CN112086680B - All-solid-state electrolyte layer and preparation method and application thereof - Google Patents

All-solid-state electrolyte layer and preparation method and application thereof Download PDF

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CN112086680B
CN112086680B CN202011010092.3A CN202011010092A CN112086680B CN 112086680 B CN112086680 B CN 112086680B CN 202011010092 A CN202011010092 A CN 202011010092A CN 112086680 B CN112086680 B CN 112086680B
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electrolyte layer
solid electrolyte
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powder
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CN112086680A (en
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李瑞杰
王磊
黄海强
陈少杰
周龙捷
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Svolt Energy Technology 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
    • 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
    • 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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to an all-solid electrolyte layer and a preparation method and application thereof; the all-solid electrolyte layer comprises a laminated three-layer structure, wherein the intermediate layer comprises solid electrolyte particles and powder M, and the powder M is selected from substances capable of forming an alloy with lithium metal; the first solid electrolyte layer and the second solid electrolyte layer on the two sides of the middle layer can prevent the powder M from directly contacting with the anode and the cathode and preventing the powder M from electronically conducting; in the solid-state battery with the lithium metal assembled by the all-solid-state electrolyte layer as the negative electrode, the growth of lithium dendrites can be effectively inhibited, the risk of short circuit of the positive electrode and the negative electrode is reduced, and the safety performance of the battery is improved.

Description

All-solid-state electrolyte layer and preparation method and application thereof
Technical Field
The invention belongs to the field of solid batteries, relates to an all-solid electrolyte layer, a preparation method and application thereof, and particularly relates to an all-solid electrolyte layer capable of inhibiting growth of lithium dendrites, and a preparation method and application thereof.
Background
With the rapid development of consumer electronics and electric vehicles, the demands for energy density, safety, reliability and service life of batteries are increasing dramatically. Lithium metal has extremely high theoretical specific capacity (3860mAh/Kg) and lowest potential (-3.04V), so that the lithium metal secondary battery is the preferred system of the next generation of high-energy-density energy storage devices. The solid-state battery has no electrolyte in the solid-state battery, so that potential safety hazards caused by the leakage of the electrolyte and other problems are well avoided, and meanwhile, the solid-state battery has the advantages of high energy density, no memory effect and the like and is widely concerned by researchers.
However, the non-uniform deposition of lithium ions on the lithium metal negative electrode may cause the growth of lithium dendrites; in addition, the solid electrolyte layer is not completely compact, and pores exist in the solid electrolyte layer, so that the solid electrolyte layer is easily pierced by lithium dendrites in the circulation process, and the anode and the cathode of the battery are short-circuited due to the existence of the lithium dendrites, so that the battery is failed and potential safety hazards are caused.
Most of the existing methods for inhibiting the growth of lithium dendrites are methods for directly protecting lithium metal, and the methods for directly protecting the lithium metal comprise the following steps: (1) preparing a protective layer on the surface of the lithium metal by a wet coating method; however, the coated protective layer is bonded with lithium metal through a binder, so that the mechanical strength and toughness are poor, and the lithium metal negative electrode can have severe volume change in the charging and discharging processes of the battery, so that the protective layer has the problems of breakage, breaking, falling off and the like, and finally the protective layer fails; in addition, because a solvent and a binder are needed in the coating process, and the existence of the solvent causes the protective layer to need to be dried for a long time, the preparation efficiency of the protective layer is further reduced; the addition of the binder can reduce the ionic conductivity of the protective layer, so that the protective effect is reduced; (2) preparing an alloy protective layer on the surface of lithium metal: the existing preparation method is generally a liquid phase method, and a solution prepared by using inorganic powder such as indium chloride, aluminum nitride and the like is coated on the surface of lithium metal to react to generate an alloy layer; the alloy protective layer prepared by the liquid phase method generally has more impurities, which affects the uniform deposition of lithium ions in the charging and discharging process and cannot well inhibit the generation of lithium dendrites; in addition, in the method, various impurities can be introduced due to the existence of the solvent, so that the impedance of the whole battery is increased, and the reaction degrees of different batches are different, so that the consistency of the alloy protective layer is poor; (3) the polymer film is used as a lithium metal negative electrode protective layer, and the interface impedance between the solid electrolyte layer and the lithium metal negative electrode can be effectively reduced by using the polymer film prepared by adding lithium salt into polymers such as PEO, PVDF and PAN, but the polymer film generally has poor mechanical strength, is difficult to prevent the penetration of lithium dendrites, and has little effect on the aspect of prolonging the cycle life of the battery; (4) forming an alloy layer on the surface of the lithium metal by physical deposition means such as evaporation, sputtering and the like; the method can form a uniform alloy protective layer on the surface of lithium metal, but due to the limitation of physical deposition equipment, the thickness of the deposited protective layer is generally only in the nanometer level and generally not more than 200nm, and the operability is poor; the operation time of the processes such as evaporation, sputtering and the like is long, and the formation of a protective layer of dozens of nanometers generally takes several hours; (5) coating a layer of graphite or other carbon layers on the surface of the lithium metal by a dry method in a scraping manner to protect the lithium metal; the method has difficulty in controlling the thickness of the protective layer and in preparing the protective layer uniformly.
