CN115911243A - Zinc cathode protective layer, zinc metal cathode, preparation method of zinc metal cathode and zinc metal battery - Google Patents
Zinc cathode protective layer, zinc metal cathode, preparation method of zinc metal cathode and zinc metal battery Download PDFInfo
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- CN115911243A CN115911243A CN202211421689.6A CN202211421689A CN115911243A CN 115911243 A CN115911243 A CN 115911243A CN 202211421689 A CN202211421689 A CN 202211421689A CN 115911243 A CN115911243 A CN 115911243A
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Abstract
The invention provides a zinc cathode protective layer which is prepared from zinc oxometallate and a high molecular polymer. The application also provides a zinc metal cathode and a preparation method thereof. The application also provides a zinc metal full cell. The zinc cathode protective layer provided by the application has the advantages of strong hydrogen evolution inhibition capability, abundant zinc-philic sites and a zinc metal protective layer with high zinc ion conductivity, can effectively inhibit water-induced side reactions and dendritic crystal growth, and is expected to be applied to industrial production. The zinc cathode protective layer is used for zinc metal symmetrical batteries and zinc | vanadium pentoxide (V2O5) In the full cell, the cell shows low polarization voltage, excellent rate capability and stable cycle performance, and has good practical prospect.
Description
Technical Field
The invention relates to the technical field of zinc metal batteries, in particular to a zinc cathode protective layer, a zinc metal cathode, a preparation method of the zinc cathode and a zinc metal battery.
Background
Zinc metal electrodeHas high volume specific capacity (5855 mAh cm) -3 ) And the redox potential is relatively low (-0.76V · vs · SHE), and the like, so the aqueous zinc metal battery taking the metal zinc as the negative electrode is expected to be applied to the large-scale energy storage field in the future. In addition, compared with the organic lithium ion battery widely applied at present, the water-based zinc metal battery has remarkable advantages in the aspects of safety, cost, environmental friendliness and the like.
However, metallic zinc is thermodynamically unstable in aqueous solution and is liable to undergo side reactions such as hydrogen evolution and self-corrosion, which cause irreversible loss of the electrolyte and the active material zinc. The large amount of hydrogen evolution can cause the swelling of the battery, so that the internal resistance of the battery is increased sharply. In addition, during charging, the uneven deposition of zinc metal tends to induce the growth of zinc dendrites, which pierce the separator, causing cell short circuit failure.
In order to improve the thermodynamic stability of zinc metal cathodes and simultaneously achieve uniform dendrite-free deposition of zinc metal, there are three strategies commonly used at present: optimizing electrolyte, constructing a three-dimensional current collector and designing an artificial protection layer; the artificial protective layer is designed as a simple and effective strategy, so that the side reaction can be obviously inhibited, and the uniform deposition of zinc can be regulated and controlled.
Generally, in an aqueous zinc metal battery, the artificial protective layer on the surface of the zinc metal negative electrode should have a high hydrogen evolution energy barrier, a strong zinc affinity, and a high ionic conductance. At present, most of reported artificial protective layers for modifying zinc metal fully meet all the requirements, the hydrogen evolution inhibition capacity is limited, the ionic conductivity is low, and the like, and the cycle life of the modified zinc metal electrode is improved to a limited extent, so that the practical application is difficult to meet. Therefore, there is a need to prepare and develop an artificial protection layer having high hydrogen evolution energy barrier, strong zinc affinity and high ionic conductance simultaneously for stabilizing the zinc metal negative electrode, so as to realize a long-life zinc metal battery.
Disclosure of Invention
The zinc cathode protective layer has strong capability of inhibiting hydrogen evolution, abundant zinc-philic sites and high ionic conductivity, can obviously inhibit side reactions and dendritic crystal growth, and realizes a zinc metal battery with ultra-long service life.
In view of the above, the present application provides a zinc negative electrode protection layer, which is prepared from a zinc oxometalate and a high molecular polymer.
Preferably, the zinc oxometallate salt has a hollow amorphous structure.
