CN113270648A - Metal ion induced aqueous zinc-manganese secondary battery - Google Patents
Metal ion induced aqueous zinc-manganese secondary battery Download PDFInfo
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- H—ELECTRICITY
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Abstract
The invention discloses a metal ion induced water system zinc-manganese secondary battery, which comprises a positive electrode current collector, a negative electrode and an electrolyte, wherein the electrolyte comprises water, manganese salt, cobalt salt, nickel salt, zinc salt and acid.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a metal ion induced aqueous zinc-manganese secondary battery.
Background
Due to the serious energy crisis and environmental pollution problems caused by the burning and consumption of traditional non-renewable fossil fuels, it is important to develop and utilize new clean renewable energy sources reasonably. Since clean energy is difficult to be directly incorporated into the power grid due to randomness and indirection, optimizing energy management and developing large-scale energy storage technology are urgent. The large-scale energy storage technology is considered as a strategic technology for supporting the popularization of renewable energy sources as an energy storage technology suitable for the scale of a power grid, and is expected to play an important role in the development and energy reformation of a power system.
Water system rechargeable MnO in various energy storage devices2the-Zn battery is receiving attention due to its high energy density, low cost, high safety and environmental friendliness and is expected to be applied to the field of large-scale energy storage. On the one hand, the cheap Zn negative electrode has a series of excellent electrochemical performances, such as low electrochemical reduction potential (-0.763V, vs SHE), high theoretical specific capacity (820mAh g)-1) And reversible Zn/Zn2+Deposition/dissolution reactions, etc. MnO of another aspect2As representative of Mn-based positive electrode materials, due to its low cost, high capacity and resistance to Zn2+The reversible intercalation/deintercalation reaction of (a) can be used for assembling an ideal positive electrode of an aqueous battery having a high energy density. However, MnO2The development of-Zn batteries is still hampered by problems such as low energy density, MnO2Poor conductivity, slow solid-state charge storage reactions, large overpotentials due to electrochemical polarization, and a tilt in voltage curve due to ion intercalation and phase transition processes, among others.
However, MnO was still hindered by low positive electrode capacity and slow reaction kinetics2The practical application and development of-Zn batteries, in particular, severely restrict their application in large-scale energy storage.
Disclosure of Invention
In view of the above, the present invention provides a metal ion-induced aqueous zinc-manganese secondary battery, which is intended to at least partially solve the above technical problems.
The invention provides a metal ion-induced aqueous zinc-manganese secondary battery, which comprises a positive electrode current collector, a negative electrode and an electrolyte, wherein the electrolyte comprises water, manganese salt, cobalt salt, nickel salt, zinc salt and acid.
According to the embodiment of the invention, the anion of manganese salt, the anion of cobalt salt, the anion of nickel salt and the anion of zinc salt are the same as the acid radical ion of acid.
According to the embodiment of the invention, the manganese salt comprises one or more of manganese sulfate, manganese chloride and manganese acetate; the cobalt salt comprises one or more of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate; the nickel salt comprises one or more of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate; the zinc salt comprises one or more of zinc sulfate, zinc chloride, zinc bromide and zinc iodide.
According to an embodiment of the invention, the acid comprises one or more of sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid.
According to an embodiment of the present invention, the positive electrode current collector includes one or more of a carbon felt, a graphite felt, a carbon cloth, a carbon paper, a carbon nanotube paper, a graphene film, a carbon nanotube film, a mesoporous carbon film, a conductive activated carbon film, a graphene net, a conductive graphite net, and a conductive graphite plate.
According to an embodiment of the present invention, the positive current collector further includes one or more of activated carbon, graphene, carbon nanotubes, polyaniline, mesoporous carbon, manganese dioxide, polypyrrole, carbon felt modified by one or more of manganese oxide and manganous oxide, graphite felt, carbon cloth, carbon paper, carbon nanotube paper, graphene film, carbon nanotube film, mesoporous carbon film, conductive activated carbon film, graphene mesh, conductive graphite mesh, and conductive graphite plate.
According to an embodiment of the invention, the negative electrode comprises one or more of a zinc foil, a zinc sheet, a zinc plate.
According to the embodiment of the invention, the concentration of the electrolyte comprises 0.1-1 g/mL.
