Solid-state zinc ion battery device

Abstract

The utility model relates to a solid-state zinc ion battery device, which comprises a packaging shell, a zinc negative electrode, an ion selective interface coating, a composite solid electrolyte layer and a positive electrode material which are connected in sequence are arranged in the packaging shell; the zinc negative electrode comprises a conductive substrate, the conductive substrate is of a three-dimensional porous structure, the porosity of the three-dimensional porous structure is 50%-70%, the aperture of the three-dimensional porous structure is 10-100 microns, and the surface of the conductive substrate is uniformly covered with nano zinc particles. The conductive substrate with a three-dimensional porous structure is adopted as the zinc negative electrode, so that the local current density can be effectively reduced, the dendritic crystal growth problem is solved, the safety performance of the battery device is improved, the energy density of the battery device is remarkably improved by the composite solid electrolyte layer, and the contact interface between the composite solid electrolyte layer and the zinc negative electrode is improved. The ion selective interface coating is adopted to reduce the interface impedance, so that the interface stability is improved, and side reactions are reduced. The battery can be widely applied to the fields of intelligent energy storage, wearable equipment, electric vehicles and the like.

Description

TECHNICAL FIELD

[0001] The utility model relates to energy storage device technical field, concretely is a kind of solid-state zinc ion battery device. BACKGROUND

[0002] Due to the environmental pollution and energy crisis caused by traditional energy storage technology, people's demand for high energy density equipment is increasing, and lithium ion battery is widely used in commercial energy storage device due to its high efficiency, high voltage, long cycle life and other advantages, but due to high cost and many safety problems, which seriously hinder the large-scale application of lithium ion battery, so zinc ion battery is concerned due to its abundant natural resources and inherent safety.

[0003] Zinc ion battery has wide application prospect in the field of energy storage due to its abundant raw materials, environmental friendliness and low cost. However, the traditional zinc ion battery still has the following technical problems:

[0004] Zinc negative electrode is easy to produce dendrite in the process of charging and discharging, which causes short circuit and safety problem. UTILITY MODEL CONTENT

[0005] In view of the problems existing in the prior art, the purpose of the utility model is to provide a kind of solid-state zinc ion battery device, can effectively inhibit the growth of zinc dendrite, improve the safety performance of battery device.

[0006] In order to achieve the above purpose, the utility model adopts the following technical scheme:

[0007] A kind of solid-state zinc ion battery device, including packaging shell;Packaging shell is equipped with zinc negative electrode, ion selective interface coating, composite solid electrolyte layer and positive material connected in sequence in it;

[0008] Zinc negative electrode includes conductive substrate, and the conductive substrate is three-dimensional porous structure, and the porosity of three-dimensional porous structure is 50%-70%, and the pore size is 10-100 μm, and the surface of conductive substrate is uniformly covered with nano-zinc particles.

[0009] Further, the conductive substrate of three-dimensional porous structure is metal porous foam or three-dimensional carbon structure.

[0010] Further, the thickness of nano-zinc particles is 5-20 μm.

[0011] Further, the ion selective interface coating is Li3PO4 coating.

[0012] Further, the thickness of composite solid electrolyte layer is 20-50 μm, and the ionic conductivity is 1×10⁻³ S / cm.

[0013] Further, the positive material is manganese oxide or vanadium oxide.

[0014] Further, the surface of the positive electrode material is coated with a conductive polymer.

[0015] Further, the conductive polymer is a titanium oxide coating.

[0016] Further, the packaging shell is provided with a heat insulation layer, and the thickness of the heat insulation layer is 5-10 mm.

[0017] Further, the surface of the packaging shell is provided with a corrosion-resistant coating layer.

[0018] In general, the utility model has the following advantages:

[0019] The solid-state zinc ion battery device adopts the three-dimensional porous structure conductive substrate as the zinc negative electrode, the porosity of the three-dimensional porous structure is 50%-70%, the pore size is 10-100 mu m, the surface of the conductive substrate is uniformly covered with nano zinc particles, the local current density can be effectively reduced, the dendrite growth problem is fundamentally solved, the safety performance of the battery device is improved, and the battery can be widely applied to the fields of intelligent energy storage, wearable equipment and electric vehicles. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 It is a structure schematic view of the solid-state zinc ion battery device of the utility model.

[0021] Figure 2 It is a structure schematic view of the conductive substrate of the metal porous foam.

