CN114335661A - Electrolyte additive for improving stability of neutral water system rechargeable zinc-manganese battery and electrolyte - Google Patents
Electrolyte additive for improving stability of neutral water system rechargeable zinc-manganese battery and electrolyte Download PDFInfo
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- CN114335661A CN114335661A CN202111534475.5A CN202111534475A CN114335661A CN 114335661 A CN114335661 A CN 114335661A CN 202111534475 A CN202111534475 A CN 202111534475A CN 114335661 A CN114335661 A CN 114335661A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 230000007935 neutral effect Effects 0.000 title claims abstract description 104
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000003792 electrolyte Substances 0.000 title claims abstract description 50
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 49
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims abstract description 29
- 229910000368 zinc sulfate Inorganic materials 0.000 claims abstract description 29
- 229960001763 zinc sulfate Drugs 0.000 claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 claims description 22
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
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- 239000011230 binding agent Substances 0.000 claims description 15
- SZKTYYIADWRVSA-UHFFFAOYSA-N zinc manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Zn++] SZKTYYIADWRVSA-UHFFFAOYSA-N 0.000 claims description 15
- 239000006258 conductive agent Substances 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000002033 PVDF binder Substances 0.000 claims description 11
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- 239000000395 magnesium oxide Substances 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- 239000003273 ketjen black Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
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- 229910021389 graphene Inorganic materials 0.000 claims description 3
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- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims 3
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims 1
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- 241000282414 Homo sapiens Species 0.000 description 4
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910003174 MnOOH Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an electrolyte additive and electrolyte for improving the stability of a neutral water system rechargeable zinc-manganese battery, and belongs to the technical field of rechargeable zinc-manganese battery electrolytes. The electrolyte additive disclosed by the invention contains PO 4 3‑ The compound is green, cheap and pollution-free, and can effectively improve the cycle stability of the neutral water system rechargeable zinc-manganese battery under the condition of not changing the charging and discharging behaviors. By further characterization, it can be found that the PO contains 4 3‑ PO in the compound of (1) 4 3‑ Can form stable Zn on the surface of the positive electrode of the neutral water system rechargeable zinc-manganese battery 3 (PO 4 ) 2 ·4H 2 The O phase can not only stabilize the electrode structure of the anode which is continuously deposited and dissolved in the charging and discharging process, but also induce basic Zinc Sulfate (ZSH) and a deposition product Zn x MnO(OH) 2 The stable nucleation and deposition are carried out, thereby achieving the purpose of improving the stability of the neutral water system rechargeable zinc-manganese batteryThe object of (1).
Description
Technical Field
The invention belongs to the technical field of electrolyte of a rechargeable zinc-manganese battery, and relates to an electrolyte additive and electrolyte for improving the stability of a neutral water system rechargeable zinc-manganese battery.
Background
Energy is the source of human society's viability and development. The effective use of various fossil energy sources (petroleum, coal, and natural gas) has led to rapid progress in human civilization since the industrial revolution. However, excessive exploitation and use of traditional fossil energy also causes serious pollution and damage to the human living environment, which makes sustainable development of human beings face serious challenges. Renewable clean energy (wind energy, solar energy, tidal energy and the like) is used to gradually replace the leading position of the traditional fossil energy in the social and economic production, and becomes the main direction of energy revolution. However, due to the intermittent and random nature of the various renewable clean energy sources, it has become critical to develop efficient large-scale energy storage systems for their development and utilization.
Among a large number of large-scale energy storage devices, electrochemical secondary batteries are considered as one of the most potential large-scale energy storage devices due to the characteristics of strong environmental adaptability, small early investment, flexible use and the like. In the secondary battery market today, lead acid batteries (VRLA) and Lithium Ion Batteries (LIBs) are firmly occupying a major share of the energy storage market. However, lead-acid batteries cannot fully meet the green development requirements due to the low energy density (about 75Wh kg-1), the heavy use of sulfuric acid and metallic lead, which are a serious pollution to the environment. Lithium ion batteries can provide high energy density, but face high price and potential safety hazards from the use of flammable and explosive electrolytes. Therefore, the development of a secondary battery that is inexpensive, safe, pollution-free, and has a relatively high energy density has become a key to the application of electrochemical secondary batteries in large-scale energy storage systems. In recent years, due to the advantages of high theoretical capacity, low cost, safety, no pollution and the like, a water system rechargeable zinc-manganese battery consisting of a manganese oxide anode, zinc salt neutral aqueous solution electrolyte and a metal zinc cathode becomes a hot spot in the research of large-scale energy storage secondary battery devices. If the energy density and the cycle stability which can be equal to or even exceed those of the lead-acid battery can be obtained by an effective means, the water system rechargeable zinc-manganese battery can be widely applied to the large-scale energy storage field and other market segments.
