Preparation method of one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank

Abstract

The invention discloses a method for preparing a one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank, comprising: obtaining a one-dimensional directional nano-reaction core precursor, and preparing a composite precursor solution based on the one-dimensional directional nano-reaction core precursor; performing one-dimensional directional nano-sizing and post-processing on the composite precursor solution to obtain a one-dimensional directional nano-reaction core; fixing the one-dimensional directional nano-reaction core on a one-dimensional gold needle; loading an alkali metal on a one-dimensional black wire, and depositing a solid electrolyte on the alkali metal; connecting the alkali metal deposited with the solid electrolyte with the one-dimensional gold needle fixed with the one-dimensional directional nano-reaction core to obtain a one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank. The directional nano-reaction tank has a simple preparation technology and can be prepared in large quantities; the diameter size, morphology, etc. of the directional nano-reaction tank are easy to control, which is conducive to observing samples with different mass thickness contrasts, thereby revealing the working mechanism of solid-state electrochemical energy storage devices.

Description

Technical Field

[0001] The invention relates to the field of preparation of directional nanometer reaction tanks, and in particular to a preparation method of a one-dimensional solid-state electrochemical in-situ TEM directional nanometer reaction tank. Background Art

[0002] In the context of energy crisis and environmental pollution, energy storage materials and their devices play a key role in the development of clean energy. However, the electrochemical reactions of energy storage materials during charging and discharging are relatively complex, especially for solid-state battery systems, where many reaction mechanisms are still unclear. In-situ transmission electron microscopy is a powerful technology that provides scientific researchers with a way to more directly correlate the microstructural changes of materials during reactions with external signals at the atomic scale and under conditions close to the real environment, thus achieving in-situ observation of the transformation process of materials during electrochemical reactions.

[0003] However, in situ transmission electron microscopy also has certain limitations: samples are not easy to find, reaction active sites are not easy to lock, contrast differences are large, and electron beam impact damage is large, etc., which makes it difficult to detect light elements such as lithium. Summary of the invention

[0004] In order to solve the problems existing in the above-mentioned prior art, the present invention provides a one-dimensional solid-state electrochemical in-situ TEM (in-situ transmission electron microscopy) directional nanoreaction tank preparation method, which can accurately realize in-situ research on the solid-state light element alkali metal negative electrode deposition / stripping electrochemical process, and at the same time can realize high-resolution observation of the solid-state electrochemical reaction process mechanism at the atomic scale.

[0005] In order to achieve the above technical objectives, the present invention provides a method for preparing a one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank, comprising:

[0006] S1, obtaining a one-dimensional oriented nanometer reaction core precursor, and preparing a composite precursor solution based on the one-dimensional oriented nanometer reaction core precursor;

[0007] S2, performing one-dimensional oriented nano-sizing and post-processing on the composite precursor solution to obtain a one-dimensional oriented nano-reaction core;

[0008] S3, fixing the one-dimensional oriented nano-reaction core on the one-dimensional gold needle;

[0009] S4, loading alkali metal onto a one-dimensional tungsten wire, and depositing a solid electrolyte on the alkali metal; connecting the alkali metal deposited with the solid electrolyte with the one-dimensional gold needle fixed with the one-dimensional directional nano-reaction core, to obtain a one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank.

[0010] Optionally, the precursor is a carbon precursor and contains dopants, which include but are not limited to oxide precursors, nitride precursors, carbide precursors and metal precursors.

[0011] Optionally, the preparation process of the composite precursor solution is:

[0012] The one-dimensional oriented nanometer reaction core precursor is obtained, and the one-dimensional oriented nanometer reaction core precursor is stirred and dissolved by a solvent to form the composite precursor solution, wherein the one-dimensional oriented nanometer reaction core precursor accounts for 9%-70% of the solvent in the composite precursor solution.

[0013] Optionally, the solvent includes but is not limited to N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide.

[0014] Optionally, the process of obtaining the one-dimensional oriented nano-reaction core precursor is:

[0015] The one-dimensional oriented nano reaction core precursor is obtained by using electrostatic spinning technology, a 2000-3000r / min high-speed roller or a parallel electrode collector with a distance of 1-2cm.

