A solid ion conductor material and preparation method thereof

Abstract

The present invention relates to the field of ion conductor technology, and more particularly to a solid-state ion conductor material and a method for preparing the same. A method for preparing a solid-state ion conductor material comprises doping a two-dimensional layered structure material with a certain proportion of atoms as a raw material, self-assembling the doped two-dimensional layered structure material to obtain a self-assembled two-dimensional material; immersing the self-assembled two-dimensional material in a saturated aqueous solution of conductive ions to transport the conductive ions between the layers of the self-assembled two-dimensional material to form a dense stack of interlayer ions, thereby obtaining the desired solid-state ion conductor material; the doped atoms are non-metallic atoms; and the conductive ions are metal ions. This method for preparing a solid-state ion conductor material can produce a solid-state ion conductor material with high ionic conductivity.

Description

Technical field

[0002] [1] The present invention relates to the field of ion conductor technology, and in particular to a solid ion conductor material and a preparation method thereof. [Background Technology]

[0004] [2] Solid-state ion conductor materials are an important foundation for the construction of low-power information devices and high-performance energy devices in the future. For example, basic components of neuromorphic computing systems such as conductive bridge resistive switching devices and energy-signal coupling devices, as well as energy devices such as high-density all-solid-state batteries, all require the support of solid-state ion conductor materials with high ionic conductivity and high electronic insulation.

[0005] [3] At present, the ionic conductivity of alkaline earth metal ion conductor materials commonly used in devices is generally limited. Among them, the ionic conductivity of liquid ion conductors is basically lower than 10 -2 S / cm, while solid ion conductors are less than 10 -3 S / cm. Liquid ion conductors significantly restrict the integration of information devices and the safety of energy devices. Solid-state ion conductors have even lower ionic conductivity, resulting in low frequency characteristics of information devices and low power characteristics of energy devices. [Summary of the invention]

[0007] [4] In order to solve the problem of low ionic conductivity of solid-state ion conductors, the present invention provides a solid-state ion conductor material and a preparation method thereof.

[0008] [5] In order to solve the above technical problems, the present invention provides a method for preparing a solid-state ion conductor material, wherein a two-dimensional layered structure material is used as a raw material and a certain proportion of atoms are doped, and the two-dimensional layered structure material after doping is self-assembled to obtain a self-assembled two-dimensional material; the self-assembled two-dimensional material is immersed in a saturated aqueous solution of conductive ions to transport the conductive ions to the interlayers of the self-assembled two-dimensional material to form a dense stacking of interlayer ions, thereby obtaining the desired solid-state ion conductor material; the doped atoms are non-metal atoms; and the conductive ions are metal ions.

[0009] [6] Preferably, the doped atoms are fluorine atoms, nitrogen atoms, sulfur atoms or oxygen atoms, and the doping ratio thereof is 2-20%.

[0010] [7] The conductive ions are lithium ions, sodium ions, potassium ions, magnesium ions or zinc ions.

[0011] [8] Preferably, the self-assembly adopts a template method or a filtration method.

[0012] [9] Preferably, the doping is achieved by N doping at 1000 degrees Celsius in an NH3 atmosphere.

[0013]

[10] Preferably, the two-dimensional layered structure material is graphene oxide.

[0014]

[11] Preferably, the self-assembly is to dissolve the doped two-dimensional layered structure material in water to prepare an aqueous solution and then perform vacuum filtration.

[0015]

[12] Preferably, the vacuum filtration is carried out using anodized aluminum oxide as a filter membrane at 0-100°C and a vacuum degree of 0-50KPa; the concentration of the aqueous solution is 1-50mg / ml.

[0016]

[13] Preferably, the method for preparing the solid-state ion conductor material further includes intercalation before or after doping a certain proportion of atoms, and then performing the self-assembly after completing the doping and intercalation; the intercalation is to insert atoms, ions or small molecules into the interlayers of the two-dimensional layered structure material.

[0017]

[14] The present invention also provides a solid ion conductor material, which is prepared according to the above-mentioned method for preparing the solid ion conductor material.

[0018]

[15] Preferably, the interlayer spacing of the solid ion conductor material is 0.5-2 nm, and the ionic conductivity is 10 -2 -10 - 1 S / cm.

[0019]

[16] Compared with the prior art, the present invention provides a method for preparing a solid-state ion conductor material. By regulating the electron cloud structure of a two-dimensional layered structure material through element doping, the electron cloud structure of the two-dimensional layered structure material is reduced, that is, the resistance of the surrounding environment of the ion channel to ion transport is effectively reduced. Self-assembly can well achieve the high order of the two-dimensional material, and by introducing pre-sequence heteroatoms, the interlayer spacing can be effectively regulated. Thus, a solid-state ion conductor material with high ionic conductivity can be obtained.