Although the water system is chargeableThe electrochemical performance of the zinc-manganese battery in a laboratory range is improved, but the energy storage mechanism of the positive electrode is controversial, which causes great uncertainty in further large-scale application of the zinc-manganese battery. MnO different from conventional ion intercalation/deintercalation viewpoint 2 In recent research, the reversible energy storage behavior of a water-based rechargeable zinc-manganese battery using a sulfate-based aqueous salt solution as an electrolyte is derived from a basic Zinc Sulfate (ZSH) assisted deposition dissolution reaction, and the specific process is as follows:
Zn 4 SO 4 ·(OH) 6 ·xH 2 O(ZSH)+Mn 2+ +2e - →Zn x MnO(OH) 2 +H + +SO 4 2- (charging Process)
Zn x MnO(OH) 2 +4H + +2e - →Mn 2+ +xZn 2+ +3H 2 O (discharge process)
4Zn 2+ +SO 4 2- +6OH - +xH 2 O→Zn 4 SO 4 ·(OH) 6 ·xH 2 O (ZSH) (discharge process)
For MnO 2 At the positive electrode, the proton solid phase reaction can occur in the first circle discharging process to cause the surface of the electrode to generate basic Zinc Sulfate (ZSH) due to the change of pH, and simultaneously, the product MnOOH of the proton solid phase reaction can occur the disproportionation reaction to dissolve, so that a great amount of Mn is dissolved in the electrolyte 2+ . Thus, during subsequent reversible charging and discharging, the above-described basic Zinc Sulfate (ZSH) assisted deposition dissolution reaction will occur at the electrode surface. Clearly, the discovery of the basic Zinc Sulfate (ZSH) assisted deposition dissolution mechanism, as distinguished completely from the description of the conventional ion intercalation/deintercalation energy storage mechanism, has led to a reconsideration and adjustment in the direction of research for sulfate-based aqueous rechargeable zinc-manganese cells.
Based on the above proposed basic Zinc Sulfate (ZSH) assisted deposition dissolution mechanism, a neutral aqueous rechargeable zinc-manganese battery (MnO free) was developed in recent research 2 Positive electrode), namely basic Zinc Sulfate (ZSH), can induce basic sulfur to generate on the surface of the electrode in a sulfate-based electrolyteAny one of zinc oxide, magnesium oxide and calcium oxide deposited by Zinc (ZSH) is taken as a battery anode, and manganese oxide is totally Mn-enriched 2+ Is added into the electrolyte, and the metal zinc is a negative electrode. The battery assembly method reduces the essence of the neutral water system zinc-manganese battery, and is more beneficial to realizing large-scale application. However, despite the MnO-free development 2 The specific capacity of the positive electrode has certain advantages, but the severe change of the surface electrode structure leads to poor cycle stability, so that the further application of the positive electrode still faces challenges.
Disclosure of Invention
In view of the above, an object of the present invention is to provide an electrolyte additive for improving the stability of a neutral aqueous rechargeable zinc-manganese battery; the invention also aims to provide the application of the electrolyte additive for improving the stability of the neutral water system rechargeable zinc-manganese battery in improving the stability of the neutral water system rechargeable zinc-manganese battery; the invention also aims to provide the electrolyte for improving the stability of the neutral water system rechargeable zinc-manganese battery.
In order to achieve the purpose, the invention provides the following technical scheme:
1. an electrolyte additive for improving the stability of a neutral water system rechargeable zinc-manganese battery, wherein the electrolyte additive in the neutral water system rechargeable zinc-manganese battery is water-soluble PO containing 4 3- The compound of (1).
Preferably, PO in the electrolyte additive 4 3- The concentration of (A) is 0.0001-0.5 mol/L.
Preferably, the PO comprises 4 3- The compound of (b) is Mn (H) 2 PO 4 ) 2 、Zn(H 2 PO 4 ) 2 、NaH 2 PO 4 、Na 2 HPO 4 、Na 3 PO 4 、 KH 2 PO 4 、K 2 HPO 4 、K 3 PO 4 、NH 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 Or (NH) 4 ) 3 PO 4 Any one or more of them.
Preferably, the positive electrode in the neutral water system rechargeable zinc-manganese battery is prepared according to the following method: mixing the positive active material, the conductive agent and the binder, dissolving in a solvent, grinding to obtain uniform slurry, then uniformly coating the uniform slurry on the surface of a smooth and clean positive current collector, and drying to obtain the positive electrode of the neutral water system rechargeable zinc-manganese battery.
