CN108365259B - Lithium ion solid electrolyte and preparation method and application thereof - Google Patents
Lithium ion solid electrolyte and preparation method and application thereof Download PDFInfo
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Abstract
A lithium ion solid electrolyte and a preparation method and application thereof belong to the technical field of batteries. The lithium ion solid electrolyte comprises an NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions and a Ge film, wherein the Ge film is plated on the surface of the NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions, and the thickness of the plated film is 10-200 nm. According to the invention, the Ge film with a certain thickness is plated on the surface of the solid electrolyte LAGP, so that on one hand, the reduction of tetravalent germanium is inhibited, and the electrolyte is protected; on the other hand, the electrolyte and the lithium metal are in closer contact, and the interfacial resistance of the solid-state battery is reduced. In addition, the solid electrolyte with the protected surface can also effectively inhibit the production of lithium dendrites, thereby improving the cycling stability and the coulombic efficiency of the battery, and playing the effects of reducing the interface impedance and improving the interface stability for the solid battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a lithium ion solid electrolyte and a preparation method and application thereof.
Background
Lithium ion batteries have received extensive attention and use because of the high specific energy density. Most lithium ion batteries currently use organic electrolytes to transport lithium ions. However, these organic electrolytes have safety hazards, and may cause problems such as leakage, burning, and explosion. In addition, in the lithium battery using metallic lithium as a negative electrode, negative electrode lithium dendrites grow and may pierce an electrolyte layer during battery cycling, causing a short circuit of the battery, thereby causing safety accidents such as combustion or explosion. To fundamentally solve this problem, researchers have used a solid electrolyte as a lithium ion conductor. The solid electrolyte has the advantages of high lithium ion conductivity, wide electrochemical window, high mechanical strength and the like. There are several solid electrolytes widely used at present, including perovskite type, NASICON type, LISICON type and garnet type. This is achieved byAmong these electrolytes, sulfur-based electrolytes are unstable in air and are difficult to prepare. While the remaining oxide electrolytes, the perovskite electrolyte and metallic lithium are unstable, and tetravalent titanium is reduced by lithium. Meanwhile, garnet-type electrolytes have recently been studied extensively, but studies have reported that the electrolytes are unstable in air and a lithium carbonate film is formed on the surface. The NASICON type solid electrolyte LAGP has high lithium ion conductivity (10)-4S/cm) and a wide electrochemical window (6V vs Li/Li)+) And it is very stable in air and thus is often used for solid-state lithium-air batteries. However, the tetravalent germanium in the lag is reduced to zero-valent or divalent germanium by the lithium metal.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the technical problems that tetravalent germanium in the NASICON type lithium ion solid electrolyte containing tetravalent germanium ions can be reduced into zero-valent or divalent germanium by lithium metal, the interface resistance between the solid electrolyte and a lithium sheet is large and the like in the prior art, the invention provides the lithium ion solid electrolyte, the preparation method and the application thereof, which can enable the contact between the electrolyte and the lithium metal to be tighter while inhibiting the reduction of the tetravalent germanium and can also effectively inhibit the production of lithium dendrite.
The technical scheme is as follows: a lithium ion solid electrolyte comprises an NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions and a Ge film, wherein the Ge film is plated on the surface of the NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions, and the thickness of the plated film is 10-200 nm.
Preferably, the mass of the NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions is 0.1 to 1.0 mg.
Preferably, the NASICON type lithium ion solid electrolyte containing tetravalent germanium ions is Li1.5Al0.5Ge1.5P3O12、Li1.4Al0.4Ge1.6O12Or Li1+x+yAlx(Ti,Ge)2-xP3-yO12Wherein 0 is<x<2, 0<y<3。
Another technical solution of the present invention is the preparation method of the lithium ion solid electrolyte, the preparation method comprises preparing an NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions by a conventional solid phase method, and the preparation method further comprises the following steps: polishing the surface of the NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions by using sand paper, then ultrasonically cleaning the NASICON type lithium ion solid electrolyte sheet in ethanol for 20-120 min, and putting the cleaned NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions into an oven to be dried for 0.5-12 h at the temperature of 40-80 ℃; and then plating a Ge film on the dried NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions, wherein the film plating method comprises evaporation, magnetron sputtering, ion beam sputtering, atomic deposition, CVD or PECVD, and finally obtaining the NASICON type lithium ion solid electrolyte containing the tetravalent germanium ions with the Ge plated surface.