[0016] Optionally, the process of obtaining the one-dimensional oriented nano-reaction core is:

[0017] Performing one-dimensional oriented nano-sizing on the composite precursor solution, with an orientation degree greater than 80 degrees;

[0018] The material after the one-dimensional oriented nano-crystallization is post-processed, and the post-processing comprises: calcining and etching for 1-10 hours at 500-1000° C. in an inert atmosphere to obtain the one-dimensional oriented nano-reaction core.

[0019] Optionally, the one-dimensional oriented nano-reaction core is composed of oriented fibers or oriented tubes with a length of 50nm-10cm;

[0020] The diameter of the oriented fibers is 10-1000 nm;

[0021] The inner diameter of the oriented tube is 10-1000nm, and the tube wall thickness is 10-100nm;

[0022] The oriented fibers and the oriented tubes are provided with small holes on their upper surfaces, and the size of the small holes is 0.1-50 nm.

[0023] Optionally, the one-dimensional oriented nano-reaction core has a Young's modulus of 0.1-200 GPa and a tensile strength of 10 MPa-10 GPa.

[0024] Optionally, the solid electrolyte is a lithium metal battery solid electrolyte, a sodium metal battery solid electrolyte or a potassium metal battery solid electrolyte.

[0025] Optionally, the alkali metal is one, a combination of two or a combination of three of lithium, sodium and potassium.

[0026] The present invention has the following technical effects:

[0027] 1. The one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank prepared by the present invention has the advantages of high efficiency and rapid locking of reaction sites, high mechanical strength, and strong ability to resist external damage;

[0028] 2. The one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank prepared by the present invention can effectively reduce the damage of electron beam to the nucleation sample during the in-situ observation of solid-state electrochemical process, and the contrast is not much different from that of light elements; the electrochemical deposition / stripping process of light elements can be studied in situ;

[0029] 3. The one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank prepared by the present invention has a wide range of applications, can accurately realize in-situ research on solid-state electrochemical processes, and can realize high-resolution observation of the mechanism of solid-state electrochemical reaction processes at the atomic scale;

[0030] 4. The one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank preparation technology of the present invention is simple and can be prepared in large quantities. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0032] Figure 1 It is a flowchart of the method for preparing a one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank according to an embodiment of the present invention. DETAILED DESCRIPTION

[0033] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] like Figure 1 As shown, the present invention discloses a method for preparing a one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank, comprising:

[0035] S1, obtaining a one-dimensional oriented nanometer reaction core precursor, and preparing a composite precursor solution based on the one-dimensional oriented nanometer reaction core precursor;

[0036] The electrospinning technology is used to obtain a one-dimensional oriented nano-reaction core precursor using a 2000-3000r / min high-speed roller or a parallel electrode collector with a distance of 1-2cm. The one-dimensional oriented nano-reaction core precursor is a carbon precursor, and is doped with one or more of an oxide precursor, a nitride precursor, a carbide precursor and a metal precursor. The one-dimensional oriented nano-reaction precursor is stirred and dissolved by a solvent to form a composite precursor solution, in which the one-dimensional oriented nano-reaction core precursor accounts for 9%-70% of the solvent; wherein the solvent is a solvent that can dissolve the one-dimensional oriented nano-reaction core precursor, such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC) and dimethyl sulfoxide (DSMO).

[0037] S2, performing one-dimensional oriented nano-sizing and post-treatment on the composite precursor solution to obtain a one-dimensional oriented nano-reaction core;

[0038] First, the composite precursor solution is subjected to one-dimensional directional nano-crystallization, with a degree of orientation greater than 80 degrees, and then further calcined and etched at 500-1000°C in an inert atmosphere such as N2 or Ar for 1-10 hours to obtain a one-dimensional directional nano-reaction core with controllable components. The one-dimensional directional nano-reaction core is mainly composed of carbon, and is doped with one or more of oxides, nitrides, carbides, metals, etc., with a doping amount of 1%-30%.

[0039] The one-dimensional oriented nano-reaction core is composed of oriented fibers or oriented tubes with a length of 50nm-10cm, wherein the diameter of the oriented fibers is 10-1000nm; the inner diameter of the oriented tube is 10-1000nm, and the wall thickness is 10-100nm; the oriented fibers or oriented tubes have many small holes with a size of 0.1-50nm. The Young's modulus of the one-dimensional oriented nano-reaction core is 0.1-200GPa, and the tensile strength is 10MPa-10GPa.