[0022] In the drawing:

[0023] 1-zinc negative electrode, 2-ion selective interface coating, 3-composite solid-state electrolyte layer, 4-positive electrode material, 5-packaging shell. DETAILED DESCRIPTION

[0024] The utility model will be further explained in detail as follows.

[0025] As shown in the drawing, Figure 1 A solid-state zinc ion battery device, comprising a lightweight and flexible packaging shell 5; the packaging shell 5 is provided with a zinc negative electrode 1, an ion selective interface coating 2, a composite solid-state electrolyte layer 3 and a positive electrode material 4 connected in sequence.

[0026] The zinc negative electrode 1 comprises a conductive substrate, the conductive substrate is a three-dimensional porous structure, the porosity of the three-dimensional porous structure is 50%-70%, the pore size is 10-100 mu m, and the surface of the conductive substrate is uniformly covered with nano zinc particles.

[0027] Preferably, as shown in the drawing, Figure 2As shown, the conductive substrate of the three-dimensional porous structure is a metal porous foam or a three-dimensional carbon structure, and the thickness of the nano-zinc particles is 5-20 pm, which can be adjusted according to actual application requirements to balance the capacity and cycle stability, effectively reduce the local current density, prevent dendrite growth, and improve the uniform deposition / stripping performance of zinc ions.

[0028] The composite solid electrolyte layer 3 has high ionic conductivity and excellent mechanical stability, and the composite solid electrolyte layer 3 of the prior art can be used, and in the present embodiment, PVDF-HFP is preferably used as a polymer matrix, and LLZO inorganic fillers with a particle size of 50 nm are added to prepare a thin film by a solvent evaporation method. The thickness of the electrolyte is controlled to be 30 pm, the ionic conductivity reaches 1x10⁻³ S / cm, and the energy density of the battery device is significantly improved.

[0029] At the contact interface between the composite solid electrolyte layer 3 and the zinc negative electrode 1, an ion-selective interface coating 2 (such as a Li3PO4 coating) is used to reduce the interface impedance, to improve the interface stability and reduce the side reaction.

[0030] The positive electrode material 4 uses manganese oxide or vanadium oxide, and the thickness is about 50 pm. The positive electrode material 4 is coated with a conductive polymer on the surface to further optimize the conductivity and interface compatibility. Preferably, the conductive polymer is a titanium oxide coating.

[0031] The packaging shell 5 of the battery device uses high-strength polymer or lightweight metal material to ensure the mechanical strength and sealing performance of the battery device, and an aerogel thermal insulation layer with a thickness of about 5 mm is arranged inside to improve the battery thermal management performance and prevent thermal runaway problems. The packaging method is vacuum hot-pressing packaging to ensure the internal airtightness.

[0032] Example One

[0033] The present embodiment provides a solid-state zinc ion battery device based on a three-dimensional porous structure negative electrode, which comprises a packaging shell 5, a zinc negative electrode 1, an ion-selective interface coating 2, a composite solid electrolyte layer 3 and a positive electrode material 4.

[0034] The zinc negative electrode 1 uses a nickel foam structure activated by acid washing, and the porosity is 60%, and a 10 pm thick zinc layer is uniformly deposited on the surface by electrochemical deposition. The positive electrode material 4 is modified MnO2, and the interface stability is further enhanced by a nano-TiO2 coating. The composite solid electrolyte layer 3 is a thin film made of PVDF-HFP and LLZO composite material, and the thickness is about 30 pm.

[0035] When the battery device is assembled, the positive and negative electrodes are tightly attached to the composite solid electrolyte layer 3, and then sealed in the packaging shell 5 by hot-pressing packaging technology. Test results show that the capacity retention rate reaches 95% after 200 cycles at a rate of 1.0 mA / cm².

[0036] Example Two

[0037] This example provides a solid-state zinc-ion battery device with carbon nanotube (CNT) negative electrode framework. The zinc negative electrode 1 adopts a carbon nanotube conductive network prepared by chemical vapor deposition method, and the surface of the network is plated with a zinc layer (thickness of about 2-5 μm) by electrochemical method.

[0038] The positive electrode material 4 adopts LiMn2O4, and the surface is coated with a polypyrrole (PPy) conductive coating. The composite solid electrolyte layer 3 is a PVDF-HFP / LLZO composite film with a thickness of about 25 μm, and contains 5% aluminum oxide to improve the ion conductivity.

[0039] In the high-rate charge and discharge test at 2.0 mA / cm², the battery device shows a coulomb efficiency of more than 97%, and still maintains excellent rate performance after 300 cycles.

