CN113241475B - Solid electrolyte and preparation method and application thereof - Google Patents

Solid electrolyte and preparation method and application thereof Download PDF

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CN113241475B
CN113241475B CN202110493313.5A CN202110493313A CN113241475B CN 113241475 B CN113241475 B CN 113241475B CN 202110493313 A CN202110493313 A CN 202110493313A CN 113241475 B CN113241475 B CN 113241475B
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solid electrolyte
mxene
active metal
layer
electrolyte membrane
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CN113241475A (en
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徐亚楠
王凯
马衍伟
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Institute of Electrical Engineering of CAS
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Institute of Electrical Engineering of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention belongs to the technical field of all-solid-state lithium batteries, and particularly relates to a solid electrolyte and a preparation method and application thereof. The solid electrolyte provided by the invention comprises an inorganic solid electrolyte and an active metal-MXene modification layer arranged on the surface of the inorganic solid electrolyte, wherein the active metal-MXene modification layer comprises an active metal and MXene chemically combined with the active metal; the active metal is a metal capable of undergoing redox reaction with an oxygen-containing functional group on the surface of MXene. According to the solid electrolyte provided by the invention, the active metal-MXene modification layer is arranged on the surface of the inorganic solid electrolyte, and the inorganic solid electrolyte is tightly contacted with the MXene material through the active metal, so that the electrochemical performance of the all-solid battery is improved.

Description

Solid electrolyte and preparation method and application thereof
Technical Field
The invention belongs to the technical field of all-solid-state lithium batteries, and particularly relates to a solid electrolyte and a preparation method and application thereof.
Background
At present, organic electrolyte such as esters and the like is adopted in commercial lithium ion batteries, and under the condition of collision or short circuit, the temperature of the batteries is increased, the organic electrolyte is decomposed or leaked, and the batteries are easy to catch fire or even explode when oxygen is encountered, so that serious potential safety hazards exist. In addition, at low temperature, the viscosity of the liquid electrolyte is increased, the ion migration rate is obviously reduced, the internal resistance of the battery is increased, and the service life, energy and power characteristics of the whole battery are seriously influenced.
Therefore, the non-flammable solid electrolyte is adopted to replace the traditional liquid electrolyte, the safety problem of the battery can be fundamentally solved, and the energy density of the system can be greatly improved. The reason is that: (1) the all-solid-state lithium battery has no problem of electrolyte leakage, and the safety of the battery is obviously improved; (2) the solid electrolyte has a wider electrochemical window, provides conditions for using a high-voltage anode material, and can improve the integral volume energy density; (3) the solid electrolyte has high stability to lithium metal and high mechanical strength, and can relieve the piercing of lithium dendrites.
However, since the solid electrolyte in the all solid-state lithium battery replaces the liquid electrolyte, the contact interface between the metallic lithium and the electrolyte becomes a solid-to-solid contact interface. The good wettability of the liquid electrolyte is lost, and a solid-solid interface can form higher interface resistance. Meanwhile, uneven contact of metallic lithium with the solid electrolyte can cause local current non-uniformity, uneven deposition of lithium metal, promote the generation of lithium dendrites, and eventually puncture the electrolyte, leading to battery failure.
Disclosure of Invention
In view of the above, the present invention provides a solid electrolyte, a method for preparing the same, and an application of the same, wherein the solid electrolyte provided by the present invention can effectively contact with a lithium metal negative electrode, reduce an interface resistance, and inhibit generation of lithium dendrites, so that a solid lithium battery can obtain excellent electrochemical performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a solid electrolyte, which comprises an inorganic solid electrolyte and an active metal-MXene modification layer arranged on the surface of the inorganic solid electrolyte, wherein the active metal-MXene modification layer comprises an active metal and MXene chemically combined with the active metal;
the active metal is a metal capable of undergoing redox reaction with an oxygen-containing functional group on the surface of MXene.
Preferably, the thickness of the active metal-MXene modification layer is 100-500 nm.
Preferably, the chemical formula of MXene in the active metal-MXene modification layer is Mn+1XnTyM is a transition metal element, X is a C element or an N element, and T is F and OH;
n is 1, 2 or 3, and y is more than or equal to 0 and less than 2.
Preferably, the M is a Ti element, a Nb element, a V element or a Mo element.
Preferably, the active metal is Mg, Al, Ti, Mn or Zn.
Preferably, the inorganic solid electrolyte is one or more of an oxide-type solid electrolyte, a sulfide-type solid electrolyte, a perovskite-type solid electrolyte, and a NASICON-type solid electrolyte.