CN108063241A discloses a method for inhibiting lithium dendrite generation on the surface of lithium metal, comprising the following steps: dissolving a manganese salt crystal in an electrolyte containing a lithium salt and an organic solvent to obtain an electrolyte containing manganese ions, wherein the manganese salt crystal is one or more of manganese nitrate, manganese acetate and manganese sulfate, and the lithium salt is selected from lithium hexafluorophosphate, lithium perchlorate or lithium bistrifluoromethanesulfonylimide; and contacting the smooth surface of the lithium metal with an electrolyte containing manganese ions until a bright black film is formed on the surface of the lithium metal. CN108365169A discloses a lithium metal negative electrode structure combination and a preparation method thereof. The utility model provides a lithium metal negative pole structural grouping, includes the negative pole structure and forms surface modification layer on the negative pole structure, the negative pole structure includes the negative pole mass flow body and forms lithium metal negative pole layer on the negative pole mass flow body, lithium metal negative pole layer and surface modification layer stack set up, lithium metal negative pole layer includes lithium metal active material, surface modification layer is including the lithium compound that has ion conduction characteristic.
The above methods for inhibiting the growth of lithium dendrites all protect directly on lithium metal, and the following obvious disadvantages are summarized: a. because lithium metal has extremely strong reaction activity, other impurities except the protective layer are inevitably introduced into the lithium metal when the lithium metal is directly protected, so that the purity of the protective layer is not high, and the protective effect is not obvious; b. lithium metal will react with N in the air 2 、O 2 、CO 2 、H 2 O and the like react to cause the damage and pollution of lithium metal, so that most of the conventional lithium metal protection methods need to be carried out in inert gas atmosphere such as vacuum atmosphere, argon atmosphere and the like, which causes that the method for directly protecting lithium metal is difficult to carry out large-scale production, and the requirement of maintaining the inert production atmosphere on energy is huge, thus causing the increase of the manufacturing cost.
Therefore, it is still important to develop a method for effectively suppressing the growth of lithium dendrites without directly protecting the lithium metal negative electrode.
Disclosure of Invention
The invention aims to provide an all-solid electrolyte layer and a preparation method and application thereof; the all-solid electrolyte layer comprises a laminated three-layer structure, wherein the intermediate layer comprises solid electrolyte particles and powder M, and the powder M is selected from substances capable of forming an alloy with lithium metal; the first solid electrolyte layer and the second solid electrolyte layer on the two sides of the middle layer can prevent the direct contact and electronic conduction of the powder M and the positive and negative electrodes.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an all-solid-state electrolyte layer, which includes a first solid-state electrolyte layer, a second solid-state electrolyte layer, and an intermediate layer located between the first solid-state electrolyte layer and the second solid-state electrolyte layer, where the intermediate layer includes solid-state electrolyte particles and a powder M selected from materials capable of forming an alloy with lithium metal.
In addition, because the solid electrolyte layer is not completely compact and has pores, the solid electrolyte layer is easily pierced by the lithium dendrites in the circulating process, and the anode and the cathode of the solid battery are short-circuited due to the existence of the lithium dendrites, so that the battery fails and potential safety hazards are caused; most of the traditional methods for inhibiting the growth of the lithium dendrites directly protect lithium metal, and have the problems of poor protection effect, high cost, high risk and long time consumption; the all-solid-state electrolyte layer disclosed by the invention effectively inhibits the growth of lithium dendrites by designing the composition and the structure of the all-solid-state electrolyte layer, avoids the adverse effect on a lithium metal cathode, and has the advantages of low process cost, low energy consumption and low risk.
The all-solid-state electrolyte layer comprises a laminated three-layer structure, wherein a first solid-state electrolyte layer and a second solid-state electrolyte layer are respectively arranged on two sides of the all-solid-state electrolyte layer, solid-state electrolyte particles and powder M are contained in an intermediate layer, and the first solid-state electrolyte layer and the second solid-state electrolyte layer on the two sides have the effect of isolating the intermediate layer from a positive electrode and a negative electrode, so that direct contact and electronic conduction between the powder M and the positive electrode and the negative electrode are avoided.