Further preferably, the positive active material is any one or more of manganese oxide, basic zinc sulfate, zinc oxide, magnesium oxide or calcium oxide;
the mass ratio of the positive electrode active material to the conductive agent to the binder is (9.1);
the mass ratio of the total mass of the positive electrode active material, the conductive agent and the binder after mixing to the solvent is 1.
Further preferably, the conductive agent is any one or more of acetylene black, ketjen black, conductive carbon black (Super P), carbon nanotubes or graphene; the binder is any one or more of polyvinylidene fluoride (PVDF), sodium alginate, sodium carboxymethylcellulose, polytetrafluoroethylene or styrene butadiene rubber; the positive current collector is any one of copper foil, aluminum foil, titanium foil, steel wire mesh, nickel mesh, carbon cloth or carbon felt; the solvent is any one or more of azomethyl pyrrolidone, methanol, ethanol or water.
More preferably, the negative electrode in the neutral water system rechargeable zinc-manganese battery is any one of metal zinc foil or zinc powder;
the diaphragm in the neutral water system rechargeable zinc-manganese dioxide battery is any one of glass fiber paper, non-woven fabric or filter paper.
2. The electrolyte additive is applied to improving the stability of the neutral water system rechargeable zinc-manganese battery.
3. The electrolyte for improving the stability of the neutral water system rechargeable zinc-manganese battery is characterized by comprising the electrolyte additive;
the electrolyte also comprises a mixed aqueous solution formed by zinc sulfate and manganese sulfate.
Preferably, the concentration of zinc sulfate in the mixed water solution is 0.01-4 mol/L, and the concentration of manganese sulfate is 0.01-4 mol/L.
The invention has the beneficial effects that: the invention discloses an electrolyte additive for improving the stability of a neutral water system rechargeable zinc-manganese battery, which contains PO 4 3- The compound of (A) containing PO 4 3- The compound as an electrolyte additive is green, cheap and pollution-free, and can effectively improve the cycle stability of a neutral water system rechargeable zinc-manganese battery under the condition of not changing the charging and discharging behaviors. By further characterization, it can be found that the PO contains 4 3- PO in the compound of (1) 4 3- Can form stable Zn on the surface of the positive electrode of the neutral water system rechargeable zinc-manganese battery 3 (PO 4 ) 2 ·4H 2 The O phase can not only stabilize the electrode structure of the anode which is continuously deposited and dissolved in the charging and discharging process, but also induce basic Zinc Sulfate (ZSH) and a deposition product Zn x MnO(OH) 2 The stable nucleation and deposition are realized, so that the aim of improving the stability of the neutral water system rechargeable zinc-manganese battery is fulfilled.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For a better understanding of the objects, aspects and advantages of the present invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 shows that the electrolyte solution formed by the assembly of example 1 contains 0.002mol/L Mn (H) 2 PO 4 ) 2 Electrolyte additionMultiplying power performance (A) and 1Ag of neutral water system rechargeable zinc-manganese dioxide battery with agent under different current densities -1 A cyclic stability curve at current density (B);
FIG. 2 shows that the electrolyte solution formed by the assembly of example 2 contains 0.002mol/L of Mn (H) 2 PO 4 ) 2 Multiplying power performance (A) and 1Ag of neutral water system rechargeable zinc-manganese battery with electrolyte additive under different current densities -1 A cyclic stability curve at current density (B);
FIG. 3 is an in-situ XRD diffraction pattern of the zinc oxide electrode of the neutral aqueous rechargeable zinc-manganese battery assembled and formed in example 2 during charging and discharging processes;
FIG. 4 shows the electrolyte solution assembled in example 3 containing 0.002mol/LMn (H) 2 PO 4 ) 2 Multiplying power performance (A) and 1Ag of neutral water system rechargeable zinc-manganese battery with electrolyte additive under different current densities -1 A cyclic stability curve at current density (B);
FIG. 5 shows the electrolyte assembled in example 4 containing 0.004mol/L NaH 2 PO 4 The electrolyte additive is added into a neutral water system rechargeable zinc-manganese battery at 1Ag -1 A cyclical stability curve at current density;
FIG. 6 shows the rate capability (A) and 1Ag of the neutral aqueous rechargeable zinc-manganese dioxide cell assembled in comparative example 1 at different current densities -1 A cyclic stability curve at current density (B);
FIG. 7 shows the rate capability (A) and 1ag of the neutral aqueous rechargeable zinc-manganese dioxide cell assembled in comparative example 2 at different current densities -1 A cyclic stability curve at current density (B);
FIG. 8 shows the rate capability (A) and 1ag of the neutral aqueous rechargeable zinc-manganese dioxide cell assembled in comparative example 3 at different current densities -1 Cycling stability curve at current density (B).
Detailed Description
The following embodiments of the present invention are provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and embodiments may be combined with each other without conflict.
