CN114094042A - Liquid metal negative pole piece and preparation method and application thereof - Google Patents

Liquid metal negative pole piece and preparation method and application thereof Download PDF

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Publication number
CN114094042A
CN114094042A CN202111328572.9A CN202111328572A CN114094042A CN 114094042 A CN114094042 A CN 114094042A CN 202111328572 A CN202111328572 A CN 202111328572A CN 114094042 A CN114094042 A CN 114094042A
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alloy
lithium
liquid
solid
metal
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张典政
陈规伟
冀亚娟
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Eve Energy Co Ltd
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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

Abstract

The invention provides a liquid metal negative pole piece and a preparation method and application thereof. And the surface of the negative pole piece is coated with liquid alloy. The invention provides a liquid metal electrode with a liquid alloy coated on the surface of metal lithium, which is used for improving the interface contact between an electrolyte and a negative electrode, greatly improving the critical current density of a solid electrolyte, filling pores generated by lithium removal in a circulating process, realizing the self-healing of an interface, avoiding the formation and growth of lithium dendrites and effectively solving the problem of interface contact.

Description

Liquid metal negative pole piece and preparation method and application thereof
Technical Field
The invention relates to a lithium ion battery, relates to a lithium ion solid-state battery, and particularly relates to a liquid metal negative electrode plate of the lithium ion solid-state battery, and a preparation method and application thereof.
Background
With the deep thought of the green environmental protection concept, the new energy lithium battery is widely applied from small and medium-sized electronic products such as mobile phones and computers to large-sized energy equipment such as electric automobiles in recent years by virtue of the advantages of high voltage, high energy density, long cycle life, wide electrochemical window and the like, and thus higher requirements are provided for the lithium battery, and the energy density of the single battery reaches 500 Wh/kg; in addition, there are higher demands for the life span, safety performance, etc. of the battery.
The solid-state lithium battery is considered as the development direction of the future lithium battery, the solid-state lithium battery adopts solid electrolyte to replace a diaphragm and electrolyte in the traditional lithium battery, the spontaneous combustion and explosion risks of the battery are obviously reduced, the battery cannot be obviously decomposed at high temperature, the safety is high, and the working temperature range is wide; the solid electrolyte is difficult to leak and volatilize, and the electrolyte cannot be dried up during long-term circulation, so that the cycle life is long, and the service life of the battery is long; and solid-state batteries may use a lithium metal negative electrode, lithium metal possessing a low electrochemical potential (-3.04V compared to a standard hydrogen electrode), low density (0.53 g/cm)3) And high theoretical capacity (3860 m A · h/g), are considered key materials for achieving high energy density batteries.
However, the existing solid electrolytes cannot be well matched with lithium metal for two main reasons: firstly, the interface between the solid electrolyte and the metal lithium is incompatible, and the chemical stability and the electrochemical stability of the interface between the solid electrolyte and the metal lithium are poor, such as solid sulfide electrolyte LGPS, solid polymer electrolyte PVDF, solid inorganic oxide electrolyte LATP, LLTO and the like; second, the formation and penetration of lithium dendrites at high current densities. When the current density is greater than the Critical Current Density (CCD), voids may form at the interface of the negative electrode and the electrolyte as the cycle progresses, further resulting in an increase in the local current density, eventually resulting in the formation of lithium dendrites inside the electrolyte to initiate short circuits.
Common methods to ameliorate the above problems include: firstly, constructing a semi-solid electrode, and coating molten metal lithium on the surface of solid electrolyte in a liquid form; secondly, a lithium-philic interface is added, and a layer of Al and Al is deposited on the surface of the solid electrolyte2O3And ZnO and other coatings, not only prevents the side reaction caused by the direct contact of lithium metal and solid electrolyte, but also improves the lithium phobicity of the electrolyte interface and promotes the uniform deposition of the lithium metal at the interface; thirdly, a multifunctional interface layer is constructed, polymer-based solid electrolyte is added to the interface, interface contact is improved, interface side reaction is prevented, such as PEO, or an artificial solid electrolyte interface film (SEI), such as LiPO, is introduced4Enhanced solid electrolyteStability with metallic lithium.