The invention provides a preparation method of the solid electrolyte in the technical scheme, which comprises the following steps:
(1) in a vacuum environment, evaporating active metal on the surface of an inorganic solid electrolyte, and forming an active metal layer on the surface of the inorganic solid electrolyte, wherein the active metal is metal capable of carrying out redox reaction with an oxygen-containing functional group on the surface of MXene;
(2) dropwise adding the single-layer MXene aqueous dispersion to the surface of the active metal layer to perform redox reaction, and forming an initial active metal-MXene modification layer on the surface of the inorganic solid electrolyte;
(3) and (3) circularly performing the step (2) on the surface of the initial active metal-MXene modified layer for N times to obtain the solid electrolyte.
Preferably, in the step (1), the thickness of the active metal layer is 50-300 nm, and the evaporation time is 30-60 s.
Preferably, in the step (2), the mass concentration of the single-layer MXene aqueous dispersion is 0.5-2 mg/mL, and the time of the oxidation-reduction reaction is 30-60 min.
Preferably, the 1 is less than or equal to N less than or equal to 3.
The invention provides the application of the solid electrolyte in the technical scheme or the solid electrolyte obtained by the preparation method in the technical scheme in an all-solid-state lithium battery.
The solid electrolyte provided by the invention comprises an inorganic solid electrolyte and an active metal-MXene modification layer arranged on the surface of the inorganic solid electrolyte, wherein the active metal-MXene modification layer comprises an active metal and MXene chemically combined with the active metal; the active metal is a metal capable of undergoing redox reaction with an oxygen-containing functional group on the surface of MXene. The solid electrolyte provided by the invention is characterized in that an active metal-MXene modification layer is arranged on the surface of an inorganic solid electrolyte, active metal in the active metal-MXene modification layer is connected with an oxygen-containing group on the surface of an MXene material through an ionic bond, and the inorganic solid electrolyte is tightly contacted with the MXene material through the active metal. The MXene material in the active metal-MXene modification layer of the solid electrolyte is a two-dimensional material, the surface of the MXene material is provided with rich oxygen-containing groups, the infiltration and the spreading of molten lithium metal are facilitated, the effective contact with a lithium metal cathode is increased, and the interface resistance is reduced; and the MXene material in the active metal-MXene modification layer can effectively buffer the volume change of the metal lithium in the deposition/stripping process, so that the metal lithium has low nucleation energy barrier and uniform electric field distribution, the metal lithium can be uniformly deposited, the generation of lithium dendrite is inhibited, and the electrochemical performance of the all-solid-state battery is improved. The results of the embodiment show that the solid electrolyte provided by the invention is in good contact with lithium metal, the discharge specific capacity of the obtained solid lithium battery is obviously improved, the discharge specific capacity is not obviously changed after 50 weeks of circulation, and the capacity retention rate is obviously increased.
The preparation method of the solid electrolyte provided by the invention has the advantages of simple process, mild reaction conditions and low equipment requirement, meets the requirement of green chemistry, and is beneficial to market popularization.
Drawings
FIG. 1 is a physical comparison of a solid electrolyte prepared in example 1 of the present invention with a starting inorganic solid electrolyte;
FIG. 2 is a comparative photograph showing an electrolytic solution of a solid electrolyte prepared in example 1 of the present invention and a contact interface between a raw inorganic solid electrolyte and lithium metal;
fig. 3 is a graph showing the change of the specific capacity of the solid lithium battery prepared in application example 1 and comparative example 1 according to the present invention with the cycle number.
Detailed Description
The invention provides a solid electrolyte, which comprises an inorganic solid electrolyte and an active metal-MXene modification layer arranged on the surface of the inorganic solid electrolyte, wherein the active metal-MXene modification layer comprises an active metal and MXene chemically combined with the active metal;
the active metal is a metal capable of undergoing redox reaction with an oxygen-containing functional group on the surface of MXene.
In the present invention, the starting materials are all commercially available products well known to those skilled in the art, unless otherwise specified.
The solid electrolyte provided by the invention comprises an inorganic solid electrolyte; in the present invention, the inorganic solid electrolyte is preferably one or more of an oxide type solid electrolyte, a sulfide type solid electrolyte, a perovskite type solid electrolyte and an NASICON type solid electrolyte, and the present invention has no special requirements for the specific chemical composition of the oxide type solid electrolyte, the present invention has no special requirements for the specific chemical composition of the sulfide type solid electrolyte, the present invention has no special requirements for the specific chemical composition of the perovskite type solid electrolyte, and the present invention has no special requirements for the specific chemical composition of the NASICON type solid electrolyte; in a specific embodiment of the present invention, the oxide-type solid electrolyte is preferably Li6.4La3Zr1.4Ta0.6O12A solid electrolyte, preferably Li3xLa2/3-xTiO3Solid electrolyte of the Li3xLa2/3-xTiO3X in the solid electrolyte is preferably 0. ltoreq. x.ltoreq.0.11.