Preferably, the coating method is an ion beam sputtering method, and the specific coating process is as follows: putting the dried NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions into a Gatan682 film plating instrument for plating a film for 2-35 min, wherein the vacuum degree of a cavity is higher than 10-3Pa, setting the energy of the electron beam to be 6-7 eV, and setting the current to be 250-350 muA, and finally obtaining the surface Ge-plated NASICON type lithium ion solid electrolyte containing the quadrivalent germanium ions.
The invention also provides an application of the lithium ion solid electrolyte in a solid-state battery with a lithium metal negative electrode.
Preferably, another technical scheme of the invention is the application of the lithium ion solid electrolyte in a solid-state lithium air battery and a solid-state lithium-lithium symmetric battery.
Preferably, another technical scheme of the invention is an application of the lithium ion solid electrolyte in a solid-state lithium-air battery, and the specific application steps are as follows:
step one, ball milling and uniformly mixing the carbon nano tube and the ruthenium dioxide by a high-energy ball mill to obtain a mixed material dispersed in [ C ]2C1im][NTf2]Stirring to form slurry, uniformly coating the slurry serving as a positive electrode on the NASICON type lithium ion solid electrolyte with the surface plated with Ge and containing tetravalent germanium ions, and welding an aluminum lug of an aluminum mesh to a positive electrode current collector;
secondly, sticking a metal lithium sheet on the other surface of the solid electrolyte to serve as a battery cathode, wherein a cathode current collector adopts a nickel tab;
and step three, coating the solid lithium-air battery with an aluminum-plastic film, forming a hole on the positive electrode surface, and sealing the aluminum-plastic film by using a hot press to finally obtain the solid lithium-air battery.
Preferably, another technical scheme of the invention is the application of the lithium ion solid electrolyte in a solid-state lithium-lithium symmetric battery, and the specific application steps are as follows:
step one, attaching metal lithium sheets to two sides of a NASICON type lithium ion solid electrolyte with the surface plated with Ge and containing tetravalent germanium ions;
and step two, coating the whole battery obtained in the step one by using an aluminum plastic film, using a nickel tab as a current collector, and sealing the aluminum plastic film by using a hot press for hot pressing for 20-60 min to finally obtain the solid lithium-lithium symmetric battery.
Has the advantages that: according to the invention, the Ge film with a certain thickness is plated on the surface of the solid electrolyte LAGP, so that on one hand, the reduction of tetravalent germanium is inhibited, and the electrolyte is protected; on the other hand, the electrolyte and the lithium metal are in closer contact, and the interfacial resistance of the solid-state battery is reduced. In addition, the surface-protected solid electrolyte can also effectively inhibit the production of lithium dendrites, thereby improving the cycling stability and the coulombic efficiency of the battery. According to the method, the lithium sheet does not need to be heated to be fused on the solid electrolyte sheet, and only a layer of nano germanium film needs to be uniformly plated on the surface of the solid electrolyte sheet, so that the reaction between the solid electrolyte and the metal lithium can be effectively inhibited, the interface impedance can be greatly reduced, and the simple protection method of the solid electrolyte is beneficial to promoting the large-scale use of the solid lithium metal battery in the future.