Example 1
An application of an electrolyte additive for improving the stability of a neutral water system rechargeable zinc-manganese battery in the water system rechargeable zinc-manganese battery specifically comprises the following steps:
(1) Preparing an electrolyte for improving the stability of a neutral water system rechargeable zinc-manganese battery: 0.002mol of Mn (H) 2 PO 4 ) 2 2mol of ZnSO 4 And 0.5mol of MnSO 4 Dissolving in 1L water to form water solution as electrolyte;
(2) Preparing a neutral aqueous rechargeable zinc-manganese battery positive electrode: mixing basic Zinc Sulfate (ZSH) powder serving as a positive electrode active material, ketjen black serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder according to a mass ratio of 7;
(3) And (3) taking the basic zinc sulfate electrode prepared in the step (2) as a positive electrode, taking a metal zinc foil with the thickness of 0.05mm as a battery negative electrode, taking glass fiber paper with the thickness of 1mm as a diaphragm, adding the mixed aqueous solution in the step (1) as an electrolyte according to the assembly of the positive electrode/the diaphragm/the negative electrode, and sealing and packaging.
Example 2
An application of an electrolyte additive for improving the stability of a neutral water system rechargeable zinc-manganese battery in the water system rechargeable zinc-manganese battery specifically comprises the following steps:
(1) Preparing an electrolyte for improving the stability of a neutral water system rechargeable zinc-manganese battery: 0.002mol of Mn (H) 2 PO 4 ) 2 ，2mol ZnSO 4 And 0.5mol of MnSO 4 The water solution formed by dissolving the electrolyte in 1L of water is the electrolyte.
(2) Preparing a neutral aqueous rechargeable zinc-manganese battery positive electrode: mixing zinc oxide (ZnO) powder serving as a positive electrode active material, ketjen black serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder according to a mass ratio of 7: 1, grinding to obtain uniform slurry, uniformly coating the uniform slurry on the surface of a smooth clean titanium foil with the thickness of 0.02mm, and drying in an oven at 80 ℃ to obtain a zinc oxide electrode which can be used as the positive electrode of a neutral water system rechargeable zinc-manganese battery;
(3) And (3) taking the zinc oxide electrode prepared in the step (2) as a positive electrode, a metal zinc foil with the thickness of 0.05mm as a battery negative electrode and glass fiber paper with the thickness of 1mm as a diaphragm, adding the mixed aqueous solution in the step (1) as an electrolyte according to the assembly of the positive electrode/the diaphragm/the negative electrode, and sealing and packaging.
Example 3
An application of an electrolyte additive for improving the stability of a neutral water system rechargeable zinc-manganese battery in the water system rechargeable zinc-manganese battery specifically comprises the following steps:
(1) Preparing an electrolyte for improving the stability of a neutral water system rechargeable zinc-manganese battery: 0.002mol of Mn (H) 2 PO 4 ) 2 ，2mol ZnSO 4 And 0.5mol of MnSO 4 The water solution formed by dissolving the electrolyte in 1L of water is the electrolyte.
(2) Preparing a neutral water system rechargeable zinc-manganese battery positive electrode: mixing magnesium oxide (MgO) powder serving as a positive electrode active material, ketjen black serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder according to a mass ratio of 7: 1, grinding to obtain uniform slurry, uniformly coating the uniform slurry on the surface of a smooth clean titanium foil with the thickness of 0.02mm, and drying in an oven at 80 ℃ to obtain a basic zinc sulfate electrode which can be used as the positive electrode of a neutral water system rechargeable zinc-manganese battery;
(3) And (3) taking the magnesium oxide electrode prepared in the step (2) as a positive electrode, taking a metal zinc foil with the thickness of 0.05mm as a battery negative electrode, taking glass fiber paper with the thickness of 1mm as a diaphragm, adding the mixed aqueous solution in the step (1) as an electrolyte according to the assembly of the positive electrode/the diaphragm/the negative electrode, and sealing and packaging.
Example 4
An application of an electrolyte additive for improving the stability of a neutral water system rechargeable zinc-manganese battery in the water system rechargeable zinc-manganese battery specifically comprises the following steps:
(1) Preparing an electrolyte for improving the stability of a neutral water system rechargeable zinc-manganese battery: adding 0.004mol of NaH 2 PO 4 ，2mol ZnSO 4 And 0.5mol of MnSO 4 Dissolving in 1L water to form water solution as electrolyte;
(2) Preparing a neutral aqueous rechargeable zinc-manganese battery positive electrode: mixing basic Zinc Sulfate (ZSH) powder serving as a positive electrode active material, ketjen black serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder according to a mass ratio of 7: 1, grinding to obtain uniform slurry, uniformly coating the uniform slurry on the surface of a smooth clean titanium foil with the thickness of 0.02mm, and drying in an oven at 80 ℃ to obtain a basic zinc sulfate electrode which can be used as the positive electrode of a neutral water system rechargeable zinc-manganese battery;
(3) And (3) taking the basic zinc sulfate electrode prepared in the step (2) as a positive electrode, a metal zinc foil with the thickness of 0.05mm as a battery negative electrode and glass fiber paper with the thickness of 1mm as a diaphragm, adding the mixed aqueous solution in the step (1) as an electrolyte according to the assembly of the positive electrode/the diaphragm/the negative electrode, and sealing and packaging.