The solid electrolyte provided by the invention comprises an active metal-MXene modification layer arranged on the surface of the inorganic solid electrolyte, wherein the active metal-MXene modification layer comprises an active metal and MXene chemically combined with the active metal, and in the invention, the MXene surface has an oxygen-containing functional group which preferably comprises OH-(ii) a The active metal is a metal capable of undergoing redox reaction with an oxygen-containing functional group on the surface of MXene, and in the invention, the active metal is preferably Ca, Mg, Al or Zn, and more preferably Zn.
In the invention, the active metal in the active metal-MXene modification layer is chemically combined with the oxygen-containing group on the surface of the MXene material through ionic bond reaction.
In the invention, the chemical formula of MXene material in the active metal-MXene modification layer is preferably Mn+1XnTyThe M is preferably a transition metal element, more preferably a Ti element, a Nb element, a V element, or a Mo element, and in a specific embodiment of the present invention, the M is specifically a Ti element; said X is preferablyIs C element or N element, the T is preferably F and OH, the N is preferably 1, 2 or 3, and the 0 ≦ y<2; in the invention, the MXene material is preferably Ti3C2TyOr Ti4N3(ii) a In an embodiment of the present invention, the active metal-MXene modification layer is preferably Zn-Ti3C2TyModified layer or Zn-Ti4N3And a finishing layer.
In the invention, the thickness of the active metal-MXene modification layer is preferably 100-500 nm, more preferably 150-450 nm, and most preferably 200-400 nm, and in the embodiment of the substrate of the invention, the thickness of the active metal-MXene modification layer is specifically 200nm, 300nm and 400 nm.
In the invention, the redox reaction is carried out on the active metal in the active metal-MXene interface layer and the oxygen-containing group on the surface of the MXene material to generate active metal ions which are connected with the negatively charged oxygen-containing group on the surface of the MXene material through ionic bonds, so that the inorganic solid electrolyte is tightly contacted with the MXene material, the MXene material in the active metal-MXene modification layer is a two-dimensional material, the surface of the MXene material is provided with rich oxygen-containing groups, the infiltration and the spreading of molten lithium metal are facilitated, the effective contact with a lithium metal cathode is increased, the interface resistance is reduced, the generation of lithium dendrite is inhibited, and the electrochemical performance of the all-solid-state battery is improved.
The invention provides a preparation method of the solid electrolyte in the technical scheme, which comprises the following steps:
(1) in a vacuum environment, evaporating an active metal on the surface of an inorganic solid electrolyte, and forming an active metal layer on the surface of the inorganic solid electrolyte, wherein the active metal is a metal capable of carrying out redox reaction with an oxygen-containing functional group on the surface of MXene;
(2) dropwise adding the single-layer MXene aqueous dispersion to the surface of the active metal layer to perform redox reaction, and forming an initial active metal-MXene modification layer on the surface of the inorganic solid electrolyte;
(3) and (3) circularly performing the step (2) on the surface of the initial active metal-MXene modified layer for N times to obtain the solid electrolyte.
In a vacuum environment, evaporating active metal on the surface of an inorganic solid electrolyte, and forming an active metal layer on the surface of the inorganic solid electrolyte; in the invention, the active metal is a metal capable of undergoing redox reaction with an oxygen-containing functional group on the surface of MXene, and is preferably Zn, Ti, Mn, Mg or Al, and is preferably Zn.
In the present invention, the degree of vacuum of the vacuum environment is preferably 10 or less-3Pa; the temperature of the evaporation is preferably 1000-1500 ℃, and more preferably 1200-1350 ℃; the time for vapor deposition is preferably 30 to 60 seconds, and more preferably 35 to 50 seconds. In a specific embodiment of the present invention, the evaporation is preferably performed in an evaporation coating apparatus, and the present invention preferably places the active metal in a tungsten boat located at the bottom of the evaporation coating apparatus, and fixedly places the solid electrolyte on the top of the evaporation coating apparatus.
In the invention, the thickness of the active metal layer is preferably 50 to 300nm, more preferably 55 to 250mm, and most preferably 100 to 200 mm.
After an active metal layer arranged on the surface of the inorganic solid electrolyte is obtained, the single-layer MXene aqueous dispersion is dripped to the surface of the active metal layer to generate redox reaction, and an initial active metal-MXene modification layer is formed on the surface of the inorganic solid electrolyte.