The principle of the all-solid-state electrolyte layer for inhibiting the growth of lithium dendrites is as follows: the "intermediate layer" is reached when lithium dendrites start to grow and pierce through the "first solid electrolyte layer" in the all-solid electrolyte layer, because the intermediate layer contains a mixture of solid electrolyte particles and powder M, and lithium dendrites have a greater tendency to grow between the solid electrolyte particles, so the lithium dendrites contact the powder M; the lithium dendrite is communicated with the negative current collector, so the potential of the lithium dendrite is the potential (0V vs Li) of the lithium metal negative electrode; since the powder M is a substance capable of forming an alloy with lithium, the powder M can perform an alloying reaction with lithium dendrites at the potential (0V vs Li), so that the lithium dendrites growing to the 'middle layer' are consumed and converted into LiM alloy compounds, thereby preventing the lithium dendrites from continuously growing and eliminating the lithium dendrites growing to the middle layer.
The technical problem to be solved by the invention is to achieve the purpose of inhibiting the growth of lithium dendrites through the design of the structure and the composition of an all-solid electrolyte layer; wherein the intermediate layer comprises solid electrolyte particles and powder M; the powder M is a substance capable of forming an alloy with lithium, and meanwhile, the first solid electrolyte layer and the second solid electrolyte layer cover the two side surfaces of the middle layer, so that direct contact and electronic conduction between the powder M and the positive and negative electrodes in the middle layer are isolated.
The all-solid-state electrolyte layer can achieve the effect of inhibiting the growth of lithium dendrites, and the aim of inhibiting the growth of the lithium dendrites in the all-solid-state electrolyte layer is achieved by introducing an intermediate layer into the all-solid-state electrolyte layer; any binder and solvent cannot be introduced into the lithium metal negative electrode, so that on one hand, impurities generated by reaction of the solvent and the lithium metal are reduced, on the other hand, pollution and time waiting caused by drying of the solvent are saved, the situation that a protective layer and the lithium metal negative electrode fall off does not exist, the cost is reduced, the environmental protection is improved, and the preparation efficiency is improved; in the present invention, since the powder M capable of consuming lithium dendrites is present in the "intermediate layer", the lithium metal surface protective layer is not pierced due to insufficient mechanical strength; the preparation method of the all-solid-state electrolyte layer can uniformly mix the powder M and the solid electrolyte particles through simple mechanical mixing, can achieve the purpose of preparing the all-solid-state electrolyte layer through using traditional equipment, and is convenient to operate and simple in process.
Preferably, the powder M is at least one selected from nano silicon, nano carbon, nano tin, nano gold and nano platinum, and is preferably nano silicon.
The powder M is preferably nano silicon, and the nano silicon can consume more lithium dendrites under the condition that the addition amount of the powder M is the same because the silicon has higher specific mass capacity (4200 mAh/g).
Preferably, the powder M is selected from a combination of at least two of nano-silicon, nano-carbon, nano-tin, nano-gold and nano-platinum, and the combination exemplarily includes a combination of nano-silicon and nano-carbon, a combination of nano-tin and nano-gold, a combination of nano-platinum and nano-silicon, a combination of nano-carbon and nano-tin, a combination of nano-gold and nano-platinum, and the like.
Preferably, the first solid electrolyte layer contains solid electrolyte particles.
Preferably, the second solid electrolyte layer contains solid electrolyte particles.
Preferably, the first solid electrolyte layer and the second solid electrolyte layer do not contain powder M.
Preferably, the particle size of the solid electrolyte particles is larger than the particle size of the powder M.
The particle size of the solid electrolyte particles is micron-sized powder, and in order to enable the powder M to be better filled in gaps of the solid electrolyte particles, the powder M is nano-sized powder.
Preferably, the solid electrolyte particles are selected from at least one of a sulfide solid electrolyte, an anti-perovskite electrolyte, a halogen electrolyte, a polymer electrolyte and an oxide electrolyte, preferably a sulfide electrolyte.
Preferably, the solid electrolyte particles have a particle size in the micron range, preferably a D50 of 0.3 μm to 10 μm, such as 1 μm, 3 μm, 5 μm, 7 μm or 9 μm, etc.
Preferably, the particle size of the powder M is in the nanometer range, preferably D50 is 10-1000 nm, such as 30nm, 50nm, 100nm, 300nm, 500nm, 700nm or 900nm, and more preferably 50-500 nm.