Example 5
An application of an electrolyte additive for improving the stability of a neutral water system rechargeable zinc-manganese battery in the water system rechargeable zinc-manganese battery specifically comprises the following steps:
(1) Preparing an electrolyte for improving the stability of a neutral water system rechargeable zinc-manganese battery: 0.0001mol of Zn (H) 2 PO 4 ) 2 0.01mol of ZnSO 4 And 0.01mol of MnSO 4 Dissolving the electrolyte in 1L of water to form an aqueous solution, namely electrolyte;
(2) Preparing a neutral water system rechargeable zinc-manganese battery positive electrode: taking basic Zinc Sulfate (ZSH) powder as a positive electrode active material, acetylene black as a conductive agent and sodium alginate as a binder, mixing according to a mass ratio of 1;
(3) And (3) taking the basic zinc sulfate electrode prepared in the step (2) as a positive electrode, taking a metal zinc foil with the thickness of 0.05mm as a battery negative electrode, taking filter paper with the thickness of 1mm as a diaphragm, adding the mixed aqueous solution in the step (1) as an electrolyte according to the assembly of the positive electrode/the diaphragm/the negative electrode, and sealing and packaging.
Example 6
An application of an electrolyte additive for improving the stability of a neutral water system rechargeable zinc-manganese battery in the water system rechargeable zinc-manganese battery specifically comprises the following steps:
(1) Preparing an electrolyte for improving the stability of a neutral water system rechargeable zinc-manganese battery: 0.5mol of Na 2 HPO 4 4mol of ZnSO 4 And 4mol of MnSO 4 Dissolving the electrolyte in 1L of water to form an aqueous solution, namely electrolyte;
(2) Preparing a neutral aqueous rechargeable zinc-manganese battery positive electrode: taking basic Zinc Sulfate (ZSH) powder as a positive electrode active material, conductive carbon black (Super P) as a conductive agent and sodium carboxymethylcellulose as a binder, mixing according to a mass ratio of 9;
(3) And (3) taking the basic zinc sulfate electrode prepared in the step (2) as a positive electrode, taking a metal zinc foil with the thickness of 0.05mm as a battery negative electrode, taking a non-woven fabric with the thickness of 1mm as a diaphragm, adding the mixed aqueous solution in the step (1) as an electrolyte according to the assembly of the positive electrode/the diaphragm/the negative electrode, and sealing and packaging.
Comparative example 1
The difference from example 1 is that 0.002mol/L Mn (H) was not added 2 PO 4 ) 2 As an electrolyte additive, 2mol of ZnSO 4 And 0.5mol of MnSO 4 The water solution formed by dissolving the electrolyte in 1L of water is the electrolyte.
Comparative example 2
The difference from example 2 is that 0.002mol/L Mn (H) was not added 2 PO 4 ) 2 As an electrolyte additive, 2mol of ZnSO 4 And 0.5mol of MnSO 4 The water solution formed by dissolving the electrolyte in 1L of water is the electrolyte.
Comparative example 3
The difference from example 3 is that 0.002mol/L Mn (H) was not added 2 PO 4 ) 2 As an electrolyte additive, 2mol of ZnSO 4 And 0.5mol of MnSO 4 The water solution formed by dissolving the electrolyte in 1L of water is the electrolyte.
Performance test
FIG. 1 shows that the electrolyte solution prepared by the assembly of example 1 contains 0.002mol/LMn (H) 2 PO 4 ) 2 Multiplying power performance (A) and 1Ag of neutral water system rechargeable zinc-manganese battery with electrolyte additive under different current densities -1 Cycling stability curve at current density (B). As shown in FIG. 1A, PO was contained in the electrolyte 4 3- When the zinc hydroxide sulfate (ZSH) is used as a positive electrode active material to assemble a neutral water system rechargeable zinc-manganese battery, the neutral water system rechargeable zinc-manganese battery can exhibit reversible acting capacitance under different current densities, and the battery capacity can be kept stable under subsequent different current density tests and is 10 Ag except for the capacity exhibiting attenuation at the first 5 circles -1 The hourly capacity is 50mAh g -1 (ii) a As shown in FIG. 1B, the neutral aqueous rechargeable zinc-manganese dioxide cell in example 1 was found to have a mass of 1ag -1 After the current density is cycled for 200 circles, the capacity retention rate is 75 percent.