Preferably, the zinc oxometalate is selected from one of zinc metastannate, zinc stannate and zinc indate, and the high molecular polymer is selected from one or more of polyvinylidene fluoride, acrylic multipolymer and polyvinylidene fluoride-hexafluoropropylene; the mass ratio of the metal oxoacid zinc salt to the high molecular polymer is (0.5-2): 1.
the application also provides a zinc metal cathode, which consists of zinc metal and a zinc cathode protective layer compounded on the surface of the zinc metal, wherein the zinc cathode protective layer is the zinc cathode protective layer.
Preferably, the zinc negative electrode protective layer has a thickness of 5 to 50 μm.
The application also provides a preparation method of the zinc metal cathode, which comprises the following steps:
mixing a high molecular polymer with an organic solvent to obtain a polymer precursor solution;
mixing zinc oxometallate and the polymer precursor solution to obtain zinc metal negative electrode precursor slurry;
and coating the zinc metal cathode precursor slurry on the surface of zinc metal, and drying to obtain the zinc metal cathode.
Preferably, the mass fraction of the high molecular polymer in the polymer precursor solution is 5 to 20wt%, and the ratio of the zinc oxometalate to the high molecular polymer (0.5 to 2): 1.
preferably, the drying temperature is 30-100 ℃ and the drying time is 5-24 h.
The application also provides a zinc metal battery, which comprises a positive electrode, a negative electrode and electrolyte, and is characterized in that the negative electrode is the zinc metal negative electrode or the zinc metal negative electrode prepared by the preparation method of any one of claims 6 to 8.
Preferably, the material of the positive electrode is selected from one or more of vanadium pentoxide and manganese dioxide, and the electrolyte is selected from one or more of zinc sulfate aqueous solution and zinc trifluoromethanesulfonate aqueous solution.
The application provides a zinc cathode protective layer which is prepared from zinc oxometallate and a high molecular polymer. The zinc oxometalate salt of the zinc cathode protective layer provided by the application greatly enhances the capability of the protective layer in inhibiting hydrogen evolution due to the introduction of high hydrogen evolution overpotential metal elements; furthermore, the amorphous crystal structure enables the zinc oxometallate salt to provide more abundant zinc-philic sites, which is beneficial to inducing the uniform nucleation and precipitation of zinc ions; the hollow structure can obviously shorten the solid phase transmission distance of zinc ions and accelerate the transmission rate of the zinc ions, so that the zinc metal full cell assembled by the zinc cathode protective layer has excellent rate performance and long cycle stability.
Drawings
FIG. 1 shows hollow ZnSnO in example 1 of the present invention 3 Transmission electron microscope pictures of (a);
fig. 2 is a time-voltage curve of a modified zn symmetric cell of example 1 of the present invention;
FIG. 3 shows solid ZnSnO in example 2 of the present invention 3 Transmission electron microscope pictures of (a);
fig. 4 is a capacity-voltage curve of a modified zn symmetric cell in example 2 of the present invention;
fig. 5 is a time-voltage curve for a modified zinc/zinc symmetric cell and an unmodified zinc/zinc symmetric cell at different current densities according to example 3 of the present invention;
FIG. 6 shows modified Zn | V in example 4 of the present invention 2 O 5 Charge and discharge curves of the full cell.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Aiming at the problems of dendritic crystal growth, hydrogen evolution, corrosion and other side reactions of a zinc metal cathode in a water system zinc metal battery in the prior art, the zinc cathode protective layer is provided, and the zinc cathode protective layer has strong capability of inhibiting hydrogen evolution due to the introduction of zinc oxometallate; especially abundant zinc-philic sites and high ionic conductivity in the hollow amorphous metal oxozinc salt can obviously inhibit side reaction and dendritic crystal growth, and obtain the zinc metal battery with ultra-long service life. Specifically, the embodiment of the invention discloses a zinc cathode protective layer which is prepared from zinc oxometalate and a high molecular polymer.
