
Claims (3)
1. A non-circulating flow battery, which comprises a battery cell, and is characterized in that: the battery cells are sequentially connected in series through bipolar plates (4) to form a galvanic pile, each battery cell comprises a positive electrolyte cavity (10) and a negative electrolyte cavity (11) which are completely sealed at the periphery, a diaphragm (7) is arranged between each positive electrolyte cavity (10) and each negative electrolyte cavity (11), and two ends of the galvanic pile are respectively provided with a drainage plate (3); the positive electrode electrolyte cavity (10) and the negative electrode electrolyte cavity (11) are respectively provided with a positive electrode electrolyte frame (5) and a negative electrode electrolyte frame (6) at the upper end and the lower end, and the positive electrode electrolyte frame (5) and the negative electrode electrolyte frame (6) are arranged onThe liquid injection holes (8) are all opened, and the liquid injection holes (8) are in sealing fit with the liquid injection hole cover (9); one of a graphite felt, a carbon felt and foamed nickel is arranged in the positive electrolyte cavity (10) and the negative electrolyte cavity (11); 3% -8% of gas-phase SiO is added into the anode electrolyte cavity (10) and the cathode electrolyte cavity (11) 2 (ii) a In the discharge state, the active component of the positive electrode is MnSO 4 0.1-2 mol/L H is added into the positive electrode electrolyte cavity (10) 2 SO 4 And 0.005-0.5 mol/L AgNO 3 (ii) a The active component of the negative electrode is ZnSO 4 0.1-2 mol/L (NH) is added into the negative electrode electrolyte cavity (11) 4 ) 2 SO 4 Or Na 2 SO 4 。
2. The non-circulating flow battery of claim 1, wherein: the galvanic pile is positioned in an insulating shell (1) with an opening at the upper end, and the opening at the upper end of the shell (1) is sealed by a cover plate (2).
3. A non-circulating flow battery, which comprises a battery cell, and is characterized in that: the battery units are sequentially connected in series through bipolar plates (4) to form a galvanic pile, each battery unit comprises a positive electrolyte cavity (10) and a negative electrolyte cavity (11) which are completely sealed with the periphery, a diaphragm (7) is arranged between each positive electrolyte cavity (10) and each negative electrolyte cavity (11), and two ends of the galvanic pile are respectively provided with a drainage plate (3); the upper end and the lower end of the positive electrolyte cavity (10) and the lower end of the negative electrolyte cavity (11) are respectively provided with a positive electrolyte frame (5) and a negative electrolyte frame (6), the positive electrolyte frame (5) and the negative electrolyte frame (6) are respectively provided with an electrolyte injection hole (8), and the electrolyte injection hole (8) is in sealing fit with an electrolyte injection hole cover (9); one of graphite felt, carbon felt and foamed nickel is arranged in the positive electrolyte cavity (10) and the negative electrolyte cavity (11); 3% -8% of gas-phase SiO is added into the anode electrolyte cavity (10) and the cathode electrolyte cavity (11) 2 (ii) a When in discharge state, the active ingredients of the positive and negative electrodes are MnSO 4 0.1-2 mol/L (NH 4) is added into the negative electrode electrolyte cavity (11) 2 SO 4 Or Na 2 SO 4 Electrolyte of positive electrodeSeO with the concentration of 0.001-0.2 mol/L is added into the cavity (10) 2 Or Na 2 SeO 3 。
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