[0040] One-dimensional directional nanoreaction core can effectively reduce the radiation damage of electron beam to nucleation samples by more than one time in observing solid-state electrochemical processes, weaken the penetration of high-energy electron beam to light elements, and protect the nucleation of light elements. In addition, the contrast between one-dimensional directional nanoreaction core and light elements is not much different, which is conducive to in-situ observation of nucleation process.

[0041] S3, using conductive resin silver paste to fix the prepared one-dimensional oriented nano-reaction core on the one-dimensional gold needle.

[0042] S4, loading the alkali metal onto the one-dimensional tungsten wire, and depositing the solid electrolyte on the alkali metal; connecting the alkali metal deposited with the solid electrolyte to the one-dimensional gold needle fixed with the one-dimensional directional nano-reaction core, to obtain a one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank;

[0043] The solid electrolyte can be lithium metal battery solid electrolyte, sodium metal battery solid electrolyte and potassium metal battery solid electrolyte according to the system being studied; the alkali metal can be lithium, sodium and potassium, or a combination of two or more according to the system being studied. The electrochemical process of solid lithium metal, sodium metal and potassium metal negative electrode deposition / stripping in the solid-state battery system can be studied in situ, and the solid-state electrochemical reaction process can be observed at the atomic scale with high resolution.

[0044] Example 1

[0045] S1, preparation of one-dimensional oriented nano-reaction core precursor: through the electrospinning equipment of the coaxial nozzle, the specific parameters of the electrospinning equipment are set as follows: the inner axis is mineral oil, the outer axis is PAN / PS / (CH3COO)2Zn mixed solution, the voltage is 18kV, the distance between the spinneret and the receiving device is 18cm, the feed flow rate of the electrospinning solution is 0.5mL / h, and a high-speed rotating drum receiver is used with a drum speed of 2500r / min for spinning to prepare PAN / PS / (CH3COO)2Zn@Oil one-dimensional oriented nano-core precursor.

[0046] Preparation of composite precursor solution: 1 g polyacrylonitrile (PAN, molecular weight = ~150 000), 0.1 g polystyrene (PS, molecular weight = ~280 000), 0.5 g (CH3COO)2Zn and 20 mL dimethylformamide were mixed and stirred at room temperature for a period of time to form a uniform composite precursor solution.

[0047] S2, the obtained PAN / PS / (CH3COO)2Zn@Oil one-dimensional oriented nano-reaction core precursor was calcined at 700 °C for 12 h in a nitrogen atmosphere, and mineral oil was etched, PAN was carbonized, and zinc acetate was converted to prepare ZnO nanoparticles with a diameter of 300 nm. x The modified porous one-dimensional directional nano-reaction core has a wall thickness of 50 to 100 nm, an inner diameter of 100 to 150 nm, and a pore size of 0.5 to 10 nm.

[0048] S3, using conductive resin silver paste to prepare ZnO x The modified one-dimensional directional nanoreaction core is fixed on the one-dimensional gold needle.

[0049] S4, lithium metal is loaded on the one-dimensional tungsten wire, and then the lithium-based solid electrolyte is deposited on the lithium metal. Finally, the one-dimensional gold needle with a one-dimensional directional nano-reaction core obtained in S3 is connected to the one-dimensional tungsten wire to form a one-dimensional solid-state electrochemical in-situ TEM directional ZnO x Modified carbon-based nanoreactor; experiments were performed using in situ TEM equipment to observe the deposition and stripping of lithium metal in solid-state electrochemical devices.

[0050] Example 2

[0051] S1, preparation of one-dimensional oriented nano-reaction core precursor: through the electrospinning equipment of the coaxial nozzle, the specific parameters of the electrospinning equipment are set as follows: the inner axis is mineral oil, the outer axis is PAN / PMMA / (CH3COO)2Zn mixed liquid, the voltage is 20kV, the distance between the spinneret and the receiving device is 18cm, the feed flow rate of the electrospinning liquid is 0.5mL / h, and the PAN / PMMA / (CH3COO)2Zn@Oil oriented nano-core precursor is prepared by spinning using parallel electrode receivers at a distance of 2cm.