Drawings
FIG. 1 is a schematic diagram showing a comparative structure between the front and rear surfaces of a LAGP solid electrolyte sheet according to the present invention before and after germanium plating, wherein a is a graph showing that the solid electrolyte sheet is in closer contact with lithium after being coated with a film, and b is a graph showing the change of valence state of germanium ions before and after the solid electrolyte sheet is coated with a film;
FIG. 2 is an analysis diagram of the morphology and chemical composition of germanium plated on the surface of a LAGP solid electrolyte, wherein a is an uncoated solid electrolyte, b is a coated solid electrolyte, c is a scanning electron microscope diagram of the section of the coated solid electrolyte, d is a scanning electron microscope diagram of the surface of the coated solid electrolyte, e is an XPS diagram of the surface etching of the coated solid electrolyte, and f is a Raman diagram of the solid electrolyte before and after coating;
FIG. 3 is a graph of electrochemical impedance spectrum and cycle of a lithium-lithium symmetric battery in example 3, wherein a is an electrochemical impedance spectrum of a lithium-lithium symmetric battery equipped with a solid electrolyte before and after coating, b is a symmetric battery equipped with a silver-blocking electrode and a lithium-lithium symmetric battery equipped with a solid electrolyte after coating, c is a charge-discharge graph of a lithium-lithium symmetric battery equipped with a solid electrolyte before and after coating, and d is a charge-discharge graph of a lithium-lithium symmetric battery equipped with a solid electrolyte after coating at different current densities;
FIG. 4 is an electrochemical impedance spectrum before and after the cycle of the lithium-lithium symmetric battery in example 3, wherein a is an impedance spectrum before the cycle reaction of the lithium-lithium symmetric battery assembled with the solid electrolyte before coating, b is an impedance spectrum after the cycle reaction of the lithium-lithium symmetric battery assembled with the solid electrolyte before coating, c is an impedance spectrum before the cycle reaction of the lithium-lithium symmetric battery assembled with the solid electrolyte after coating, and d is an impedance spectrum after the cycle reaction of the lithium-lithium symmetric battery assembled with the solid electrolyte after coating;
FIG. 5 is a graph of the morphology of the solid electrolyte before and after the circulation of the germanium-plating process of the present invention, wherein a is a scanning electron microscope of the surface of the solid electrolyte before the circulation reaction after the plating of the germanium film, b and c are scanning electron microscopes of the surface of the solid electrolyte after the circulation reaction after the plating of the germanium film, d is a scanning electron microscope of the surface of the solid electrolyte before the circulation reaction without the plating of the germanium film, and e and f are scanning electron microscopes of the surface of the solid electrolyte after the circulation reaction without the plating of the germanium;
FIG. 6 is a XPS characterization of solid electrolytes before and after germanium plating according to the present invention, wherein a is an XPS map of a surface of an uncoated solid electrolyte before a cyclic reaction, b is an XPS map of a surface of an uncoated solid electrolyte after a cyclic reaction, c is an XPS map of a surface of a coated solid electrolyte before a cyclic reaction, and d is an XPS map of a surface of a coated solid electrolyte after a cyclic reaction;
fig. 7 is a graph showing the cycle curves of the solid state lithium air battery in example 4, wherein a is a schematic diagram of the solid state lithium air battery, b is an electrochemical impedance spectrum of the solid state lithium air battery assembled with the solid electrolyte before and after coating, c is a charge-discharge cycle curve of the solid state lithium air battery assembled with the solid electrolyte after coating, and d is a charge-discharge cycle curve of the solid state lithium air battery assembled with the solid electrolyte without coating.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention, but the present invention is not limited to the following embodiments.
Example 1
A lithium ion solid electrolyte comprises a NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions and a Ge film, wherein the Ge film is plated on the surface of the NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions, and the thickness of the plated film is 10 nm. The mass of the NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions was 0.1 mg. The NASICON type lithium ion solid electrolyte containing tetravalent germanium ions is Li1.4Al0.4Ge1.6O12。
The preparation method of the lithium ion solid electrolyte comprises the step of preparing the NASICON type lithium ion solid electrolyte sheet Li containing the quadrivalent germanium ions by the traditional solid phase method1.4Al0.4Ge1.6O12The preparation method also comprises the following steps: the lithium ion solid electrolyte sheet Li of NASICON type containing quadrivalent germanium ions1.4Al0.4Ge1.6O12Polishing the surface by using sand paper, then ultrasonically cleaning in ethanol for 20min, and putting the cleaned NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions into an oven to be dried for 0.5 h at 40 ℃; and then plating a Ge film on the dried NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions, wherein the plating method is an ion beam sputtering method, and the specific plating process is as follows: placing the dried NASICON type lithium ion solid electrolyte sheet containing quadrivalent germanium ions into a Gatan682 film plating instrument for film plating for 2 min, wherein the vacuum degree of the cavity is higher than 10-3Pa, the energy of the electron beam is set to be 6eV, the current is set to be 250 muA, and finally the NASICON type lithium ion solid electrolyte which is plated with Ge on the surface and contains quadrivalent germanium ions is obtained.