The particle diameters of the solid electrolyte particles and the powder M are in the range, so that the powder M can be better filled in the gaps of the solid electrolyte particles, and the following effects are realized: (1) the filling of the nano powder M does not influence the continuous contact among solid electrolyte particles, so that the ionic conduction and the conductivity of an electrolyte layer are not influenced; (2) nanometer powder M distributes more evenly between solid electrolyte granule, when lithium dendrite grows to "intermediate level", just can contact with nanometer powder M more, and then can fall lithium dendrite "digestion" fast, further promotes the security of battery, avoids the battery inefficacy.
Preferably, the thickness of the first solid electrolyte layer is 2 to 50 μm, for example, 3 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, or 45 μm, and more preferably 8 to 15 μm.
Preferably, the thickness of the second solid electrolyte layer is 2 to 50 μm, for example, 3 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, or 45 μm, and more preferably 8 to 15 μm.
Preferably, the thickness of the intermediate layer is 5 to 30 μm, for example, 10 μm, 15 μm, 20 μm, or 25 μm, and more preferably 3 to 15 μm.
The thickness of the interlayer is within the range, so that lithium dendrite generated by nonuniform deposition of lithium ions can be consumed more conveniently, and ion conduction and conductivity of the all-solid electrolyte layer are prevented from being influenced.
Preferably, in the intermediate layer, the mass ratio of the solid electrolyte particles to the powder M is (2 to 20):1, for example, 3:1, 5:1, 8:1, 10:1, 12:1, 15:1 or 18:1, and preferably (3 to 10): 1.
The content of the powder M in the intermediate layer is within the range, so that lithium dendrites generated by uneven deposition of lithium ions can be consumed quickly, the electrical property of the solid electrolyte can be prevented from being influenced, the risk of short circuit of a positive electrode and a negative electrode can be reduced, and the safety of the battery can be improved.
Preferably, in the intermediate layer, the powder M is dispersed in the gaps of the solid electrolyte particles.
In the intermediate layer of the present invention, the solid electrolyte particles and the powder M are stacked on each other, and the powder M is dispersed and filled in the gaps between the solid electrolyte particles
Preferably, the first solid electrolyte layer, the intermediate layer and the second solid electrolyte layer are sequentially stacked.
Preferably, the all-solid-state electrolyte layer further comprises a binder.
In a second aspect, the present invention provides a method for producing an all-solid electrolyte layer according to the first aspect, the method comprising:
preparing a first solid electrolyte layer; and
forming an intermediate layer on the first solid electrolyte layer; and
and forming a second solid electrolyte layer on the intermediate layer to obtain the all-solid-state electrolyte layer.
The all-solid-state electrolyte layer is prepared by the method, is different from the traditional method for directly forming a protective layer for inhibiting the growth of lithium dendrites on the surface of lithium metal, and has the advantages of simple and convenient operation, low risk and low cost.
Preferably, the method of preparing the first solid electrolyte layer includes mixing solid electrolyte particles, a binder and a solvent, homogenizing, coating, and drying.
Preferably, the method of forming the intermediate layer includes mixing the solid electrolyte particles, the powder M, the binder, and the solvent, homogenizing, coating, and drying.
Preferably, the method of forming the second solid electrolyte layer includes mixing the solid electrolyte particles, the binder, and the solvent, homogenizing, coating, and drying.
The preparation method of the all-solid-state electrolyte layer has the characteristics of simple preparation process and low cost.
In a third aspect, the present invention provides a solid-state battery employing the all-solid-state electrolyte layer according to the first aspect.
Preferably, the negative electrode of the solid-state battery includes lithium metal.
The solid-state battery provided by the invention adopts the all-solid-state electrolyte layer as described in the first aspect, and the growth of lithium dendrites can be effectively inhibited, so that the risk of short circuit of the anode and the cathode is reduced, the safety of the battery is improved, and the battery is prevented from losing efficacy.
Compared with the prior art, the invention has the following beneficial effects:
(1) the all-solid-state electrolyte layer can effectively inhibit the growth of lithium dendrites in the solid-state battery, so that the risk of short circuit of the positive electrode and the negative electrode caused by the growth of the lithium dendrites in the battery is reduced, the safety of the battery is improved, meanwhile, the direct protection of the lithium metal negative electrode is avoided, and further the adverse effect on the lithium metal is avoided;
(2) the preparation process of the all-solid-state electrolyte layer is simple, low in cost and easy to industrialize.
Drawings
FIG. 1 is a schematic view of the structure of an all-solid electrolyte layer according to the present invention;
fig. 2 is a schematic diagram of mixing of solid electrolyte particles and nano-powder M in the intermediate layer of the all-solid-state electrolyte layer according to the present invention;
fig. 3 is a schematic view of internal particle packing of a conventional solid electrolyte.