According to the embodiment of the invention, the cations in the electrolyte comprise divalent manganese ions, divalent cobalt ions, divalent nickel ions, hydrogen ions and zinc ions, wherein the ion concentrations of the divalent manganese ions and the zinc ions comprise 10-210 mol/L; the ion concentration of hydrogen ions includes 10-510 mol/L; the ion concentrations of the divalent cobalt ions and the divalent nickel ions both comprise 10-3～10-1mol/L。
According to the embodiment of the invention, the anions in the electrolyte comprise hydroxide ions, manganese salt anions, cobalt salt anions, nickel salt anions, zinc salt anions and acid radical anions of acid, wherein the ion concentration of the hydroxide ions comprises 0.5-1.5 mol/L; the ion concentrations of the anion of the manganese salt, the anion of the cobalt salt, the anion of the nickel salt, the anion of the zinc salt and the anion of the acid radical of the acid all comprise 10-3～10mol/L。
The metal ion induced water system zinc-manganese secondary battery adopts the synergistic effect of cobalt ions and nickel ions to induce the electrolytic effect, and is favorable for carrying out electrochemical redox reaction because the cobalt element and the nickel element have multiple valence states. Because the atomic numbers of the cobalt element and the nickel element are close to the atomic number of the manganese element, the reaction process of co-deposition and co-dissolution of cobalt, nickel and manganese dioxide is facilitated, so that the conductivity of the co-deposited manganese dioxide on the battery anode is improved, and the battery can keep high rate performance and high coulombic efficiency under high capacity.
Meanwhile, due to the strong electronegativity of cobalt and nickel, manganese dioxide codeposited on the positive electrode of the battery has a more active electronic state, easier charge transfer and good conductivity, and effectively catalyzes the kinetics of the deposition and dissolution of the manganese dioxide.
Drawings
FIG. 1 schematically shows Co-Ni-MnO2V/deposition/dissolution reaction mechanism diagram of Zn cell (aqueous Zn-Mn secondary cell induced by metal ion);
FIG. 2 schematically shows MnO2Half cell and Co-Ni-MnO2The half cell is charged to 10mAh cm at a constant voltage of 1.13V-2The surface capacity of (1) is the relationship between the charging current response and the time;
FIG. 3 schematically shows MnO2Half cell and Co-Ni-MnO2Rate performance of the half cell at 1C and 10C discharge rates;
FIG. 4 schematically shows MnO2Half cell and Co-Ni-MnO2Testing the cycling stability of the half cell;
FIG. 5 schematically shows MnO2// Zn cell and Co-Ni-MnO2V/impedance spectrum of Zn cell;
FIG. 6 schematically shows MnO2// Zn cell and Co-Ni-MnO2v/Zn cell charge-discharge curve from low surface capacity to high surface capacity;
FIG. 7 schematically shows Co-Ni-MnO2Schematic diagram of the electrical connection of the Zn battery to the LED.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
In the process of implementing the present invention, it was found that the electrolyte added to the electrolyte of the zinc-manganese secondary battery in the related art is mainly a zinc salt, a manganese salt, or a potassium salt, etc. as a supporting electrolyte. The positive electrode capacity of the battery in the related art is low mainly due to the positive electrode MnO2Excessive deposition amountResulting in insufficient conductivity.
The invention provides a metal ion-induced aqueous zinc-manganese secondary battery, which comprises a positive electrode current collector, a negative electrode and an electrolyte, wherein the electrolyte comprises water, manganese salt, cobalt salt, nickel salt, zinc salt and acid.
In the embodiment of the invention, the electrolytic effect is induced by the synergistic action of the cobalt ions and the nickel ions, and the cobalt elements and the nickel elements have multiple valence states, so that the electrochemical oxidation-reduction reaction is favorably carried out. Because the atomic numbers of the cobalt element and the nickel element are close to the atomic number of the manganese element, the reaction process of co-deposition and co-dissolution of cobalt, nickel and manganese dioxide is facilitated, so that the conductivity of the co-deposited manganese dioxide on the battery anode is improved, and the battery can keep high rate performance and high coulombic efficiency under high capacity.
Meanwhile, due to the strong electronegativity of cobalt and nickel, manganese dioxide codeposited on the positive electrode of the battery has a more active electronic state, easier charge transfer and good conductivity, and effectively catalyzes the kinetics of the deposition and dissolution of the manganese dioxide.
According to the embodiment of the invention, the anion of manganese salt, the anion of cobalt salt, the anion of nickel salt and the anion of zinc salt are the same as the acid radical ion of acid.