The application of the lithium ion solid electrolyte in the solid-state lithium-air battery comprises the following specific application steps:
step one, ball milling the carbon nano tube and ruthenium dioxide for 2 hours at the rotating speed of 500 rpm by a high-energy ball mill according to the mass ratio of 8:1, and dispersing 5mg of the obtained mixed material in 0.5mL of [ C ]2C1im][NTf2]Adding 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide, 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide) into an ionic liquid, stirring for 12 hours to form slurry, taking 0.3mg of the slurry as a positive electrode, uniformly coating the slurry on the NASICON type lithium ion solid electrolyte with Ge-plated surface and containing tetravalent germanium ions, and welding an aluminum tab of an aluminum net as a positive electrode current collector;
step two, attaching a metal lithium sheet with the thickness of 0.5mm and the diameter of 12 mm to the other surface of the solid electrolyte to be used as a battery cathode, and using a nickel electrode lug as a cathode current collector;
and step three, coating the solid-state lithium-air battery with an aluminum-plastic film, opening a hole on the positive electrode surface, wherein the hole diameter is 10 mm, and the film thickness is 0.1mm, and sealing the aluminum-plastic film by using a hot press (PFS-300 hand press sealing machine) for 20min to finally obtain the solid-state lithium-air battery.
Example 2
A lithium ion solid electrolyte comprises a NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions and a Ge film, wherein the Ge film is plated on the surface of the NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions, and the thickness of the plated film is 200 nm. The mass of the NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions was 1.0 mg. The NASICON type lithium ion solid electrolyte containing tetravalent germanium ions is Li1.4Al0.4Ge1.6O12。
The preparation method of the lithium ion solid electrolyte comprises the following steps of preparing an NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions by a traditional solid phase method: grinding and polishing the surface of a NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions by using sand paper, then ultrasonically cleaning the NASICON type lithium ion solid electrolyte sheet in ethanol for 120 min, and then cleaning the cleaned NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ionsPutting the ionic NASICON type lithium ion solid electrolyte sheet into an oven to be baked for 12 hours at the temperature of 80 ℃; and then plating a Ge film on the dried NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions, wherein the plating method is an ion beam sputtering method, and the specific plating process is as follows: placing the dried NASICON type lithium ion solid electrolyte sheet containing quadrivalent germanium ions into a Gatan682 film coating instrument for film coating for 35 min, wherein the vacuum degree of the cavity is higher than 10-3Pa, setting the energy of an electron beam to be 7eV, and setting the current to be 350 muA, and finally obtaining the surface Ge-plated NASICON type lithium ion solid electrolyte containing the quadrivalent germanium ions.
The application of the lithium ion solid electrolyte in the solid-state lithium-air battery comprises the following specific application steps:
step one, ball milling the carbon nano tube and ruthenium dioxide for 6 hours at the rotating speed of 800 rpm by a high-energy ball mill according to the mass ratio of 10:1, and dispersing 5mg of the obtained mixed material in 0.5mL of [ C ]2C1im][NTf2]Stirring in ionic liquid (1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide, 1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide) for 24 hours to form slurry, taking 1mg of the slurry as a positive electrode to be uniformly coated on the NASICON type lithium ion solid electrolyte with the surface being plated with Ge and containing tetravalent germanium ions, and welding an aluminum tab of an aluminum net to serve as a positive electrode current collector;
step two, attaching a metal lithium sheet with the thickness of 0.8mm and the diameter of 16 mm to the other surface of the solid electrolyte to be used as a battery cathode, and using a nickel electrode lug as a cathode current collector;
and step three, coating the solid-state lithium-air battery with an aluminum-plastic film, opening a hole on the positive electrode surface, wherein the hole diameter is 12 mm, and the film thickness is 0.3mm, and sealing the aluminum-plastic film by using a hot press (PFS-300 hand press sealing machine) for 60min to finally obtain the solid-state lithium-air battery.