[0020]

[17] The present invention also provides a solid ion conductor material, the ion conductivity of which can reach 10 -2 -10 -1 S / cm.

Brief Description of the Drawings

[0022]

[18] Figure 1 It is a schematic structural diagram of the solid-state ion conductor material provided by the present invention. [Specific implementation method]

[0024]

[19] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and implementation examples. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0025]

[20] See Figure 1 The first embodiment of the present invention provides a method for preparing a solid-state ion conductor material, which comprises doping a two-dimensional layered structure material with a certain proportion of atoms as a raw material, and self-assembling the doped two-dimensional layered structure material to obtain a self-assembled two-dimensional material; immersing the self-assembled two-dimensional material in a saturated aqueous solution of conductive ions to transport the conductive ions to the interlayers of the self-assembled two-dimensional material to form a dense stacking of interlayer ions, thereby obtaining the desired solid-state ion conductor material; the doped atoms are non-metal atoms; and the conductive ions are metal ions.

[0026]

[21] The preparation method of the solid-state ion conductor material regulates the electron cloud structure of the two-dimensional layered structure material by element doping, thereby reducing its force on ions, that is, effectively reducing the resistance of the surrounding environment of the ion channel to ion transport; self-assembly can well achieve the high order of the two-dimensional material, and through the introduction of pre-sequence heteroatoms, it can achieve effective regulation of its interlayer spacing; thereby, a solid-state ion conductor material with high ionic conductivity can be obtained.

[0027]

[22] It can be understood that the present invention is based on a two-dimensional layered structure material, in which ion-conducting channels are formed between the layers. The ionic conductivity of solid-state ion conductor materials is mainly determined by two factors. One is the size of the ion transmission channel; the other is the resistance of the ion channel's surrounding environment to ion transport, which is essentially the force exerted on the ions by the electron cloud of the atoms / molecules / crystals that constitute the ion channel. In the present invention, the above two factors are well resolved, thereby producing a solid-state ion conductor material with high ionic conductivity.

[0028]

[23] The doped atoms are preferably fluorine atoms, nitrogen atoms, sulfur atoms, or oxygen atoms, more preferably nitrogen atoms; the doping ratio is preferably 2-20%, more preferably 3-5%. By determining the doping element and doping ratio, the effect of regulating the electron cloud structure and interlayer spacing of the two-dimensional layered structure material is ensured.

[0029]

[24] Preferably, the doping is performed by a high temperature reaction or a liquid phase reaction. In some specific embodiments, N doping is performed at 1000 degrees Celsius in an NH3 atmosphere.

[0030]

[25] The conductive ions are preferably lithium ions, sodium ions, potassium ions, magnesium ions or zinc ions.

[0031]

[26] The self-assembly can be performed by a template method or a filtration method; for example, the self-assembly can be performed by filtration of an aqueous solution of a two-dimensional layered structure material.

[0032]

[27] The transport of conductive ions can be carried out by an immersion method or an electric field control method. Furthermore, the transport of conductive ions is carried out by immersing the self-assembled two-dimensional material in a saturated aqueous solution of the conductive ions. Specifically, the self-assembled two-dimensional material can be immersed in an aqueous solution of LiCl to achieve spontaneous diffusion between ion layers and dense accumulation of conductive ions between the two-dimensional material layers. The electric field control method can specifically be to apply a gate voltage to the two-dimensional material to control its interlayer spacing and charge state, thereby achieving spontaneous entry of conductive ions.

[0033]

[28] The two-dimensional layered structure material may be graphene oxide, boron nitride, MXene or a hybrid structure thereof. Preferably, the two-dimensional layered structure material is graphene oxide. The two-dimensional layered structure material may be purchased directly or prepared. For example, nanosheets of the two-dimensional layered structure material may be synthesized by oxidation exfoliation, solvent exfoliation, direct synthesis, or the like. In some specific embodiments, graphene nanosheets may be obtained by Hummer oxidation.

[0034]

[29] When the two-dimensional layered structure material is graphene oxide, preferably, the self-assembly is performed by dissolving the doped two-dimensional layered structure material in water to prepare an aqueous solution and then vacuum filtering the solution. Furthermore, the vacuum filtration is performed using anodized aluminum oxide as a filter membrane at 0-100°C and a vacuum degree of 0-50 kPa; the concentration of the aqueous solution is 1-50 mg / ml.