In the invention, the mass concentration of the single-layer MXene aqueous dispersion liquid is preferably 0.5-2 mg/mL, and more preferably 1-1.5 mg/mL. In the present invention, the single-layer MXene aqueous dispersion is preferably prepared by the following method:
mixing the MAX phase material and HF aqueous solution, etching to obtain a multilayer MXene material,
and mixing the multilayer MXene material with a stripping agent solution, and sequentially carrying out intercalation stripping and dispersion to obtain a single-layer MXene aqueous dispersion.
The MAX phase material and the HF aqueous solution are mixed and etched to obtain the multilayer MXene material.
In the present invention, the MAX phase material preferably has a chemical formula of Mn+1AXnSaid n is preferably 1, 2 or 3; what is needed isThe M is preferably a transition metal element, more preferably a Ti element, a Nb element, a V element or a Mo element, and the A is preferably an Al element or a Si element, more preferably an Al element; the X is preferably C or N, and in the specific embodiment of the invention, the MAX phase material is preferably Ti2AlC or TiAlN3. The present invention has no particular requirement on the source of the MAX phase material.
In the invention, the mass concentration of the HF aqueous solution is preferably 0.4-0.5 g/mL, and the volume ratio of the mass of the MAX phase material to the HF aqueous solution is preferably 1-2 g: 20 mL.
In the invention, the etching time is preferably 10-60 min, and more preferably 30-45 min.
In the invention, the etching is preferably carried out under the condition of stirring, and the invention has no special requirements on the specific implementation process of the stirring.
After the etching is finished, the etched suspension is preferably subjected to post-treatment to obtain the multi-layer MXene material; in the present invention, the post-treatment preferably comprises: carrying out solid-liquid separation and washing in sequence; in the invention, the solid-liquid separation is preferably centrifugal separation, the invention has no special requirements on the specific implementation process of the centrifugal separation, the invention preferably washes the solid obtained by the centrifugal separation, the washing is preferably water washing, and the invention has no special requirements on the frequency of the water washing until the pH value of the washing liquid is more than or equal to 5.
After obtaining the multilayer MXene material, the invention mixes the multilayer MXene material with the intercalation agent solution, and carries out intercalation and stripping dispersion in sequence to obtain the single-layer MXene water dispersion.
In the present invention, the intercalating agent solution is preferably one or more of an aqueous tetrabutylammonium hydroxide (TBAOH), an aqueous cetyltrimethylammonium bromide (CTAB) and an aqueous ethylenediamine solution, more preferably an aqueous tetrabutylammonium hydroxide (TBAOH); in the invention, the mass concentration of the intercalation agent solution is preferably 20-40 wt%.
The invention has no special requirement on the mass ratio of the multi-layer MXene material to the intercalation agent solution, and ensures that the stripping agent solution is excessive.
In the invention, the time of intercalation is preferably 12-24 h, more preferably 18-20 h, the intercalation is preferably carried out under the condition of stirring, and the invention has no special requirement on the specific implementation process of stirring; in the invention, the stripping and dispersing time is preferably 1-6 h, more preferably 2-5 h, the stripping and dispersing is preferably carried out under the ultrasonic condition, and the specific implementation process of the ultrasonic is not specially required.
After stripping and dispersing are finished, the invention preferably carries out post-treatment on the suspension obtained by dispersing to obtain the single-layer MXene aqueous dispersion liquid; in the present invention, the post-treatment preferably comprises: carrying out solid-liquid separation and dilution in sequence; in the invention, the solid-liquid separation is preferably centrifugal separation, the invention has no special requirement on the specific implementation process of the centrifugal separation, and the invention preferably dilutes the supernatant obtained by the centrifugal separation, the dilution is preferably diluted by water, and the water is preferably deionized water to obtain the monolayer MXene aqueous dispersion.
The invention has no special requirement on the dripping amount of the single-layer MXene aqueous dispersion, and the single-layer MXene aqueous dispersion can be completely paved and soaked on the surface of the active metal layer; in the invention, the time of the oxidation-reduction reaction is preferably 30-60 min, and more preferably 35-55 min.
After the redox reaction is finished, the post-treatment is preferably carried out on the reacted active metal layer to obtain an initial active metal-MXene modification layer; in the invention, the post-treatment preferably comprises drying, in the invention, the drying temperature is preferably 60-80 ℃, and the drying is preferably carried out in an air-blowing drying oven.
The invention etches A in the MAX phase material by hydrofluoric acid etching, and introduces functional groups at the same time, so that the MAX phase material becomes a multi-layer M containing the functional groupsn+1XnTyThen Mn+1XnTyIntercalation is carried out by using intercalation agent solution, and then ultrasonic stripping is carried out to obtain monolayer M containing functional groupsn+1XnTy。
After the initial active metal-MXene modification layer is obtained, the redox reaction is circularly carried out on the surface of the initial active metal-MXene modification layer for N times to obtain the solid electrolyte.