Example 3
A lithium ion solid electrolyte comprises a NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions and a Ge film, wherein the Ge film is plated on the surface of the NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions. Wherein the NASICON type lithium ion solid electrolyte containing tetravalent germanium ionsThe tablet is LAGP (Li)1.5Al0.5Ge1.5P3O12) A solid electrolyte sheet. Fig. 1 is a schematic diagram showing a structure comparing before and after germanium plating on the surface of a lag solid electrolyte sheet according to the present invention, wherein a is a diagram showing that the solid electrolyte sheet is in closer contact with lithium after being plated with a film, and b is a diagram showing a valence state change of germanium ions before and after being plated with a film. As shown in the figure, the LAGP solid electrolyte sheet is in closer contact with lithium after being coated, tetravalent germanium ions are reduced into divalent germanium ions or zero-valent germanium ions when the LAGP sheet is in contact with lithium before coating, and the valence state of the tetravalent germanium ions is unchanged when the LAGP sheet is in contact with lithium after coating.
The preparation method of the lithium ion solid electrolyte comprises the following steps: preparation of LAGP (Li) by conventional solid phase method1.5Al0.5Ge1.5P3O12) The mass of the LAGP solid electrolyte sheet is 0.75 mg, the surface of the LAGP solid electrolyte sheet is polished by abrasive paper, then the LAGP solid electrolyte sheet is ultrasonically cleaned in ethanol for 30min, and the cleaned LAGP solid electrolyte sheet is placed in an oven to be dried for 2 h at the temperature of 60 ℃; then putting the dried LAGP solid electrolyte sheet into a Gatan682 film coating instrument for film coating for 10 min, wherein the vacuum degree of a cavity is higher than 10-3Pa, setting the energy of an electron beam to be 7eV, setting the current to be 300 muA, and setting the thickness of the coating film to be 60 nm, thereby finally obtaining the NASICON type lithium ion solid electrolyte with the Ge-plated surface and containing the quadrivalent germanium ions. The specific morphology and chemical composition analysis chart of the coated LAGP solid electrolyte is shown in figure 2, and the LAGP solid electrolyte sheet is white before coating; and after film coating, covering a gray germanium film on the surface of the LAGP solid electrolyte sheet. The thickness of the germanium film is about 60 nm as shown by a section scanning electron microscope. And the film is amorphous germanium film in a front electron microscope image. Raman spectrum shows that the germanium-plated film is 270 to 150cm-1There are two broad peaks, consistent with those of amorphous germanium films in the literature.
The lithium ion solid electrolyte prepared in the example is applied to a lithium-lithium symmetrical battery. Namely, the lithium-lithium symmetric battery prepared from the prepared LAGP solid electrolyte sheet with the Ge plated surface comprises an aluminum plastic film, the LAGP sheet with the Ge plated surface, a lithium foil and a nickel current collector, and has the following specific application steps:
step one, attaching metal lithium sheets to two sides of a NASICON type lithium ion solid electrolyte with the surface plated with Ge and containing tetravalent germanium ions;
and step two, coating the battery whole obtained in the step one by using an aluminum plastic film, using a nickel tab as a current collector, and carrying out hot pressing for 30min by using a hot press (PFS-300 hand pressing sealing machine) to seal the aluminum plastic film, thereby finally obtaining the solid lithium-lithium symmetric battery.
And (3) replacing the LAGP sheet with the Ge plated surface with the LAGP sheet without the Ge plated surface, and preparing the solid lithium-lithium symmetrical battery without the Ge plated surface without changing other steps for comparison.
Referring to fig. 3, it can be seen that the impedance of the symmetric cell without germanium plating is 2506 ohms, and after germanium plating, the impedance is reduced to 147 ohms, which indicates that the interface impedance can be effectively reduced by germanium plating. In addition, the germanium-plated electrolyte sheet was impedance-measured for a symmetric cell assembled with gold electrodes, with a long tail at low frequency band, representing the lithium ion diffusion impedance. The comparison of the two shows that the germanium film can effectively pass lithium ions. If the germanium film is unable to pass lithium ions, the impedance to the lithium battery should be similar to that of the gold electrode. The electrochemical performance of the germanium-plated thin film electrolyte is shown in fig. 3c and d. As shown in the figure, after germanium plating, the charging and discharging overpotential is obviously reduced under the same current. The germanium film plated electrolyte can be stably cycled for 200 hours. To test the stability of the germanium-plated film, we studied the impedance spectrum and XPS spectrum before and after charging and discharging. As shown in fig. 4, the impedance of the symmetrical cell assembled with the non-germanium plated LAGP sheet increased from 2506 ohms before discharge to thirty thousand ohms after discharge. After germanium plating, the impedance of the symmetrical cell was 147 ohms before discharge and increased to 1150 ohms after discharge. In contrast, after germanium plating, the impedance of the symmetrical cell before discharge is significantly reduced; in addition, the resistance of the germanium-plated samples increased very little after discharge, which indicates that the germanium-plating electrolyte was stable to lithium. FIG. 5 is a graph of the morphology of the solid electrolyte before and after cycling, before and after germanium plating. The uncoated LAGP sheet surface had many fragments formed after cycling. And the surface of the plated LAGP sheet forms a plurality of small flower-shaped products after circulation, and the products should be Li-Ge alloy intermediate layers. To accurately analyze the change in the valence state of germanium, we tested XPS spectra of the germanium element in the electrolyte. As can be seen from fig. 6, the peak position of tetravalent germanium in lag is around 32.3eV, and after cycling, the germanium is reduced to divalent and elemental germanium. The Ge peak of the germanium-plated LAGP before discharge is about 29.2eV, which corresponds to the peak of the simple substance germanium, and the Ge peak position after discharge is about 26eV, which corresponds to the Ge position in the Li-Ge alloy. These results indicate that the stability of the germanium-plated electrolyte is significantly improved, the interfacial resistance is also significantly reduced, and the improvement of the performance of the solid-state battery is facilitated.