In the zinc anode protective layer provided by the application, the zinc oxometallate is in a hollow amorphous structure and is selected from zinc metastannate (ZnSnO) 3 ) Zinc stannate (Zn) 2 SnO 4 ) And zinc (Zn) indium oxide 3 In 2 O 6 ) The zinc oxometallate salt has the following characteristics: the composition comprises Zn, O and high hydrogen evolution overpotential elements (such as Sn, in or Bi); amorphous materials are preferred in crystalline structure; geometrically, materials with a hollow structure are preferred. In a specific embodiment, the zinc oxometallate is selected from the group consisting of hollow amorphous ZnSnO 3 。
The invention is to the amorphous hollow ZnSnO 3 The source of (b) is not particularly limited and may be prepared according to a method well known to those skilled in the art, and in the present invention, the ZnSnO 3 Preferably prepared as follows: adding a zinc source and sodium citrate into a solvent, stirring at a certain temperature to dissolve the zinc source and the sodium citrate, then adding a mixed solution of a tin source and an alcohol solvent into the solution, continuously stirring strongly, then sequentially adding NaOH solutions with different concentrations into the solution to obtain a precursor, and finally annealing the precursor in an inert atmosphere for a certain time to obtain ZnSnO 3 . Other hollow amorphous zinc oxometalates can be prepared according to methods well known to those skilled in the art.
In the preparation process, the annealing temperature is 150-500 ℃, and more preferably 450 ℃; the annealing time is preferably 1 to 6 hours, more preferably 2 hours. The zinc source is preferably one or more of zinc acetate, zinc nitrate and zinc chloride, and is more preferably zinc chloride; the tin source is one or more of tin nitrate, tin acetate and tin chloride, and tin chloride is more preferably selected; the alcohol solvent is preferably one of methanol or ethanol, and more preferably ethanol.
The high molecular polymer is mainly used for forming a film and has a certain effect of delaying side reactions, and is selected from one of polyvinylidene fluoride (PVDF), acrylic multipolymer and polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP).
The mass ratio of the metal oxoacid zinc salt to the high molecular polymer is (0.5-2): 1, specifically, the mass ratio of the zinc oxometallate to the high molecular polymer is (0.8-1.5): 1. the zinc oxometallate salt with too high content can enhance the zinc ion conduction capability of the film layer, but the high molecular polymer with less content can cause the mechanical stability of the film layer to be weakened, thus causing the long cycle stability to be reduced; the high molecular polymer with too little zinc oxometallate content is correspondingly increased in proportion, so that the mechanical property of the film layer can be improved, but the zinc ion conduction rate is reduced, and the corresponding polarization voltage is increased.
The application also provides a zinc metal cathode, which consists of zinc metal and a zinc cathode protective layer compounded on the surface of the zinc metal, wherein the zinc cathode protective layer is the zinc cathode protective layer in the scheme.
In the present application, the thickness of the zinc negative electrode protection layer is 5 to 50 μm, and specifically, the thickness of the zinc negative electrode protection layer is 8 to 40 μm. The zinc negative electrode protective layer is too thin, so that the zinc ion conduction capability of the zinc negative electrode protective layer is enhanced, but the mechanical property is poor, and the capability of inhibiting dendritic crystal growth is weakened; if the thickness is too large, the mechanical properties are enhanced, but the rate of conducting zinc ions is reduced, concentration polarization is easily generated, and the polarization voltage is increased.
Further, the application provides a preparation method of the zinc metal negative electrode, which comprises the following steps:
mixing a high molecular polymer with an organic solvent to obtain a polymer precursor solution;
mixing zinc oxometallate and the polymer precursor solution to obtain zinc metal negative electrode precursor slurry;
and coating the zinc metal cathode precursor slurry on the surface of zinc metal, and drying to obtain the zinc cathode protective layer.
In the preparation process of the zinc metal cathode, firstly, mixing a high molecular polymer and an organic solvent to obtain a polymer precursor solution; in this process, the organic solvent may be selected from solvents that can dissolve the high molecular polymer, and specifically may be selected from N-methylpyrrolidone (NMP), acetone or N, N-Dimethylformamide (DMF), and more specifically acetone. The polymer is described above in detail, and is not described herein in detail. The mass fraction of the high molecular polymer in the polymer precursor solution is 5 to 20wt%, more specifically 8 to 12wt%.