[0035]

[30] In some preferred embodiments, the method for preparing the solid-state ion conductor material further includes intercalation before or after doping a certain proportion of atoms, and the self-assembly is performed after the doping and intercalation are completed; the intercalation is to insert atoms, ions or small molecules into the interlayers of the two-dimensional layered structure material. By inserting atoms, ions or small molecules into the interlayers of the two-dimensional layered structure material, the interlayer spacing and electron cloud structure of the graphene oxide can be further regulated, thereby improving the conductivity of the solid-state ion conductor material. The intercalated atoms can be sulfur atoms, the ions can be sodium ions or potassium ions, and the small molecules can be water.

[0036]

[31] Furthermore, intercalation of two-dimensional layered materials can be achieved through gas phase, electrochemical or liquid phase methods. For example, electrochemical methods can be used to introduce potassium ions between graphene layers to change the interlayer spacing.

[0037]

[32] It can be understood that the present invention is based on the method of doping atoms to change the interlayer spacing of the two-dimensional layered structure material, so that the interlayer spacing of the prepared solid-state ion conductor material is 0.5-2nm. It can also be regulated by inserting atoms, ions or small molecules into the interlayer of the two-dimensional layered structure material through intercalation.

[0038]

[33] See Figure 1 The second embodiment of the present invention provides a solid ion conductor material, which is prepared according to the preparation method of the solid ion conductor material in the first embodiment. Preferably, the interlayer spacing of the solid ion conductor material is 0.5-2nm, and the ionic conductivity is 10 -2 -10 -1 S / cm.

[0039]

[34] It should be understood that the references to "one embodiment" or "an embodiment" throughout the specification mean that the specific features, structures, or characteristics associated with the embodiment are included in at least one embodiment of the present invention. Therefore, the references to "in one embodiment" or "in an embodiment" throughout the specification do not necessarily refer to the same embodiment. In addition, these specific features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. Those skilled in the art should also be aware that the embodiments described in the specification are all optional embodiments, and the actions and modules involved are not necessarily required by the present invention.

[0040]

[35] The above is a detailed introduction to a solid ion conductor material and its preparation method disclosed in the embodiment of the present invention. Specific examples are used in this article to illustrate the principle and implementation method of the present invention. The description of the above embodiment is only used to help understand the method and core idea of ​​the present invention. At the same time, for those skilled in the art, according to the idea of ​​the present invention, there will be changes in the specific implementation method and application scope. In summary, the content of this specification should not be understood as a limitation of the present invention. Any modifications, equivalent replacements and improvements made within the principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a solid ion conductor material, characterized in that: Using a two-dimensional layered structure material as a raw material, doping a certain proportion of atoms, and self-assembling the doped two-dimensional layered structure material to obtain a self-assembled two-dimensional material; The self-assembled two-dimensional material is immersed in a saturated aqueous solution of conductive ions to transport the conductive ions to the interlayers of the self-assembled two-dimensional material to form a dense stacking of interlayer ions, thereby obtaining the desired solid-state ion conductor material; The doped atoms are non-metal atoms; and the conductive ions are metal ions.

2. The method for preparing a solid ion conductor material according to claim 1, wherein: The doping atoms are fluorine atoms, nitrogen atoms, sulfur atoms or oxygen atoms, and the doping ratio is 2-20%; The conductive ions are lithium ions, sodium ions, potassium ions, magnesium ions or zinc ions.

3. The method for preparing a solid ion conductor material according to claim 1, wherein: The self-assembly adopts a template method or a filtration method.

4. The method for preparing a solid ion conductor material according to claim 1, wherein: The doping is performed by N-doping at 1000 degrees Celsius in an NH 3 atmosphere.

5. The method for preparing a solid ion conductor material according to claim 1, wherein: The two-dimensional layered structure material is graphene oxide.

6. The method for preparing a solid ion conductor material according to claim 5, wherein: The self-assembly is performed by dissolving the doped two-dimensional layered structure material in water to prepare an aqueous solution and then vacuum filtering the solution.

7. The method for preparing a solid ion conductor material according to claim 6, wherein: The vacuum filtration is performed using anodized aluminum as a filter membrane at 0-100° C. and a vacuum degree of 0-50 KPa; the concentration of the aqueous solution is 1-50 mg / ml.

8. The method for preparing a solid ion conductor material according to claim 5, wherein: It also includes intercalation before or after doping a certain proportion of atoms, and then performing the self-assembly after completing the doping and intercalation; the intercalation is to insert atoms, ions or small molecules into the interlayers of the two-dimensional layered structure material.

9. A solid ion conductor material, characterized in that: The material is prepared according to the method for preparing the solid ion conductor material according to any one of claims 1 to 8.

10. The solid ion conductor material according to claim 9, wherein: Its interlayer spacing is 0.5-2nm and its ionic conductivity is 10 -2 -10 -1 S / cm.

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