In the present invention, N is preferably 1. ltoreq. N.ltoreq.3, and in the specific embodiment of the present invention, N is preferably 2 times or 3 times.
According to the invention, firstly, an active metal is evaporated on the surface of the inorganic solid electrolyte, after a compact active metal layer is formed on the surface of the inorganic solid electrolyte, MXene aqueous dispersion liquid is contacted with the active metal layer, the active metal in the active metal layer and an oxygen-containing group on the surface of MXene in the MXene aqueous dispersion liquid are subjected to redox reaction, and positively charged active metal ions are bonded with a negatively charged oxygen-containing group on the surface of MXene, so that self-assembly of Mxene on the surface of the active metal layer is realized, and the active metal-MXene modification layer is obtained.
The invention provides the application of the solid electrolyte in the technical scheme or the solid electrolyte obtained by the preparation method in the technical scheme in an all-solid-state lithium battery.
In the invention, the active metal-MXene modification layer of the solid electrolyte is preferably in contact with the lithium metal negative electrode.
In the present invention, the all-solid-state lithium battery preferably includes a positive electrode, a solid electrolyte, and a lithium metal negative electrode; the solid electrolyte is preferably the solid electrolyte described in the above technical scheme or the solid electrolyte obtained by the preparation method described in the above technical scheme.
In the present invention, the positive electrode preferably includes a positive electrode material, a conductive agent, a binder, and an organic solvent; the invention has no special requirements on the anode material, the conductive agent and the binder, and can be prepared by adopting the anode material, the conductive agent and the binder of the lithium battery, which are well known by the technical personnel in the field; in the present invention, the organic solvent is preferably N-methylpyrrolidone.
The invention has no special requirements on the mass ratio of the positive electrode material, the conductive agent, the binder and the organic solvent.
In the present invention, the positive electrode is preferably prepared by the following method: and mixing the positive electrode material, the conductive agent, the binder and the organic solvent to obtain the positive electrode. The present invention has no particular requirement for the mixing.
In the present invention, the all-solid-state lithium battery is preferably prepared by the following method:
and coating molten metal lithium on one side of an active metal-MXene modification layer of the solid electrolyte, coating an anode on the other side of the solid electrolyte, and drying, sealing and pressing to obtain the all-solid-state lithium battery.
The invention has no special requirements on the thickness of the coating and the specific implementation process of the coating, and the conventional coating thickness and operation which are well known to the technical personnel in the field can be adopted; in the invention, the drying temperature is preferably 70-120 ℃, and more preferably 80-100 ℃; the drying time is preferably 8-12 h, and more preferably 10 h; in the invention, the pressure of the sealing pressure is preferably 8 MPa; the invention has no special requirements on the specific implementation process of the sealing and pressing.
In the present invention, the all-solid-state lithium battery is preferably prepared in a glove box.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the disclosed embodiments are merely exemplary of the invention, and are not intended to be exhaustive or exhaustive. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Weighing 200mg of metal zinc, placing the metal zinc in a tungsten boat at the bottom of an evaporation coating instrument, and fixing Li at the top6.4La3Zr1.4Ta0.6O12Solid electrolyte in vacuum condition (vacuum degree less than or equal to 10)-3Pa) in Li6.4La3Zr1.4Ta0.6O12Evaporating a metal zinc layer with the thickness of 100nm on the surface at the temperature of 1500 ℃ for 30 s;
weighing 2g of Ti2AlC material and 20mLHFMixing water solution (mass concentration is preferably 0.4g/mL), etching for 30min, centrifuging and washing the suspension to obtain multilayer Ti3C2Ty；
A plurality of layers of Ti3C2TyStirring and intercalating with TBAOH aqueous solution (with mass concentration of 40 wt% preferably and excessive) for 12h, performing ultrasonic stripping and dispersing for 2h, centrifuging, taking supernatant, and diluting with deionized water to obtain single-layer Ti with mass concentration of 0.5mg/mL3C2TyAn aqueous solution;
a single layer of Ti3C2TyDropwise addition of an aqueous solution to Li6.4La3Zr1.4Ta0.6O12The surface of the metallic zinc layer of the solid electrolyte surface is made of Ti3C2TySpreading the water solution completely to wet the metal zinc layer, reacting for 30min, and evaporating the solvent in a 70 deg.C blast drying oven to obtain initial zinc metal-Ti3C2TyA finishing layer;
repeatedly dropping single-layer Ti3C2TyThe aqueous solution was 2 times to obtain the final product in Li6.4La3Zr1.4Ta0.6O12Zn-Ti on surface of solid electrolyte3C2TyModification of the layer to obtain a solid electrolyte, Zn-Ti3C2TyThe total thickness of the decoration layer is 200 nm.