In the embodiment of the invention, only one kind of anion exists in the electrolyte except hydroxide radicals, so that side reactions between other anions and cations are avoided.
According to the embodiment of the invention, the manganese salt comprises one or more of manganese sulfate, manganese chloride and manganese acetate; the cobalt salt comprises one or more of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate; the nickel salt comprises one or more of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate; the zinc salt comprises one or more of zinc sulfate, zinc chloride, zinc bromide and zinc iodide.
According to an embodiment of the invention, the acid comprises one or more of sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid.
According to an embodiment of the present invention, the positive electrode current collector includes one or more of a carbon felt, a graphite felt, a carbon cloth, a carbon paper, a carbon nanotube paper, a graphene film, a carbon nanotube film, a mesoporous carbon film, a conductive activated carbon film, a graphene net, a conductive graphite net, and a conductive graphite plate.
According to an embodiment of the present invention, the positive current collector further includes one or more of activated carbon, graphene, carbon nanotubes, polyaniline, mesoporous carbon, manganese dioxide, polypyrrole, carbon felt modified by one or more of manganese oxide and manganous oxide, graphite felt, carbon cloth, carbon paper, carbon nanotube paper, graphene film, carbon nanotube film, mesoporous carbon film, conductive activated carbon film, graphene mesh, conductive graphite mesh, and conductive graphite plate.
In the embodiment of the invention, the contact area between the electrolyte and the electrode can be increased by modifying the carbon felt, the graphite felt, the carbon cloth, the carbon paper, the carbon nanotube paper, the graphene film, the carbon nanotube film, the mesoporous carbon film, the conductive activated carbon film, the graphene net, the conductive graphite net and the conductive graphite plate by one or more of activated carbon, graphene, carbon nanotubes, polyaniline, mesoporous carbon, manganese dioxide, polypyrrole, manganese oxide and manganous manganic oxide.
According to an embodiment of the invention, the negative electrode comprises one or more of a zinc foil, a zinc sheet, a zinc plate.
According to the embodiment of the invention, the concentration of the electrolyte comprises 0.1-1 g/mL, such as 0.1g/mL, 0.2g/mL, 0.5g/mL, 0.8g/mL, 1 g/mL.
According to the embodiment of the invention, the cations in the electrolyte comprise divalent manganese ions, divalent cobalt ions, divalent nickel ions, hydrogen ions and zinc ions, wherein the ion concentrations of the divalent manganese ions and the zinc ions comprise 10-210mol/L, for example: 0.01mol/L, 0.05mol/L, 1mol/L, 5mol/L and 10 mol/L; the ion concentration of hydrogen ions includes 10-510mol/L, for example: 10-5mol/L、10-2mol/L, 1mol/L, 3mol/L, 5mol/L and 10 mol/L; the ion concentrations of the divalent cobalt ions and the divalent nickel ions both comprise 10-3～10-1mol/L, for example: 10-3mol/L、10-2mol/L、0.09mol/L、0.06mol/L、10- 1mol/L。
According to an embodiment of the present invention, anions are present in the electrolyteComprises hydroxide ions, manganese salt anions, cobalt salt anions, nickel salt anions, zinc salt anions and acid radical anions, wherein the ion concentration of the hydroxide ions comprises 0.5-1.5 mol/L, such as 0.5mol/L, 1mol/L and 1.5 mol/L; the ion concentrations of the anion of the manganese salt, the anion of the cobalt salt, the anion of the nickel salt, the anion of the zinc salt and the anion of the acid radical of the acid all comprise 10-310mol/L, for example: 10-3mol/L、10-2mol/L、0.09mol/L、0.06mol/L、1mol/L、4mol/L、6mol/L、10mol/L。
In the embodiment of the invention, the aqueous zinc-manganese secondary battery induced by metal ions adopts a single-liquid battery system, and a diaphragm is not required, so that the limitation of the battery performance on the ion conductivity of the battery diaphragm can be completely avoided, and the production cost of the battery is obviously reduced.
The present invention is described in further detail below in connection with electrochemical testing.