FIG. 2 shows an assembled electrolysis cell of example 2The solution contains 0.002mol/LMn (H) 2 PO 4 ) 2 Multiplying power performance (A) and 1Ag of neutral water system rechargeable zinc-manganese battery with electrolyte additive under different current densities -1 Cycling stability curve at current density (B). As can be seen from A in FIG. 2, PO was contained in the electrolyte solution 4 3- In addition, the neutral water system zinc-manganese battery formed by assembling zinc oxide (ZnO) as a positive electrode active material can show reversible acting capacitance under different current densities, and the battery capacity can be kept stable under subsequent different current density tests and 10 Ag under the condition that the capacity shows attenuation at the first 5 circles -1 The time capacity is about 100mAh g -1 . In FIG. 2B, it can be seen that the neutral water system rechargeable zinc-manganese dioxide cell in example 1 has a weight of 1ag -1 After the current density is cycled for 200 circles, the capacity is basically kept unchanged without any attenuation.
Fig. 3 is an in-situ XRD diffraction pattern of the zinc oxide electrode of the neutral aqueous rechargeable zinc-manganese battery assembled and formed in example 2 during charging and discharging. As can be seen from fig. 3, in the charging and discharging processes, the deposition and dissolution of basic Zinc Sulfate (ZSH) phase on the surface of the zinc oxide (ZnO) electrode meet the deposition-dissolution reversible energy storage reaction mechanism assisted by basic Zinc Sulfate (ZSH); meanwhile, stable Zn exists on the surface of the electrode 3 (PO 4 ) 2 ·4H 2 Formation of O phase, and thus stable Zn 3 (PO 4 ) 2 ·4H 2 The generation of O phase is the reason for the improved stability of the battery, and Zn 3 (PO 4 ) 2 ·4H 2 The O phase is derived from a composition containing 0.002mol/LMn (H) 2 PO 4 ) 2 So that water-soluble PO containing is added to a neutral water system rechargeable zinc-manganese battery 4 3- The compound can be used as an electrolyte additive to improve the stability of a neutral water system rechargeable zinc-manganese battery.
FIG. 4 shows the electrolyte solution assembled in example 3 containing 0.002mol/LMn (H) 2 PO 4 ) 2 Multiplying power performance (A) and 1Ag of neutral water system rechargeable zinc-manganese battery with electrolyte additive under different current densities -1 Cyclic stability curve at current densityAnd (B). As shown in FIG. 4A, PO was contained in the electrolyte 4 3- When, except at 10 ag -1 Next, a neutral water-based rechargeable zinc-manganese battery formed by assembling magnesium oxide (MgO) as a positive active material can exhibit reversible acting capacitance at different current densities; as shown in FIG. 4B, the neutral water rechargeable zinc-manganese battery of example 3 was operated at 1ag -1 After 200 cycles of current density, the capacity retention rate was 95%.
FIG. 5 shows the electrolyte solution assembled and formed in example 4 containing 0.004mol/L NaH 2 PO 4 The neutral water system rechargeable zinc-manganese battery of the electrolyte additive is 1Ag -1 Cycling stability curve at current density. As can be seen from FIG. 5, the additive of the neutral aqueous rechargeable zinc-manganese battery of example 4 is NaH 2 PO 4 When the zinc oxide is used as a positive electrode active material, the alkaline Zinc Sulfate (ZSH) is assembled into a neutral water system rechargeable zinc-manganese battery with the weight of 1Ag -1 After 200 cycles under the current density, the capacity retention rate is about 75 percent.
FIG. 6 shows the rate capability (A) and 1Ag of the neutral aqueous rechargeable zinc-manganese dioxide cell assembled in comparative example 1 at different current densities -1 Cycling stability curve at current density (B). As can be seen from A in FIG. 6, there is no PO 4 3- In the neutral water system rechargeable zinc-manganese battery of the electrolyte additive, the neutral water system rechargeable zinc-manganese battery formed by assembling basic Zinc Sulfate (ZSH) as a positive electrode active material shows rapid capacity decay under different current densities, and the capacity decay is 10 Ag -1 The capacity is only 23mAh g -1 (ii) a From B in FIG. 6, it can be seen that the neutral water system rechargeable zinc-manganese dioxide cell assembled in comparative example 1 has a weight of 1ag -1 After 200 cycles of current density, the battery capacity retention rate was 42%.