CN108933258A discloses a preparation method of an all-solid-state lithium ion battery of a three-dimensional composite metal lithium cathode, wherein metal lithium is loaded on a carrier material by a chemical or physical method of electrochemical deposition or melt infiltration to prepare the three-dimensional composite metal lithium cathode, and the carrier material is activated carbon fiber cloth; preparing a PMMA-PEI-based all-solid-state polymer electrolyte membrane; tearing the PMMA-PEI-based all-solid-state polymer electrolyte membrane from the surface of a poly tetrachloroethylene plate, and cutting the membrane into a proper size for later use; with LiFePO4And (3) assembling the positive electrode, the PMMA-PEI-based all-solid-state polymer electrolyte membrane and the three-dimensional composite metal lithium negative electrode in sequence to obtain the all-solid-state lithium ion button cell. But the active carbon fiber is used as a negative electrode carrier, and the prepared all-solid-state electrolyte has large interface resistance.
CN105470466A discloses an all-solid-state battery with a framework-supported alloy negative electrode and a preparation method thereof, wherein a lithium boron alloy foil is used as a negative electrode material of the all-solid-state lithium battery, but after the lithium boron alloy foil is alloyed with boron, the density of lithium ions in the negative electrode is reduced, and the lithium ion conductivity of the system is reduced.
CN113381055A discloses a lithium/garnet-based solid electrolyte interface with low interface impedance and a method for preparing the same, the lithium metal battery comprises: the lithium ion battery includes a substrate, a positive electrode disposed on the substrate, a garnet-based solid electrolyte disposed on the positive electrode, and a metallic lithium negative electrode disposed on the garnet-based solid electrolyte. Wherein, the discoloration layer sets up in the interface department of metal lithium negative pole and garnet base solid state electrolyte, and this discoloration layer includes: a first part and a second part, wherein the first part comprises a lithium-containing compound and the second part comprises a garnet-based solid-state electrolyte composition. The metallic lithium negative electrode can be lithium simple substance or/and lithium alloy. However, garnet solid electrolytes are expensive and not suitable for industrial production.
How to industrially produce a solid-state battery with high critical current density and good interface contact at low cost is an important research direction in the field.
Disclosure of Invention
The invention aims to provide a liquid metal electrode with a liquid alloy coated on the surface of metal lithium, which effectively solves the problem of interface contact.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a liquid metal negative pole piece, wherein the surface of the negative pole piece is coated with liquid alloy.
According to the invention, the liquid alloy is coated on the surface of the metal lithium, so that a liquid metal electrode is constructed, the interface contact between the electrolyte and the negative electrode is improved, the Critical Current Density (CCD) of the solid electrolyte is greatly improved, the pores generated by lithium removal can be filled in the circulation process, the self-healing of the interface is realized, the formation and the growth of lithium dendrites are avoided, and the problem of interface contact is effectively solved.
As a preferred technical solution of the present invention, the liquid alloy includes any one of a tin-based alloy, an aluminum-based alloy, a silicon-based alloy, a silver-based alloy, an antimony-based alloy, and a sodium-based alloy.
Preferably, the alloy includes any one of Na-K alloy, Cu-Sn alloy, Sn-C alloy, Sn-Zr alloy, Al-Cu alloy, Al-Mn alloy, Al-Ni alloy, Si-Mn alloy, Si-Mg alloy, or Si-Cr.
The second purpose of the invention is to provide a preparation method of the liquid metal negative pole piece, which comprises the following steps:
heating the two metal simple substances to a single-phase liquid state, mixing, and cooling to obtain a liquid alloy;
and coating the liquid alloy on a substrate to obtain the liquid metal negative pole piece.
As a preferable technical scheme of the invention, the metal simple substance comprises any one of Na, K, Cu, Sn, C, Zr, Al, Mn, Ni, Si, Cr or Mg.
Preferably, the ratio of the two simple metals is 0.25-4, wherein the ratio can be 0.25, 0.5, 1, 1.5, 2, 2.5, 3, 3.5 or 4.
As a preferred embodiment of the present invention, the substrate includes lithium metal.
Preferably, the thickness of the lithium metal is 8 to 9mm, wherein the thickness may be 8mm, 8.1mm, 8.2mm, 8.3mm, 8.4mm, 8.5mm, 8.6mm, 8.7mm, 8.8mm, 8.9mm, or 9mm, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the liquid alloy coating has a volume of 4 to 5 μ L, wherein the volume may be 4 μ L, 4.1 μ L, 4.2 μ L, 4.3 μ L, 4.4 μ L, 4.5 μ L, 4.6 μ L, 4.7 μ L, 4.8 μ L, 4.9 μ L, or 5 μ L, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
In a preferred embodiment of the present invention, the liquid alloy is coated in a thickness of 1 to 100% of the thickness of the substrate, wherein the coating thickness may be 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 100% in percentage by weight, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
The invention also provides a solid-state battery, which comprises the liquid metal negative pole piece.