Mixing zinc oxometallate and the polymer precursor solution to obtain zinc metal negative electrode precursor slurry; after obtaining the zinc metal negative electrode precursor slurry, coating the zinc metal negative electrode precursor slurry on the surface of zinc metal, and drying to obtain a zinc negative electrode protective layer; the coating may be carried out in a manner known to those skilled in the art, and the application is not particularly limited, and for example, a knife coating, a drop coating, or a spin coating may be used. The drying is vacuum drying. The drying time is 5-24 h, and specifically, the drying time is 10-18 h.
Further, the application provides a zinc metal battery, which is characterized in that the zinc metal cathode is applied to the zinc metal battery; specifically, the zinc metal battery comprises a negative electrode with a protective layer, a positive electrode and an electrolyte; the negative electrode is the zinc metal negative electrode in the scheme.
In the zinc metal battery provided herein, the material of the positive electrode is selected from one or more of vanadium pentoxide and manganese dioxide, and in the present application, the material of the positive electrode is selected from vanadium pentoxide, and the source of the vanadium pentoxide is not particularly limited, and can be prepared according to a method well known to those skilled in the art, and in the present invention, the V is 2 O 5 The preparation method is preferably as follows: will V 2 O 5 And oxalic acid addAdding the solution into deionized water, stirring at a certain temperature to dissolve the solution to obtain vanadyl oxalate, adding Graphene Oxide (GO) dispersion liquid into the solution, and then freezing and drying the solution; annealing in an inert atmosphere for a time to obtain V 2 O 5 @ rGO. The electrolyte is selected from one or more of zinc sulfate aqueous solution and zinc trifluoromethanesulfonate aqueous solution.
The zinc metal full cell provided by the invention can effectively inhibit hydrogen evolution side reaction and corrosion side reaction, promote uniform deposition of zinc ions, reduce internal resistance of the cell and improve long-cycle stability of the cell.
For further understanding of the present invention, the zinc negative electrode protection layer, the zinc metal electrode and the preparation method thereof provided by the present invention are described in detail below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
0.1g of amorphous hollow ZnSnO 3 1g of acrylic multipolymer precursor solution (the mass fraction is 10wt percent) is evenly mixed and stirred and is coated on the surface of the zinc foil by blade coating; drying in a vacuum oven at 60 ℃, and shearing to obtain the modified zinc metal electrode with the protective layer.
By 2M ZnSO 4 And (3) assembling the modified zinc metal electrode into a zinc | zinc button type symmetrical battery as an electrolyte. FIG. 1 is a hollow ZnSnO 3 The ZnSnO can be obviously observed in the transmission electron microscope picture 3 The square block is a hollow structure. FIG. 2 is a 2mA cm zinc/zinc cell of symmetry -2 As can be seen from the time-voltage curve under the current density, the polarization voltage of the zinc | zinc symmetrical cell is 26mV, and the cycle life exceeds 650h.
Example 2
0.1g of amorphous solid ZnSnO 3 1g of PVDF-HFP acetone solution (the mass fraction is 10 wt%) are uniformly mixed and stirred, and the mixture is blade-coated on the surface of a zinc foil; drying in a vacuum oven at 60 ℃, and shearing to obtain the modified zinc metal electrode with the protective layer.
By 2M ZnSO 4 And (3) assembling the modified zinc metal electrode plate into a zinc | zinc button type symmetrical battery as an electrolyte. FIG. 3 is a schematic view ofSolid ZnSnO 3 The ZnSnO can be obviously observed in the transmission electron microscope picture 3 The square block is of a solid structure. FIG. 4 is a zinc | zinc cell at 2mA cm -2 Current density of 2mAh cm -2 The voltage-capacity curve of (2) shows that the polarization voltage of the zinc | zinc cell after stabilization is 35mV.
Example 3
0.1g of amorphous hollow ZnSnO 3 1g of PVDF-HFP acetone solution (the mass fraction is 10 wt%) are uniformly mixed and stirred, and the mixture is blade-coated on the surface of a zinc foil; drying in a vacuum oven at 60 ℃, and shearing to obtain the modified zinc metal electrode with the protective layer.