FIG. 7 shows the rate capability (A) and 1ag of the neutral aqueous rechargeable zinc-manganese dioxide cell assembled in comparative example 2 at different current densities -1 Cycling stability curve at current density (B). As can be seen from A in FIG. 7, there is no PO 4 3- Neutral water system chargeable zinc-manganese cell with electrolyte additive, zinc oxide (ZnO) as positive electrode active material assemblyThe formed neutral water system rechargeable zinc-manganese dioxide battery shows rapid capacity decay under different current densities, and the capacity decay is 10 Ag -1 At that time, the capacity is only 60 mAh g -1 (ii) a From FIG. 7B, it can be seen that the neutral water system rechargeable zinc-manganese dioxide cell assembled in comparative example 2 has a weight of 1ag -1 After 200 cycles of current density, the capacity retention rate of the battery is 73%.
FIG. 8 shows the rate capability (A) and 1ag of the neutral aqueous rechargeable zinc-manganese dioxide cell assembled in comparative example 3 at different current densities -1 Cycling stability curve at current density (B). As can be seen from A in FIG. 7, in the absence of PO 4 3- In the neutral water system rechargeable zinc-manganese battery of the electrolyte additive, magnesium oxide (MgO) is used as a positive electrode active material to assemble the neutral water system rechargeable zinc-manganese battery to form the neutral water system rechargeable zinc-manganese battery which shows rapid capacity decay under different current densities; as shown in FIG. 8B, the neutral water system rechargeable zinc-manganese dioxide cell assembled in comparative example 3 was found to have a mass of 1ag -1 After the current density is cycled for 200 circles, the capacity retention rate of the battery is 20%.
Similarly, the neutral water-based rechargeable zinc-manganese batteries assembled in examples 5 and 6 were tested in the same manner as described above, and the performance results were similar to those of the neutral water-based rechargeable zinc-manganese batteries of examples 1 to 4. In other embodiments, PO is included 4 3- The compound (b) may also be Na 3 PO 4 、KH 2 PO 4 、K 2 HPO 4 、K 3 PO 4 、NH 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 Or (NH) 4 ) 3 PO 4 Any one or more of the components are used as electrolyte additives to improve the stability of the neutral water system rechargeable zinc-manganese battery, the positive electrode in the neutral water system rechargeable zinc-manganese battery can be used as a positive electrode active material and can also be carbon nano tube or graphene, the binder in the neutral water system rechargeable zinc-manganese battery can be polytetrafluoroethylene or styrene butadiene rubber, the positive electrode current collector in the neutral water system rechargeable zinc-manganese battery can be any one of steel foil, steel wire mesh, nickel mesh, carbon cloth or carbon felt, and the neutral water system rechargeable zinc-manganese battery formed by assembly has the advantages of implementationThe neutral water system rechargeable zinc-manganese batteries of examples 1 to 4 have similar performances.
In summary, the invention discloses an electrolyte additive for improving the stability of a neutral water system rechargeable zinc-manganese battery, wherein the electrolyte additive contains PO 4 3- The compound of (2), the compound containing PO 4 3- The compound as an electrolyte additive is green, cheap and pollution-free, and can effectively improve the cycle stability of a neutral water system rechargeable zinc-manganese battery under the condition of not changing the charging and discharging behaviors. By further characterization, it can be found that the PO contains 4 3- PO in the compound of (1) 4 3- Can form stable Zn on the surface of the positive electrode of the neutral water system rechargeable zinc-manganese battery 3 (PO 4 ) 2 ·4H 2 The O phase can not only stabilize the electrode structure of the anode which is continuously deposited and dissolved in the charging and discharging process, but also induce basic Zinc Sulfate (ZSH) and a deposition product Zn x MnO(OH) 2 The stable nucleation and deposition are realized, so that the aim of improving the stability of the neutral water system rechargeable zinc-manganese battery is fulfilled.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. The electrolyte additive for improving the stability of the neutral water system rechargeable zinc-manganese battery is characterized in that the electrolyte additive in the neutral water system rechargeable zinc-manganese battery is water-soluble PO (phosphorus oxide) -containing electrolyte 4 3- The compound of (1).
2. The electrolyte additive of claim 1 wherein the electrolyte additive is PO 4 3- The concentration of (A) is 0.0001-0.5 mol/L.
3. The electrolyte additive according to claim 1, wherein the PO is contained 4 3- The compound of (A) is Mn (H) 2 PO 4 ) 2 、Zn(H 2 PO 4 ) 2 、NaH 2 PO 4 、Na 2 HPO 4 、Na 3 PO 4 、KH 2 PO 4 、K 2 HPO 4 、K 3 PO 4 、NH 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 Or (NH) 4 ) 3 PO 4 Any one or more of them.