Preferably, the solid-state battery further comprises a positive electrode sheet and a solid-state electrolyte.
As a preferable technical scheme of the invention, the positive pole piece comprises any one of a ternary positive pole, a lithium iron phosphate positive pole, a lithium manganate positive pole, a lithium cobaltate positive pole or a lithium sulfur positive pole.
As a preferred embodiment of the present invention, the solid electrolyte includes any one of a PEO-based polymer electrolyte, a PVDF-based polymer electrolyte, a PMMA-based polymer electrolyte, LLZTO, LLTO, LATP, LGPS, or LPS.
Compared with the prior art, the invention has the following beneficial effects:
(1) the liquid metal negative pole piece prepared by the method can greatly improve the critical current density of the solid electrolyte, and the critical current density can reach 1.34mA/cm2Above, get togetherThe flow impedance can be reduced to below 19.9 omega, and the problem of interface contact is effectively solved.
(2) The preparation method of the liquid metal negative pole piece is simple and efficient, can be used for continuous large-scale production, and is suitable for industrialization.
(3) The liquid metal cathode of the present invention can be applied to a variety of different solid electrolytes, and has wide applicability.
Drawings
Fig. 1 is a structural diagram of a lithium battery in examples 1 to 14 of the present invention.
FIG. 2 is a graph showing the critical current densities in example 1 of the present invention, examples 10 to 14 and comparative example 3.
FIG. 3 is a graph of AC impedances in inventive example 1, examples 10-14, and comparative example 3.
In the figure: 1-a solid electrolyte; 2-liquid alloy; 3-lithium metal sheet.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a solid-state battery containing a liquid metal negative pole piece, which comprises the following steps:
the method comprises the following steps: taking LLTO with the thickness of about 1mm and the diameter of 10mm as a solid electrolyte 1, and removing LiCO by polishing, ultrasonic cleaning and heat treatment at 500 ℃ for 3h3And LiOH, performing blowing treatment on the electrolyte by using nitrogen to remove impurities, dust and the like remained on the surface;
step two: melting pure sodium and pure potassium, transferring into a glass bottle according to the proportion of 1:1, heating to a single-phase liquid state, uniformly mixing, and cooling to prepare a Na-K alloy, namely a liquid alloy 2;
step three: taking a lithium metal sheet 3 with the diameter of 8mm, and coating 4 mu L of Na-K alloy, namely liquid alloy 2, on one surface of the lithium sheet uniformly;
step four: and (3) contacting one surface of the lithium metal sheet coated with the Na-K alloy with the LLTO sheet, assembling the lithium battery, measuring the critical current density, and evaluating the improvement effect. The structure of the lithium battery is shown in fig. 1.
Example 2
The embodiment provides a preparation method of a solid-state battery containing a liquid metal negative pole piece, which comprises the following steps:
the method comprises the following steps: taking LLZTO with thickness of 1mm and diameter of 12mm as solid electrolyte 1, polishing LLZTO, ultrasonic cleaning, and heat treating at 500 deg.C for 3 hr to remove LiCO3And LiOH, performing blowing treatment on the electrolyte by using nitrogen to remove impurities, dust and the like remained on the surface;
step two: melting pure tin and pure copper, transferring the melted pure tin and pure copper into a glass bottle according to the proportion of 4:1, heating the mixture until a single-phase liquid state is uniformly mixed, and cooling the mixture to prepare a Cu-Sn alloy, namely a liquid alloy 2;
step three: taking a lithium metal sheet 3 with the diameter of 9mm, coating 5 mu L of Cu-Sn alloy on one surface of the lithium sheet, and uniformly coating;
step four: and (3) contacting one surface of the lithium metal sheet coated with the Cu-Sn alloy with the LLZTO sheet, assembling the lithium battery, measuring the critical current density, and evaluating the improvement effect. The structure of the lithium battery is shown in fig. 1.