By 2M ZnSO 4 And (3) assembling the modified zinc metal electrode plate into a zinc | zinc button type symmetrical battery as an electrolyte. FIG. 5 is a comparison of the rate performance of unmodified and modified zinc/zinc symmetric cells at 6.0mA cm -2 Under the current density of the battery, the rate performance of the unmodified and the modified symmetrical batteries is obviously superior to that of the unmodified symmetrical battery, wherein the voltage of the unmodified and the modified symmetrical batteries is respectively 122mV and 47 mV.
Example 4
0.7g of V 2 O 5 Mixing and grinding @ rGO, 0.2g of conductive carbon black and 0.1g of PVDF binder, uniformly stirring, and coating the mixture on a stainless steel foil; drying in a vacuum oven at 60 ℃, and shearing to obtain a positive plate; 0.1g of amorphous hollow ZnSnO 3 1g of PVDF-HFP acetone solution (the mass fraction is 10 wt%) are uniformly mixed and stirred, and the mixture is blade-coated on the surface of a zinc foil; drying in a vacuum oven at 60 ℃, and shearing to obtain the modified zinc metal cathode with the protective layer. By 3M ZnSO 4 Saturated V 2 O 5 Using the solution as electrolyte, assembling Zn | V 2 O 5 A battery. FIG. 6 is Zn | V 2 O 5 The charging and discharging curves of the battery under different current densities are shown in the figure, and the modified Zn | V is obtained under the current densities of 0.3, 0.5, 1, 3, 5 and 10A/g 2 O 5 The specific discharge capacity of the battery is 375, 319, 293, 275, 261 and 235mAh g in sequence -1 。
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A zinc cathode protective layer is prepared from zinc oxometallate and high-molecular polymer.
2. The zinc negative electrode protective layer of claim 1, wherein the zinc oxometalate salt is a hollow amorphous structure.
3. The zinc anode protective layer according to claim 1 or 2, wherein the zinc salt of a metal oxyacid is selected from one of zinc metastannate, zinc stannate and zinc indate, and the high molecular polymer is selected from one or more of polyvinylidene fluoride, acrylic multipolymer and polyvinylidene fluoride-hexafluoropropylene; the mass ratio of the metal oxoacid zinc salt to the high molecular polymer is (0.5-2): 1.
4. a zinc metal negative electrode, which consists of zinc metal and a zinc negative electrode protective layer compounded on the surface of the zinc metal, wherein the zinc negative electrode protective layer is the zinc negative electrode protective layer as claimed in any one of claims 1 to 3.
5. The zinc metal negative electrode of claim 4, wherein the zinc negative electrode protective layer has a thickness of 5 to 50 μm.
6. A preparation method of a zinc metal negative electrode comprises the following steps:
mixing a high molecular polymer with an organic solvent to obtain a polymer precursor solution;
mixing zinc oxometallate and the polymer precursor solution to obtain zinc metal negative electrode precursor slurry;
and coating the zinc metal cathode precursor slurry on the surface of zinc metal, and drying to obtain the zinc metal cathode.
7. The method according to claim 6, wherein the polymer precursor solution contains 5 to 20wt% of the high molecular polymer, and the ratio of the zinc oxometalate to the high molecular polymer is (0.5 to 2): 1.
8. the method according to claim 6, wherein the drying is carried out at a temperature of 30 to 100 ℃ for 5 to 24 hours.
9. A zinc metal battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the negative electrode is the zinc metal negative electrode according to any one of claims 4 to 5 or the zinc metal negative electrode prepared by the preparation method according to any one of claims 6 to 8.
10. The zinc-metal battery of claim 9, wherein the positive electrode material is selected from one or more of vanadium pentoxide and manganese dioxide, and the electrolyte is selected from one or more of aqueous zinc sulfate solution and aqueous zinc trifluoromethanesulfonate solution.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116504911A (en) * | 2023-06-25 | 2023-07-28 | 吉林大学 | Amorphous zinc oxide coating modified zinc anode, preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116504911A (en) * | 2023-06-25 | 2023-07-28 | 吉林大学 | Amorphous zinc oxide coating modified zinc anode, preparation method and application thereof |
| CN116504911B (en) * | 2023-06-25 | 2023-09-05 | 吉林大学 | Amorphous zinc oxide coating modified zinc anode, preparation method and application thereof |
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