[0052] Preparation of composite precursor solution: 1 g polyacrylonitrile (PAN, molecular weight = ~150 000), 0.3 g polymethyl methacrylate (PMMA, molecular weight = ~60 000), 0.5 g (CH3COO)2Zn and 20 mL dimethylformamide were mixed and stirred at room temperature for a period of time to form a uniform composite precursor solution.

[0053] S2, the obtained PAN / PMMA / (CH3COO)2Zn@Oil one-dimensional oriented nano-reaction core precursor was calcined at 700 °C in a nitrogen atmosphere for 12 h, and the mineral oil and PMMA were etched, PAN was carbonized, and zinc acetate was converted to prepare ZnO nanoparticles with a diameter of 150-250 nm. x The modified porous one-dimensional directional nano-reaction core has a wall thickness of 50 to 100 nm, an inner diameter of 100 to 150 nm, and a pore size of 1 to 20 nm.

[0054] S3, using conductive resin silver paste to prepare ZnO x The modified one-dimensional directional nanoreaction core is fixed on the one-dimensional gold needle.

[0055] S4, sodium metal is loaded on a one-dimensional tungsten wire, and then a sodium-based solid electrolyte is deposited on the sodium metal. Finally, the one-dimensional gold needle with a one-dimensional directional nano-reaction core obtained in S3 is connected to the one-dimensional tungsten wire to form a one-dimensional solid-state electrochemical in-situ TEM directional ZnO x Modified carbon-based nanoreactor; experiments were performed using in situ TEM equipment to observe the deposition and stripping of sodium metal in solid-state electrochemical devices.

[0056] Example 3

[0057] S1, preparation of one-dimensional oriented nano-reaction core precursor: through a single-axis nozzle electrospinning device, the specific parameters of the electrospinning device are set as follows: voltage of 25 kV, distance between the spinneret and the receiving device of 18 cm, feed flow rate of the electrospinning liquid of 0.4 mL / h, and a high-speed rotating drum receiver with a drum speed of 3000 r / min for spinning to prepare PAN / PMMA / AgNO3 oriented nano-core precursor.

[0058] Preparation of composite precursor solution: 1 g polyacrylonitrile (PAN, molecular weight = ~150 000), 1 g polymethyl methacrylate (PMMA, molecular weight = ~60 000)), 1 g silver nitrate and 40 mL dimethylformamide were mixed and stirred at room temperature for a period of time to form a uniform composite precursor solution.

[0059] S2, calcining the obtained PAN / PMMA / AgNO3 one-dimensional oriented nano-reaction core precursor under nitrogen atmosphere at 700°C for 12h, decomposing PMMA, carbonizing PAN and converting AgNO3 to prepare a porous one-dimensional oriented nano-reaction core modified with Ag nanoparticles. The oriented fiber diameter of the nano-reaction core is 100-200nm, the Ag nanoparticles are 1-10nm, and the pore size on the fiber is 1-20nm.

[0060] S3, the prepared Ag nanoparticle-modified porous one-dimensional oriented nanoreaction core is fixed on the one-dimensional gold needle using conductive resin silver paste.

[0061] S4, sodium metal is loaded on a one-dimensional tungsten wire, and then a sodium-based solid electrolyte is deposited on the sodium metal. Finally, the one-dimensional gold needle with a one-dimensional directional nanoreaction core fixed thereon obtained in S3 is connected to the one-dimensional tungsten wire to form a one-dimensional solid-state electrochemical in-situ TEM directional Ag-modified carbon-based nanoreaction tank; experiments are carried out using in-situ TEM equipment to observe the deposition and stripping of sodium metal in solid-state electrochemical devices.

[0062] Example 4

[0063] S1, preparation of one-dimensional oriented nano-reaction core precursor: through a single-axis nozzle electrospinning device, the specific parameters of the electrospinning device are set as follows: voltage of 30 kV, distance between the spinneret and the receiving device of 20 cm, feed flow rate of the electrospinning liquid of 0.5 mL / h, and use parallel electrode receivers at a distance of 2 cm to prepare PAN / PS / AgNO3 oriented nano-core precursor by spinning.

[0064] Preparation of composite precursor solution: 1 g polyacrylonitrile (PAN, molecular weight = ˜150 000), 1 g PS, 1 g silver nitrate and 40 mL dimethylformamide were mixed and stirred at room temperature for a period of time to form a uniform composite precursor solution.