FIG. 1 shows a solid electrolyte prepared in example 1 of the present invention and Li as a raw material6.4La3Zr1.4Ta0.6O12A physical contrast map of the solid electrolyte; a in FIG. 1 is Li6.4La3Zr1.4Ta0.6O12Optical photograph of solid electrolyte, wherein b in FIG. 1 is the solid electrolyte prepared in example 1, Zn-Ti was visually observed3C2TyThe modification layer is successfully coated on Li6.4La3Zr1.4Ta0.6O12A solid electrolyte surface.
FIG. 2 shows a solid electrolyte prepared in example 1 of the present invention and Li as a raw material6.4La3Zr1.4Ta0.6O12Comparative picture of electrolytic photograph of solid electrolyte and lithium metal contact interface; as can be seen from c in FIG. 2, Li before modification6.4La3Zr1.4Ta0.6O12There is a clear interface between the solid electrolyte and the metallic lithium, as can be seen from d in FIG. 2, via Zn-Ti3C2TyLi coated with decorative layer6.4La3Zr1.4Ta0.6O12The solid electrolyte has good contact with lithium metal, and no obvious interface is seen; furthermore, by comparing the small diagram at the upper right corner of FIG. 2 c with the small diagram at the upper right corner of FIG. 2d, it can be intuitively obtained that the images are compared with the images before maintenance via Zn-Ti3C2TyLi coated with decorative layer6.4La3Zr1.4Ta0.6O12The solid electrolyte is capable of being in substantially wetting contact with the lithium metal.
Example 2
Weighing 200mg of metal zinc, placing the metal zinc in a tungsten boat at the bottom of an evaporation coating instrument, and fixing Li at the top6.4La3Zr1.4Ta0.6O12Solid electrolyte in vacuum condition (vacuum degree less than or equal to 10)-3Pa) in Li6.4La3Zr1.4Ta0.6O12A metal zinc layer with the thickness of 100nm is evaporated on the surface, the evaporation temperature is 1000 ℃, and the time is 30 s;
weighing 1g of Ti2Mixing AlC material and 20mL HF aqueous solution (mass concentration is preferably 0.4g/mL) for etching, after etching for 30min, centrifuging and washing suspension to obtain multilayer Ti3C2Ty；
A plurality of layers of Ti3C2TyStirring and intercalating with TBAOH aqueous solution (with mass concentration of 40 wt% and excessive) for 12h, performing ultrasonic stripping and dispersing for 2h, centrifuging, taking supernatant, and diluting with deionized water to obtain single-layer Ti with mass concentration of 1mg/mL3C2TyAn aqueous solution;
a single layer of Ti3C2TyDropwise addition of an aqueous solution to Li6.4La3Zr1.4Ta0.6O12Surface of metallic zinc layer on the surface of solid electrolyte, so that Ti3C2TySpreading the water solution completely to wet the metal zinc layer, reacting for 40min, and evaporating the solvent in a 70 deg.C blast drying oven to obtain initial zinc metal-Ti3C2TyA finishing layer;
repeatedly dropping single-layer Ti3C2TyThe aqueous solution was 2 times to finally obtain a solution set at Li6.4La3Zr1.4Ta0.6O12Zn-Ti on surface of solid electrolyte3C2TyModification layer to obtain solid electrolyte, Zn-Ti3C2TyThe total thickness of the decoration layer is 300 nm.
Example 2 photo-photographs of the obtained solid electrolyte and the effect of contact with metallic lithium were the same as those of example 1.
Example 3
Weighing 200mg of metal zinc, placing the metal zinc in a tungsten boat at the bottom of an evaporation coating instrument, and fixing Li at the top6.4La3Zr1.4Ta0.6O12Solid electrolyte in vacuum condition (vacuum degree less than or equal to 10)-3Pa) in Li6.4La3Zr1.4Ta0.6O12A metal zinc layer with the thickness of 100nm is evaporated on the surface, the evaporation temperature is 1200 ℃, and the time is 30 s;
weighing 2g of Ti2Mixing AlC material and 20mL HF aqueous solution (mass concentration is preferably 0.4g/mL) for etching, after etching for 30min, centrifuging and washing suspension to obtain multilayer Ti3C2Ty；
A plurality of layers of Ti3C2TyStirring and intercalating with TBAOH aqueous solution (with mass concentration of 40 wt% preferably and excessive) for 12h, performing ultrasonic stripping and dispersing for 2h, centrifuging, taking supernatant, and diluting with deionized water to obtain single-layer Ti with mass concentration of 1.5mg/mL3C2TyAn aqueous solution;
a single layer of Ti3C2TyDropwise addition of an aqueous solution to Li6.4La3Zr1.4Ta0.6O12The surface of the metallic zinc layer of the solid electrolyte surface is made of Ti3C2TySpreading the water solution completely to wet the metal zinc layer, reacting for 50min, and evaporating the solvent in a 70 deg.C blast drying oven to obtain initial zinc metal-Ti3C2TyA finishing layer;
repeatedly dropping single-layer Ti3C2TyThe aqueous solution was 2 times to obtain the final product in Li6.4La3Zr1.4Ta0.6O12Zn-Ti on surface of solid electrolyte3C2TyModification of the layer to obtain a solid electrolyte, Zn-Ti3C2TyThe total thickness of the decoration layer is 400 nm.