Example 3
The embodiment provides a preparation method of a solid-state battery containing a liquid metal negative pole piece, which comprises the following steps:
the method comprises the following steps: PEO polymer electrolyte with the thickness of about 1mm and the diameter of 11mm is taken as the solid electrolyte 1, and LiCO is removed by grinding and polishing, ultrasonic cleaning and heat treatment at 500 ℃ for 3h3And LiOH, performing blowing treatment on the electrolyte by using nitrogen to remove impurities, dust and the like remained on the surface;
step two: melting pure aluminum and pure copper, transferring the melted pure aluminum and pure copper into a glass bottle according to the proportion of 4:1, heating the mixture until a single-phase liquid state is uniformly mixed, and cooling the mixture to prepare an Al-Cu alloy, namely a liquid alloy 2;
step three: taking a lithium metal sheet 3 with the diameter of 9mm, coating 5 mu L of Al-Cu alloy on one surface of the lithium sheet, and uniformly coating;
step four: and (3) contacting one surface of the lithium metal sheet coated with the Al-Cu alloy with a PEO polymer electrolyte sheet, assembling the lithium battery, measuring the critical current density, and evaluating the improvement effect. The structure of the lithium battery is shown in fig. 1.
Example 4
The embodiment provides a preparation method of a solid-state battery containing a liquid metal negative pole piece, which comprises the following steps:
the method comprises the following steps: taking LLTO with thickness of 1mm and diameter of 12mm as solid electrolyte 1, polishing LLTO, ultrasonic cleaning, and heat treating at 500 deg.C for 3 hr to remove LiCO3And LiOH, performing blowing treatment on the electrolyte by using nitrogen to remove impurities, dust and the like remained on the surface;
step two: melting pure aluminum and pure magnesium, transferring the molten pure aluminum and pure magnesium into a glass bottle according to the ratio of 3:1, heating the molten pure aluminum and pure magnesium to a single-phase liquid state, uniformly mixing the single-phase liquid state and the liquid state, and cooling the mixture to prepare an Al-Mn alloy, namely a liquid alloy 2;
step three: taking a lithium metal sheet 3 with the diameter of 9mm, coating 4 mu L of Al-Mn alloy on one surface of the lithium sheet, and uniformly coating;
step four: and (3) contacting one surface of the lithium metal sheet coated with the Al-Mn alloy with a solid electrolyte sheet, assembling the lithium battery, measuring the critical current density, and evaluating the improvement effect. The structure of the lithium battery is shown in fig. 1.
Example 5
The embodiment provides a preparation method of a solid-state battery containing a liquid metal negative pole piece, which comprises the following steps:
the method comprises the following steps: taking LLTO with thickness of 1mm and diameter of 12mm as solid electrolyte 1, polishing LLTO, ultrasonic cleaning, and heat treating at 500 deg.C for 3 hr to remove LiCO3And LiOH, performing blowing treatment on the electrolyte by using nitrogen to remove impurities, dust and the like remained on the surface;
step two: melting pure silicon and pure manganese, transferring the melted pure silicon and pure manganese into a glass bottle according to the ratio of 2:1, heating the mixture to a single-phase liquid state, uniformly mixing the mixture, and cooling the mixture to prepare a Si-Mn alloy, namely a liquid alloy 2;
step three: taking a lithium metal sheet 3 with the diameter of 9mm, coating 5 mu L of Si-Mn alloy on one surface of the lithium sheet, and uniformly coating;
step four: and (3) contacting one surface of the lithium metal sheet coated with the Si-Mn alloy with a solid electrolyte sheet, assembling the lithium battery, measuring the critical current density, and evaluating the improvement effect. The structure of the lithium battery is shown in fig. 1.
Example 6
In this example, pure sodium and pure potassium in the second step were replaced with pure aluminum and pure nickel to prepare an Al — Ni alloy, and the other conditions were the same as in example 1.
Example 7
In this example, pure sodium and pure potassium in the second step were replaced with pure silicon and pure magnesium to prepare a Si — Mg alloy, and the other conditions were the same as in example 1.
Example 8
This example was carried out under the same conditions as in example 1 except that the coating volume of the Na-K alloy in step three was changed to 3. mu.L.
Example 9
This example was carried out under the same conditions as in example 1 except that the coating volume of the Na-K alloy in step three was changed to 6. mu.L.
Example 10
In this example, the ratio of pure sodium to pure potassium was changed to 7:3 instead of 1:1, and the other conditions were the same as in example 1.
Example 11
In this example, the ratio of pure sodium to pure potassium was changed to 6:4 instead of 1:1, and the other conditions were the same as in example 1.
Example 12
In this example, the ratio of pure sodium to pure potassium was changed to 4:6 instead of 1:1, and the other conditions were the same as in example 1.
Example 13
In this example, the ratio of pure sodium to pure potassium was changed to 3:7 instead of 1:1, and the other conditions were the same as in example 1.
Example 14
In this example, the ratio of pure sodium to pure potassium was changed to 2:8, and the other conditions were the same as in example 1.