[0065] S2, calcining the obtained PAN / PS / AgNO3 one-dimensional oriented nano-reaction core precursor at 700°C in a nitrogen atmosphere for 12 hours, decomposing PS, carbonizing PAN and converting AgNO3 to prepare a porous one-dimensional oriented nano-reaction core modified with Ag nanoparticles. The oriented fiber diameter of the nano-reaction core is 100-200nm, the Ag nanoparticles are 1-10nm, and the pore size on the fiber is 1-20nm.

[0066] S3, the prepared Ag nanoparticle-modified porous one-dimensional oriented nanoreaction core is fixed on the one-dimensional gold needle using conductive resin silver paste.

[0067] S4, potassium metal is loaded on a one-dimensional tungsten wire, and then a potassium-based solid electrolyte is deposited on the potassium metal. Finally, the one-dimensional gold needle with a one-dimensional directional nanoreaction core fixed thereon obtained in S3 is connected to the one-dimensional tungsten wire to form a one-dimensional solid-state electrochemical in-situ TEM directional Ag-modified carbon-based nanoreaction tank; experiments are carried out using in-situ TEM equipment to observe the deposition and stripping of potassium metal in solid-state electrochemical devices.

[0068] The above shows and describes the basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank preparation method, characterized in that: The following steps are involved: S1, obtaining a one-dimensional oriented nanometer reaction core precursor, and preparing a composite precursor solution based on the one-dimensional oriented nanometer reaction core precursor; The process of obtaining the one-dimensional oriented nano-reaction core precursor is as follows: Using electrospinning technology, a high-speed roller at 2000-3000 r / min or a parallel electrode collector at a distance of 1-2 cm is used to obtain the one-dimensional oriented nano-reaction core precursor; The preparation process of the composite precursor solution is: Obtaining the one-dimensional oriented nanometer reaction core precursor, stirring and dissolving the one-dimensional oriented nanometer reaction precursor with a solvent to form the composite precursor solution, wherein the one-dimensional oriented nanometer reaction core precursor accounts for 9% to 70% of the solvent in the composite precursor solution; S2, performing one-dimensional oriented nano-sizing and post-processing on the composite precursor solution to obtain a one-dimensional oriented nano-reaction core; The process of obtaining the one-dimensional oriented nano-reaction core is as follows: Performing one-dimensional oriented nano-sizing on the composite precursor solution, with an orientation degree greater than 80 degrees; Post-processing the material after the one-dimensional directional nano-crystallization, wherein the post-processing comprises: calcining and etching for 1-10 hours at 500-1000° C. in an inert atmosphere to obtain the one-dimensional directional nano-reaction core; The one-dimensional oriented nano-reaction core is composed of oriented fibers or oriented tubes with a length of 50nm-10cm; The diameter of the oriented fibers is 10-1000 nm; The inner diameter of the oriented tube is 10-1000nm, and the tube wall thickness is 10-100nm; The oriented fibers and the oriented tubes are provided with small holes on the top, and the size of the small holes is 0.1-50 nm; The one-dimensional oriented nano-reaction core has a Young's modulus of 0.1-200 Gpa and a tensile strength of 10 MPa-10 Gpa; S3, fixing the one-dimensional oriented nano-reaction core on the one-dimensional gold needle; S4, loading alkali metal onto a one-dimensional tungsten wire, and depositing a solid electrolyte on the alkali metal; connecting the alkali metal deposited with the solid electrolyte with the one-dimensional gold needle fixed with the one-dimensional directional nano-reaction core, to obtain a one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank.

2. The method for preparing a one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank according to claim 1, characterized in that: The one-dimensional oriented nanometer reaction core precursor is a carbon precursor and contains dopants, wherein the dopants include an oxide precursor, a nitride precursor, a carbide precursor and a metal precursor.

3. The method for preparing a one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank according to claim 1, characterized in that: The solvent includes N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide.

4. The method for preparing a one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank according to claim 1, characterized in that: The solid electrolyte is a lithium metal battery solid electrolyte, a sodium metal battery solid electrolyte or a potassium metal battery solid electrolyte.

5. The method for preparing a one-dimensional solid-state electrochemical in-situ TEM directional nano-reaction tank according to claim 1, characterized in that: The alkali metal is one, a combination of two or a combination of three of lithium, sodium and potassium.

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