Example 1
The carbon felt is used as a positive current collector, the zinc foil is used as a negative electrode, 200mL of electrolyte is prepared, and the electrolyte is 1mol/L MnSO4+0.1mol/L H2SO4+0.09mol/L CoSO4+0.06mol/L NiSO4+1mol/L ZnSO4The mixed solution of (1). 20mL of the prepared electrolyte was poured into an electrolytic cell, a 2X 1cm (length. times. width) carbon felt was placed in the electrolytic cell containing the electrolyte so that the carbon felt was completely immersed in the electrolyte, and then the carbon felt was taken out with ceramic tweezers and held with platinum clips. Then, a 2X 1cm (length. times. width) piece of zinc foil was sandwiched by platinum clips. Inserting the two platinum clips on the cover of the electrolytic cell, screwing the cover and the electrolytic cell tightly, and adjusting the height of the platinum clips on the cover to ensure that the areas of the carbon felt and the zinc foil entering the electrolyte are both 1cm2. Aqueous zinc-manganese secondary battery (Co-Ni-MnO) for accomplishing metal ion induction2// Zn cell), the main electrode reactions of the cell are as follows:
and (3) positive electrode:
negative electrode:
the method comprises the following steps:
the working principle of the battery during charging and discharging is shown in figure 1, and the working mechanism of the negative electrode of the battery can be attributed to Zn in the charging and discharging processes2+Zn undergoes a reversible liquid/solid phase two electron transfer redox reaction. During charging, a large amount of Mn2+Ionic, small amount of Co2+Ions and Ni2+The ions deposit on the anode to form Co-Ni-MnO2And (3) a solid. Co ions and Ni ions in the electrolyte not only react with MnO in the charging process2Simultaneous deposition can also promote MnO to some extent2And (4) depositing. Solid Co-Ni-MnO during discharge2Gradually decompose to form Mn2+、Co2+And Ni2+And returned to the electrolyte.
Co-Ni-MnO in examples of the invention2the/Zn battery adopts double-electron transfer solid/liquid phase deposition dissolution reaction, and can effectively avoid the diffusion and phase inversion of ions in the crystal structure of the electrode material.
Example 2
Mixing carbon felt (1 cm)-2) As a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum electrode is used as a counter electrode, and the three electrodes are immersed in a solution prepared from 1mol/L MnSO4+0.1mol/L H2SO4+0.09mol/L CoSO4+0.06mol/L NiSO4In the electrolyte composed of the mixed solution, Co-Ni-MnO is assembled2Half-cells and tested for electrochemical performance.
Example 3
Mixing carbon felt (1 cm)-2) As a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum electrode is used as a counter electrode, and the three electrodes are immersed in a solution prepared from 1mol/L MnSO4+0.1mol/L H2SO4+ mixed solution to form MnO2Half cell and for itAnd carrying out electrochemical performance test.
MnO in example 32Half cell as a comparison with Co-Ni-MnO in example 22The half cells were individually electrochemically tested.
As shown in fig. 2, there is a large instantaneous current when the carbon felt is used as a current collector for constant voltage charging, and thus the current response of the battery is drastically reduced during the initial test of the half-cell. Co-Ni-MnO2The current response value of the half cell is higher than MnO2The current response value of the half cell can reach 10mAh cm in a shorter time-2Surface capacity of (B), indicating Co2+And Ni2+The introduction of ions is beneficial to promoting the MnO of the positive electrode2And (4) depositing.
As shown in FIG. 3, at a low discharge rate (1C, 10mAh cm)-2)，MnO2Half cell and Co-Ni-MnO2The discharge curve of the half cell shows an ultra-gentle plateau around about 1V. Co-Ni-MnO2Half cell at high discharge rate (10C, 100mAh cm)-2) The high discharging platform and the high coulombic efficiency are maintained, and the application advantage of the water-based battery in the large-scale energy storage field is highlighted.
As shown in FIG. 4, MnO was compared2Half cell and Co-Ni-MnO2The cycling stability of the half cell was found to be that the MnO2 half cell was at high surface capacity (10mAh cm)-2Discharge rate of 3C) can only cycle around 70 cycles, and Co-Ni-MnO2The half cell was able to cycle more cycles (about 120 cycles) under the same conditions, indicating Co-Ni-MnO2The electrode material has good cycling stability.
Example 4
The half cell prepared in example 2 is assembled into MnO by taking zinc foil as a negative electrode2// Zn cell.
Co-Ni-MnO prepared in example 12V/Zn cell with MnO prepared in example 42The electrochemical tests were carried out separately for Zn cells.