Comparative example 1
In the comparative example, pure sodium in the step two is replaced by pure potassium with equal mass to prepare the potassium liquid metal, and other conditions are the same as those in the example 1.
Comparative example 2
In the comparative example, pure potassium in the second step is replaced by pure sodium with equal mass to prepare sodium liquid metal, and other conditions are the same as those in example 1.
Comparative example 3
This comparative example did not prepare a liquid alloy. Lithium pair batteries were made by combining metallic lithium sheets directly with LLTO solid-state electrolyte, wherein the critical current densities of examples 1, 10-14 and comparative example 3 are shown in FIG. 2 and the AC impedance plot is shown in FIG. 3.
The solid-state batteries of examples 1 to 14 and comparative examples 1 to 3 were subjected to critical current density tests, and the results are shown in table 1.
TABLE 1
Figure BDA0003348046020000101
Figure BDA0003348046020000111
The results show that: the critical current density of the solid electrolyte can be remarkably improved by coating a layer of liquid metal electrodes such as Na-K alloy, Cu-Sn alloy, Al-Cu alloy and the like on the surface of the metal lithium to construct the liquid metal electrodes, and compared with the embodiment 1, the critical current density is reduced and the alternating current impedance is increased in the comparative examples 1-3, so that the interface contact between the electrolyte and the negative electrode is improved by the liquid alloy, the internal resistance of the battery is greatly reduced, and the problem of poor interface contact between the solid electrolyte and a pole piece in the solid lithium battery is well solved. Compared with the embodiment 1, the embodiment 8 and the embodiment 9 have the advantage that the interface contact is better when the coating volume of the alloy is replaced and the coating volume of the alloy is 4-5 mu L. Comparing example 1 with examples 10-14, it can be seen that when the ratio of the two simple metals is 0.25-4, the critical current density is large and the AC impedance is small. Comparing examples 6-7 with example 1, it can be seen that the resistance values of pure sodium and pure potassium alloys are the smallest.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. The liquid metal negative pole piece is characterized in that the surface of the negative pole piece is coated with liquid alloy.
2. The negative electrode plate as claimed in claim 1, wherein the liquid alloy comprises any one of tin-based alloy, aluminum-based alloy, silicon-based alloy, silver-based alloy, antimony-based alloy or sodium-based alloy;
preferably, the alloy includes any one of Na-K alloy, Cu-Sn alloy, Sn-C alloy, Sn-Zr alloy, Al-Cu alloy, Al-Mn alloy, Al-Ni alloy, Si-Mn alloy, Si-Mg alloy, or Si-Cr.
3. The preparation method of the liquid metal negative electrode plate as claimed in claim 1 or 2, wherein the preparation method comprises the following steps:
heating the two metal simple substances to a single-phase liquid state, mixing, and cooling to obtain a liquid alloy;
and coating the liquid alloy on a substrate to obtain the liquid metal negative pole piece.
4. The production method according to claim 3, wherein the elemental metal includes any one of Na, K, Cu, Sn, C, Zr, Al, Mn, Ni, Si, Cr, or Mg;
preferably, the ratio of the two metal simple substances is 0.25-4.
5. The production method according to claim 3 or 4, wherein the substrate comprises lithium metal;
preferably, the thickness of the lithium metal is 8-9 mm.
6. The method according to any one of claims 3 to 5, wherein the liquid alloy is applied in a volume of 4 to 5 μ L.
7. The method according to any one of claims 3 to 6, wherein the liquid alloy is applied to a thickness of 1 to 100% of the thickness of the substrate.
8. A solid-state battery comprising the liquid metal negative electrode sheet according to claim 1 or 2;
preferably, the solid-state battery further comprises a positive electrode sheet and a solid-state electrolyte.
9. The solid-state battery according to claim 8, wherein the positive electrode sheet includes any one of a ternary positive electrode, a lithium iron phosphate positive electrode, a lithium manganese oxide positive electrode, a lithium cobalt oxide positive electrode, or a lithium sulfur positive electrode.
10. The solid-state battery according to claim 8 or 9, wherein the solid-state electrolyte comprises any one of a PEO-based polymer electrolyte, a PVDF-based polymer electrolyte, a PMMA-based polymer electrolyte, LLZTO, LLTO, LATP, LGPS, or LPS.
CN202111328572.9A 2021-11-10 2021-11-10 Liquid metal negative pole piece and preparation method and application thereof Pending CN114094042A (en)

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