4. The electrolyte additive according to claim 1 wherein the positive electrode in the neutral water system rechargeable zinc manganese battery is prepared as follows:
mixing the positive active material, the conductive agent and the binder, dissolving the mixture in a solvent, grinding the mixture to obtain uniform slurry, then uniformly coating the uniform slurry on the surface of a smooth and clean positive current collector, and drying the smooth and clean positive current collector to obtain the positive electrode of the neutral water system rechargeable zinc-manganese battery.
5. The electrolyte additive according to claim 4, wherein the positive electrode active material is any one or more of manganese oxide, basic zinc sulfate, zinc oxide, magnesium oxide or calcium oxide;
the mass ratio of the positive electrode active material to the conductive agent to the binder is 9.1 to 1;
the mass ratio of the total mass of the positive electrode active material, the conductive agent and the binder after mixing to the solvent is 1.
6. The electrolyte additive as claimed in claim 4, wherein the conductive agent is any one or more of acetylene black, ketjen black, conductive carbon black, carbon nanotubes or graphene; the binder is any one or more of polyvinylidene fluoride, sodium alginate, sodium carboxymethylcellulose, polytetrafluoroethylene or styrene butadiene rubber; the positive current collector is any one of copper foil, aluminum foil, titanium foil, steel wire mesh, nickel mesh, carbon cloth or carbon felt; the solvent is any one or more of azomethyl pyrrolidone, methanol, ethanol or water.
7. The electrolyte additive as claimed in claim 1, wherein the negative electrode of the neutral water system rechargeable zinc-manganese battery is any one of a metal zinc foil or zinc powder;
the diaphragm in the neutral water system rechargeable zinc-manganese dioxide battery is any one of glass fiber paper, non-woven fabric or filter paper.
8. Use of an electrolyte additive as claimed in any one of claims 1 to 7 to improve the stability of a neutral water system rechargeable zinc manganese cell.
9. An electrolyte for improving the stability of a neutral water system rechargeable zinc-manganese battery, which is characterized by comprising the electrolyte additive of any one of claims 1 to 7;
the electrolyte also comprises a mixed aqueous solution formed by zinc sulfate and manganese sulfate.
10. The electrolyte according to claim 9, wherein the concentration of zinc sulfate in the mixed aqueous solution is 0.01 to 4mol/L, and the concentration of manganese sulfate is 0.01 to 4mol/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115911248A (en) * | 2022-11-11 | 2023-04-04 | 天津大学 | Interface phase of manganese dioxide electrode of water-based zinc battery and preparation method thereof |
| CN117558998A (en) * | 2024-01-11 | 2024-02-13 | 吉林大学 | Modified zinc sulfate electrolyte, preparation method and application thereof, and water-system zinc ion symmetrical battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110085800A (en) * | 2019-04-24 | 2019-08-02 | 浙江浙能技术研究院有限公司 | Structure and preparation method of high-utilization-rate manganese oxide electrode of neutral zinc-manganese battery |
| CN110770949A (en) * | 2017-05-01 | 2020-02-07 | 赛伦能源公司 | Electrolyte additive for zinc metal electrodes |
| CN112234195A (en) * | 2019-07-15 | 2021-01-15 | 浙江大学 | Chargeable and dischargeable water system zinc ion full cell |
| CN112599865A (en) * | 2020-12-10 | 2021-04-02 | 浙江浙能中科储能科技有限公司 | Neutral chargeable zinc ion battery based on large-area-capacity manganese-free positive electrode and preparation method thereof |
-
2021
- 2021-12-15 CN CN202111534475.5A patent/CN114335661A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110770949A (en) * | 2017-05-01 | 2020-02-07 | 赛伦能源公司 | Electrolyte additive for zinc metal electrodes |
| CN110085800A (en) * | 2019-04-24 | 2019-08-02 | 浙江浙能技术研究院有限公司 | Structure and preparation method of high-utilization-rate manganese oxide electrode of neutral zinc-manganese battery |
| CN112234195A (en) * | 2019-07-15 | 2021-01-15 | 浙江大学 | Chargeable and dischargeable water system zinc ion full cell |
| CN112599865A (en) * | 2020-12-10 | 2021-04-02 | 浙江浙能中科储能科技有限公司 | Neutral chargeable zinc ion battery based on large-area-capacity manganese-free positive electrode and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115911248A (en) * | 2022-11-11 | 2023-04-04 | 天津大学 | Interface phase of manganese dioxide electrode of water-based zinc battery and preparation method thereof |
| CN117558998A (en) * | 2024-01-11 | 2024-02-13 | 吉林大学 | Modified zinc sulfate electrolyte, preparation method and application thereof, and water-system zinc ion symmetrical battery |
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