Example 4
A lithium ion solid electrolyte comprises a NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions and a Ge film, wherein the Ge film is plated on the surface of the NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions. Wherein the NASICON type lithium ion solid electrolyte sheet containing quadrivalent germanium ions is LAGP (Li)1.5Al0.5Ge1.5P3O12) A solid electrolyte sheet.
The preparation method of the lithium ion solid electrolyte comprises the following steps: preparation of LAGP (Li) by conventional solid phase method1.5Al0.5Ge1.5P3O12) The mass of the LAGP solid electrolyte sheet is 0.75 mg, the surface of the LAGP solid electrolyte sheet is polished by abrasive paper, then the LAGP solid electrolyte sheet is ultrasonically cleaned in ethanol for 30min, and the cleaned LAGP solid electrolyte sheet is placed in an oven to be dried for 2 h at the temperature of 60 ℃; then putting the dried LAGP solid electrolyte sheet into a Gatan682 film coating instrument for film coating for 10 min, wherein the vacuum degree of a cavity is higher than 10-3Pa, setting the energy of an electron beam to be 7eV, setting the current to be 300 muA, and setting the thickness of the coating film to be 60 nm, thereby finally obtaining the NASICON type lithium ion solid electrolyte with the Ge-plated surface and containing the quadrivalent germanium ions. The specific morphology and chemical composition analysis chart of the coated LAGP solid electrolyte is shown in figure 2, and the LAGP solid electrolyte sheet is white before coating; and after film coating, covering a gray germanium film on the surface of the LAGP solid electrolyte sheet. The thickness of the germanium film is about 60 nm as shown by a section scanning electron microscope. And the film is amorphous germanium film in a front electron microscope image. Raman spectrum shows that the germanium-plated film is 270 to 150cm-1There are two broad peaks, consistent with those of amorphous germanium films in the literature.
The lithium ion solid electrolyte prepared in this example is applied to a solid-state lithium air battery. The specific application steps are as follows: the carbon nanotubes and ruthenium dioxide were ball milled for 2 hours at 700 rpm in a 9:1 mass ratio by a high energy ball mill. 5mg of the resulting mixture was dispersed in 0.5mL of [ C ]2C1im][NTf2]Ionic liquid (1-ethyl-3-methylimidazoline bis (trifluoromethylsulfonyl) imide, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide) and stirred for 12 hours to form a slurry. Taking 1mg of the slurry as a positive electrode, uniformly coating the slurry on NASICON type lithium ion solid electrolyte which is plated with Ge on the surface and contains tetravalent germanium ions, and welding an aluminum lug of an aluminum net as a positive electrode current collector; a metal lithium sheet with the thickness of 0.5mm and the diameter of 14 mm is attached to the other surface of the solid electrolyte to be used as a battery cathode, and a nickel electrode lug is used as a cathode current collector; and then coating the solid-state lithium-air battery with an aluminum-plastic film, opening a hole on the positive electrode surface, wherein the hole diameter is 12 mm, and the film thickness is 0.1mm, and sealing the aluminum-plastic film by using a hot press (PFS-300 hand press sealing machine) for 30min to finally obtain the solid-state lithium-air battery.