Example 3 photo-graphs of the obtained solid electrolyte and the effect of contact with metallic lithium were the same as in example 1.
Example 4
Weighing 200mg of metal zinc, placing the metal zinc in a tungsten boat at the bottom of an evaporation coating instrument, and fixing perovskite Li on the top3xLa2/3-xTiO3Solid electrolyte in vacuum condition (vacuum degree less than or equal to 10)-3Pa) in Li6.4La3Zr1.4Ta0.6O12Evaporating a metal zinc layer with the thickness of 100nm on the surface at the temperature of 1500 ℃ for 30 s;
weighing 2g of Ti2Mixing AlC material and 20mLHF water solution (mass concentration is preferably 0.4g/mL) for etching, after etching for 30min, centrifuging and washing suspension to obtain multilayer Ti3C2Ty；
A plurality of layers of Ti3C2TyStirring and intercalating with TBAOH aqueous solution (with mass concentration of 40 wt% preferably and excessive) for 12h, performing ultrasonic stripping and dispersing for 2h, centrifuging, taking supernatant, and diluting with deionized water to obtain single-layer Ti with mass concentration of 0.5mg/mL3C2TyAn aqueous solution;
a single layer of Ti3C2TyDropwise addition of an aqueous solution to perovskite Li3xLa2/3-xTiO3The surface of the metal zinc layer on the surface of the solid electrolyte,make Ti3C2TySpreading the water solution completely to wet the metal zinc layer, reacting for 30min, and evaporating the solvent in a 70 deg.C blast drying oven to obtain initial zinc metal-Ti3C2TyA finishing layer;
repeatedly dropping single-layer Ti3C2TyThe aqueous solution is processed for 3 times to obtain the final product of the perovskite Li3xLa2/3-xTiO3Zn-Ti on surface of solid electrolyte3C2TyModification of the layer to obtain a solid electrolyte, Zn-Ti3C2TyThe total thickness of the decoration layer is 200 nm.
Example 4 photo-photographs of the obtained solid electrolyte and the effect of contact with metallic lithium were the same as those of example 1.
Example 5
Weighing 200mg of metal zinc, placing the metal zinc in a tungsten boat at the bottom of an evaporation coating instrument, and fixing Li at the top6.4La3Zr1.4Ta0.6O12Solid electrolyte in vacuum condition (vacuum degree less than or equal to 10)-3Pa) in Li6.4La3Zr1.4Ta0.6O12Evaporating a metal zinc layer with the thickness of 100nm on the surface at the temperature of 1500 ℃ for 30 s;
weighing 2g of Ti4AlN3Mixing the material with 20mLHF water solution (mass concentration is preferably 0.4g/mL) for etching, centrifuging and washing the suspension after etching for 30min to obtain multilayer Ti3C2Ty；
A plurality of layers of Ti3C2TyStirring and intercalating with TBAOH aqueous solution (with mass concentration of 40 wt% preferably and excessive) for 12h, performing ultrasonic stripping and dispersing for 2h, centrifuging, taking supernatant, and diluting with deionized water to obtain single-layer Ti with mass concentration of 0.5mg/mL4N3An aqueous solution;
a single layer of Ti4N3Dropwise addition of an aqueous solution to Li6.4La3Zr1.4Ta0.6O12The surface of the metallic zinc layer of the solid electrolyte surface is made of Ti4N3The aqueous solution is completely spread and moistenedWet metallic zinc layer, reacting for 30min, and evaporating solvent in a 80 deg.C air-blast drying oven to obtain initial zinc metal Ti4N3A finishing layer;
repeatedly dropping a single layer of Ti4N3The aqueous solution was 2 times to obtain the final product in Li6.4La3Zr1.4Ta0.6O12Zn-Ti on surface of solid electrolyte4N3Modification of the layer to obtain a solid electrolyte, Zn-Ti4N3The total thickness of the decoration layer is 300 nm.