As shown in FIG. 5, Co-Ni-MnO2The internal resistance and charge transfer resistance of the/Zn cell were 5.87 Ω and 0.815 Ω, respectively (as shown in FIG. 5), both less than MnO2Internal resistance and charge transfer resistance of// Zn cell (9.26 Ω, 2.342 Ω), revealing Co-Ni-MnO2The electrolytic catalysis kinetics of (3) have higher electron mobility and electrochemical activity.
As shown in FIG. 6, with MnO2v/Zn cell comparison, Co-Ni-MnO2The coulombic efficiency and the discharge voltage platform of the Zn battery under large surface capacity are obviously improved and prolonged, and the Co-Ni-MnO is highlighted2Excellent electrochemical performance of the Zn cell at large area capacity.
Example 5
Co-Ni-MnO prepared in example 12V/Zn cell was charged to 10mAh cm at a constant voltage of 2.2V-2And then connected into the LED circuit (as shown in fig. 7), it was found that the LED lamp could be caused to light 266 s. Co-Ni-MnO2The excellent performance of the/Zn battery under large surface capacity is beneficial to the practical energy storage application, in particular to the application in large-scale power grid energy storage.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A metal ion-induced water system zinc-manganese secondary battery comprises a positive electrode current collector, a negative electrode and an electrolyte, wherein the electrolyte comprises water, manganese salt, cobalt salt, nickel salt, zinc salt and acid.
2. The secondary battery according to claim 1, wherein an anion of the manganese salt, an anion of the cobalt salt, an anion of the nickel salt, and an anion of the zinc salt are the same as an acid radical ion of the acid.
3. The secondary battery according to claim 1,
the manganese salt comprises one or more of manganese sulfate, manganese chloride and manganese acetate;
the cobalt salt comprises one or more of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate;
the nickel salt comprises one or more of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate;
the zinc salt comprises one or more of zinc sulfate, zinc chloride, zinc bromide and zinc iodide.
4. The secondary battery of claim 1, wherein the acid comprises one or more of sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid.
5. The secondary battery according to claim 1, wherein the positive electrode current collector comprises one or more of a carbon felt, a graphite felt, a carbon cloth, a carbon paper, a carbon nanotube paper, a graphene film, a carbon nanotube film, a mesoporous carbon film, a conductive activated carbon film, a graphene net, a conductive graphite net, and a conductive graphite plate.
6. The secondary battery according to claim 5, wherein the positive electrode current collector further comprises one or more of activated carbon, graphene, carbon nanotubes, polyaniline, mesoporous carbon, manganese dioxide, polypyrrole, manganese oxide, and manganous oxide modified carbon felt or more, graphite felt, carbon cloth, carbon paper, carbon nanotube paper, graphene film, carbon nanotube film, mesoporous carbon film, conductive activated carbon film, graphene mesh, conductive graphite sheet.
7. The secondary battery of claim 1, wherein the negative electrode comprises one or more of a zinc foil, a zinc sheet, and a zinc plate.
8. The secondary battery according to claim 1, wherein the electrolyte concentration comprises 0.1 to 1 g/mL.
9. The secondary battery according to claim 1, the cation in the electrolyte includes a divalent manganese ion, a divalent cobalt ion, a divalent nickel ion, a hydrogen ion, and a zinc ion, wherein,
the ion concentrations of the divalent manganese ion and the zinc ion are both 10-2～10mol/L；
The ion concentration of the hydrogen ions comprises 10-5～10mol/L；
The ion concentrations of the divalent cobalt ions and the divalent nickel ions both comprise 10-3～10-1mol/L。
10. The secondary battery according to claim 1, wherein anions in the electrolyte include hydroxide ions, anions of the manganese salt, anions of the cobalt salt, anions of the nickel salt, anions of the zinc salt, and acid anions of the acid, wherein,
the ion concentration of the hydroxide ions comprises 0.5-1.5 mol/L;
the ion concentrations of the anion of the manganese salt, the anion of the cobalt salt, the anion of the nickel salt, the anion of the zinc salt and the anion of the acid radical of the acid all comprise 10-3～10mol/L。
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| CN113937268A (en) * | 2021-10-11 | 2022-01-14 | 西北工业大学 | Fibrous flexible water-based zinc ion battery with ultra-long cycle life and preparation method thereof |
| WO2023234283A1 (en) * | 2022-06-01 | 2023-12-07 | 国立大学法人山口大学 | Aqueous electrolytic liquid and secondary battery |
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