[0040] Example Three

[0041] This example provides a solid-state zinc-ion battery with a gradient-pore nickel-copper alloy foam as the negative electrode. The inner layer of the nickel-copper alloy foam has a pore size of 20 μm, and the outer layer has a pore size of 100 μm. A zinc active layer with a thickness of 15 μm is formed by layer-by-layer electrochemical deposition.

[0042] The positive electrode material 4 is Mn3O4 doped with 3% aluminum, and a coating process can be used to optimize its conductivity. The composite solid electrolyte layer 3 is a PVDF-HFP composite film containing 5% graphite nanoparticles, with a thickness of 20 μm.

[0043] Under high-temperature conditions of 60°C, the capacity retention rate of the battery device reaches 92% after 250 cycles, showing excellent thermal stability.

[0044] Example Four

[0045] This example provides a negative electrode design for nickel foam treated by a magnesium oxide coating to reduce the hydrogen evolution side reaction during zinc deposition. The nickel foam is treated by acid washing and coated with a 1 μm thick magnesium oxide coating on the surface, and further electro-deposited with an 8 μm thick zinc active layer.

[0046] The positive electrode material 4 is MnO2 doped with magnesium. The composite solid electrolyte layer 3 adopts a PVDF-HFP and LLZO composite film, and is coated with a Li3BO3 protective layer on the surface, with a thickness of about 30 μm.

[0047] After 200 cycles at low temperature of -10°C, the capacity retention rate is as high as 90%, showing good low-temperature adaptability.

[0048] Example Five

[0049] The present embodiment provides a high-performance solid-state zinc ion battery based on graphite-reinforced negative electrode. The negative electrode is made of nickel foam, and the surface is electroplated with a zinc layer containing 5% graphite nanoparticles (thickness 10 μm).

[0050] The positive electrode material 4 is a manganese oxide and graphite composite material, with a graphite content of 10% to optimize the electrical conductivity. The composite solid electrolyte layer 3 uses a PVDF-HFP / LLZO composite film containing nano-aluminum oxide to improve the ionic conductivity.

[0051] Under normal temperature conditions, the battery device has a capacity retention rate of more than 93% after 500 cycles, and exhibits excellent electrochemical stability.

[0052] The solid-state zinc ion battery device has the advantages of high ionic conductivity, high interface stability, and long cycle life. The battery device is modularly designed, and can be connected in parallel or series in multiple units. The device has the advantages of high safety, high energy density, and long cycle life, and is suitable for use in the fields of smart home energy storage, wearable devices, and portable electronic devices.

[0053] The above embodiment is a preferred embodiment of the present application, but the embodiments of the present application are not limited by the above embodiment. Any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present application are equivalent replacement methods and are included in the protection scope of the present application.

Claims

1. A solid-state zinc-ion battery device, characterized by: The package shell comprises a zinc negative electrode, an ion-selective interface coating, a composite solid electrolyte layer and a positive electrode material connected in sequence. The zinc negative electrode comprises a conductive substrate, the conductive substrate is a three-dimensional porous structure, the porosity of the three-dimensional porous structure is 50%-70%, the pore size is 10-100 μm, and the surface of the conductive substrate is uniformly covered with nano-zinc particles. The conductive substrate of the three-dimensional porous structure is a metal porous foam or a three-dimensional carbon structure.

2. The solid-state zinc-ion battery device of claim 1, wherein: The thickness of the nano-zinc particles is 5-20 μm.

3. The solid-state zinc-ion battery device of claim 1, wherein: The ion-selective interface coating is a Li3PO4 coating.

4. The solid-state zinc-ion battery device of claim 1, wherein: The thickness of the composite solid electrolyte layer is 20-50 μm, and the ionic conductivity is 1×10⁻³ S / cm.

5. The solid-state zinc-ion battery device of claim 1, wherein: The positive electrode material is a manganese oxide or a vanadium oxide.

6. The solid-state zinc-ion battery device of claim 1, wherein: The surface of the positive electrode material is coated with a conductive polymer.

7. The solid-state zinc-ion battery device of claim 1, wherein: The conductive polymer is a titanium oxide coating.

8. The solid-state zinc-ion battery device of claim 7, wherein: The package shell is provided with a heat insulation layer, and the thickness of the heat insulation layer is 5-10 mm.

9. The solid-state zinc-ion battery device of claim 1, wherein: The surface of the package shell is provided with a corrosion-resistant coating layer.

10. The solid-state zinc-ion battery device of claim 1, wherein: ​

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