Example 5 photo-photographs of the obtained solid electrolyte and the effect of contact with metallic lithium were the same as those of example 1.
Application example 1
In a glove box, a lithium iron phosphate positive electrode material, acetylene black and polyvinylidene fluoride are mixed according to the mass ratio of 8:1:1, mixed and then mixed with N-methyl-2-pyrrolidone to form positive electrode slurry, the positive electrode slurry is coated on the unmodified side of the solid electrolyte prepared in example 1, and molten metal lithium is coated on Zn-Ti of the solid electrolyte prepared in example 13C2TyAnd (3) drying the coated solid electrolyte at the constant temperature of 80 ℃ for 10 hours on one side of the modification layer, placing the dried solid electrolyte on a button sealing press, and pressing the dried solid electrolyte under the pressure of 8MPa to obtain the all-solid-state lithium battery.
Comparative example 1
The preparation method is basically the same as that of the application example, except that: with unmodified Li6.4La3Zr1.4Ta0.6O12A solid electrolyte.
Test example 1
The Landt battery test system is adopted to perform constant-current charge-discharge test on the all-solid-state lithium batteries prepared in the example 1 and the comparative example 1, the voltage range is 2.8-4.0V, and the current density is 0.1mA/cm-2. The test result is shown in fig. 3, and it can be seen from fig. 3 that the initial discharge capacity of the positive electrode of the all-solid-state lithium battery prepared in application example 1 is 148.5mAh/g, the capacity retention rate after 50 cycles is close to 100%, and the capacity retention rate after 50 cycles is only 77% compared with the initial discharge capacity 133mAh/g of the positive electrode of comparative example 1, and the discharge of the all-solid-state lithium battery prepared in application example 1 of the present inventionThe specific capacity is obviously improved, the capacity retention rate is obviously increased, and the Zn-Ti is proved3C2TyThe modification layer can reduce the interface resistance between the solid electrolyte and the lithium metal cathode and improve the electrochemical performance of the battery.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A method of making a solid electrolyte membrane for a lithium battery, comprising the steps of:
(1) in a vacuum environment, evaporating active metal on the surface of an inorganic solid electrolyte membrane to form an active metal zinc layer on the surface of the inorganic solid electrolyte membrane, wherein the active metal is metal Zn capable of carrying out redox reaction with oxygen-containing functional groups on the surface of MXene;
(2) dropwise adding the monolayer MXene aqueous dispersion with the oxygen-containing functional group on the surface to the surface of the active metal Zn layer to perform redox reaction, and forming an initial active metal Zn-MXene modification layer on the surface of the inorganic solid electrolyte membrane; the mass concentration of the single-layer MXene aqueous dispersion is 0.5-2 mg/mL;
(3) and (3) circularly performing the step (2) on the surface of the initial active metal Zn-MXene modified layer for N times to obtain the solid electrolyte membrane.
2. The method according to claim 1, wherein in the step (1), the thickness of the active metal zinc layer is 50 to 300nm, and the evaporation time is 30 to 60 seconds.
3. The method according to claim 1, wherein in the step (2), the time of the redox reaction is 30 to 60 min.
4. A solid electrolyte membrane prepared by the preparation method of claim 1, comprising an inorganic solid electrolyte membrane and an active metal Zn-MXene modification layer disposed on the surface of the inorganic solid electrolyte membrane, wherein the active metal Zn-MXene modification layer comprises an active metal Zn and MXene chemically bonded to the active metal Zn; the active metal is metal Zn which can perform redox reaction with oxygen-containing functional groups on the surface of MXene.
5. The solid electrolyte membrane according to claim 4, wherein the active metal Zn-MXene modification layer has a thickness of 100 to 500 nm.
6. The solid electrolyte membrane according to claim 4, wherein the MXene has a chemical formula of Mn+1XnTyM is a transition metal element, X is a C element or an N element, and T is F and OH;
n is 1, 2 or 3, and y is more than or equal to 0 and less than 2.
7. The solid electrolyte membrane according to claim 6, wherein the M is a Ti element, a Nb element, a V element, or a Mo element.
8. The solid electrolyte membrane according to claim 6, wherein the inorganic solid electrolyte in the inorganic solid electrolyte membrane is one or more of an oxide-type solid electrolyte, a sulfide-type solid electrolyte, a perovskite-type solid electrolyte, and a NASICON-type solid electrolyte.
9. Use of the solid electrolyte membrane obtained by the production method according to any one of claims 1 to 3 or the solid electrolyte membrane according to any one of claims 4 to 8 in an all-solid lithium battery.
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