The prepared solid-state lithium-air battery, referring to fig. 7, employs carbon nanotubes/gel as the positive electrode, germanium-plated LAGP as the electrolyte layer and lithium as the negative electrode. Impedance spectrum comparison shows that the impedance of the germanium-plated solid-state battery is obviously reduced. In addition, the stable interface enables the germanium electrolyte plated lithium-air battery to stably circulate for thirty circles; and the capacity of the battery without the germanium plating is greatly attenuated after nine cycles. These results indicate that the germanium-plated LAGP solid electrolyte sheet can use metallic lithium as the negative electrode and effectively provide the electrochemical performance of the battery.
In summary, the solid electrolyte sheet containing tetravalent germanium and protected by surface coating designed by the application inhibits the reduction of tetravalent germanium and protects the electrolyte; on the other hand, the electrolyte and the lithium metal are in closer contact, and the interfacial resistance of the solid-state battery is reduced. In addition, the scheme can be extended to high-energy-density systems such as solid lithium air batteries and lithium sulfur batteries, and can also be applied to other solid batteries using lithium metal cathodes, so that the effects of reducing interface impedance and improving interface stability are achieved for the solid batteries. The battery impedance can be obviously reduced, and the cycling stability and the coulombic efficiency of the battery can be improved.
Claims (3)
1. The lithium ion solid electrolyte is characterized by comprising a NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions and a Ge film, wherein the Ge film is plated on the surface of the NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions, the thickness of the plated film is 60 nm, the mass of the NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions is 0.75 mg, and the NASICON type lithium ion solid electrolyte containing the tetravalent germanium ions is Li1.5Al0.5Ge1.5P3O12The preparation method of the lithium ion solid electrolyte comprises the step of preparing an NASICON type lithium ion solid electrolyte sheet containing tetravalent germanium ions by a traditional solid phase method, and further comprises the following steps: polishing the surface of the NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions by using sand paper, then ultrasonically cleaning the NASICON type lithium ion solid electrolyte sheet in ethanol for 30min, and putting the cleaned NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions into an oven to be dried for 2 h at the temperature of 60 ℃; and then plating a Ge film on the dried NASICON type lithium ion solid electrolyte sheet containing the tetravalent germanium ions, wherein the film plating method is an ion beam sputtering method, and the specific film plating process is as follows: placing the dried NASICON type lithium ion solid electrolyte sheet containing quadrivalent germanium ions into a Gatan682 film plating instrument for film plating for 10 min, wherein the vacuum degree of the cavity is higher than 10-3Pa, setting the energy of an electron beam to be 7eV, and setting the current to be 300 muA, and finally obtaining the surface Ge-plated NASICON type lithium ion solid electrolyte containing the quadrivalent germanium ions.
2. The application of the lithium ion solid electrolyte in the solid-state lithium-air battery based on the claim 1 comprises the following specific application steps:
step one, ball milling and uniformly mixing the carbon nano tube and the ruthenium dioxide by a high-energy ball mill to obtain a mixed material dispersed in [ C ]2C1im][NTf2]Stirring to form slurry, uniformly coating the slurry serving as a positive electrode on the NASICON type lithium ion solid electrolyte with the surface plated with Ge and containing tetravalent germanium ions, and welding an aluminum lug of an aluminum mesh to a positive electrode current collector;
secondly, sticking a metal lithium sheet on the other surface of the solid electrolyte to serve as a battery cathode, wherein a cathode current collector adopts a nickel tab;
and step three, coating the solid lithium-air battery with an aluminum-plastic film, forming a hole on the positive electrode surface, and sealing the aluminum-plastic film by using a hot press to finally obtain the solid lithium-air battery.
3. The application of the lithium ion solid electrolyte in the solid-state lithium-lithium symmetrical battery based on the claim 1 comprises the following specific application steps:
step one, attaching metal lithium sheets to two sides of a NASICON type lithium ion solid electrolyte with the surface plated with Ge and containing tetravalent germanium ions;
and step two, coating the battery whole obtained in the step one by using an aluminum plastic film, using a nickel tab as a current collector, and sealing the aluminum plastic film by using a hot press to finally obtain the solid lithium-lithium symmetric battery.
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