Fig. 4 is a schematic view of a lithium metal solid-state battery;
FIG. 5 is a schematic diagram of a lithium metal solid state battery employing a conventional solid electrolyte layer with lithium dendrites piercing through the solid electrolyte layer;
fig. 6 is a cycle curve of a symmetrical battery assembled with all solid electrolyte layers in example 1 of the present invention;
FIG. 7 is a cycle curve of a symmetrical cell assembled with all solid electrolyte layers of comparative example 1 according to the present invention;
fig. 8 is a time-voltage cycle curve of a full cell assembled with all solid electrolyte layers in example 1 of the present invention;
fig. 9 is a time-voltage cycle curve of a full cell assembled with the all-solid electrolyte layer in comparative example 1 according to the present invention;
1-first solid electrolyte layer, 2-intermediate layer, 3-second solid electrolyte layer, 20-solid electrolyte particles, 21-powder M, 4-positive layer, 5-solid electrolyte layer, 6-lithium metal negative electrode, 7-lithium dendrite.
Detailed Description
The technical solution of the present invention is further described below by way of specific 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.
The structural schematic diagram of the all-solid-state battery of the present invention is shown in fig. 1, and includes a first solid-state electrolyte layer 1, an intermediate layer 2, and a second solid-state electrolyte layer 3 stacked in sequence; the structure of the intermediate layer is schematically shown in fig. 2, and the intermediate layer includes solid electrolyte particles 20 and powder M21, wherein the solid electrolyte particles and the nano powder M are stacked one on another, and the particle size of the solid electrolyte particles is micron-sized; the powder M is in a nanometer level, and the following effects can be achieved by adopting the particle size: (1) the nano powder M does not influence the continuous contact among solid electrolyte particles, so that the ionic conduction and the conductivity of the all-solid electrolyte layer are not influenced; (2) the nano powder M is more uniformly distributed, and can be fully contacted with the nano powder M when the lithium dendritic crystal grows to the middle layer, so that the lithium dendritic crystal can be rapidly digested, and the safety of the battery is further improved.
The internal particle stacking structure of the conventional all-solid electrolyte layer is shown in fig. 3, which is formed by stacking solid electrolyte particles together; fig. 4 is a schematic structural view of a conventional solid-state battery with a lithium metal negative electrode; when the solid electrolyte layer is an all-solid electrolyte layer as shown in fig. 3, the growth of lithium dendrite 7 pierces the all-solid electrolyte layer, which causes short circuit between the positive and negative electrodes, as shown in fig. 5.
Example 1
In this embodiment, the solid electrolyte particles adopt sulfide solid electrolyte (lithium silicon phosphorus sulfur chloride) with D50 of 5.4 μ M, and the nano powder M is selected from nano silicon with D50 of 80 nm; the mass ratio of the sulfide solid electrolyte to the nano-silicon in the middle layer is 5: 1; the thicknesses of the first solid electrolyte layer, the second solid electrolyte layer and the third solid electrolyte layer are all 10 micrometers;
the preparation method comprises the following steps:
(1) uniformly mixing a sulfide solid electrolyte, a binder and a solvent, and homogenizing, coating and drying to obtain a first solid electrolyte layer;
(2) uniformly mixing sulfide solid electrolyte particles and nano-silicon according to the mass ratio of 5:1, uniformly mixing the mixture with a binder and a solvent, homogenizing, coating the homogenized mixture on the first solid electrolyte layer prepared in the step (1), controlling the coating thickness to be 10 microns, and drying to form an intermediate layer;
(3) and (3) uniformly mixing the sulfide solid electrolyte particles with a binder and a solvent, homogenizing, coating on the intermediate layer prepared in the step (2), controlling the coating thickness to be 10 mu m, and drying to form a second solid electrolyte layer to obtain the all-solid electrolyte layer.
Example 2
This example is different from example 1 in that the mass-equivalent particle diameter of nano-silicon is replaced with nano-carbon, and other parameters and conditions are exactly the same as those in example 1.
Example 3
The present example is different from example 1 in that nano tin is substituted for nano silicon and the like in terms of mass and the like, and other parameters and conditions are exactly the same as those in example 1.
Example 4
The present example is different from example 1 in that nano-gold is substituted for nano-silicon and the like in terms of mass and the like, and other parameters and conditions are exactly the same as those in example 1.
Example 5
The present example differs from example 1 only in that the mass ratio of sulfide solid electrolyte particles to nano silicon was replaced with 2:1, and other parameters and conditions were exactly the same as in example 1.
Example 6
The present example differs from example 1 only in that the mass ratio of sulfide solid electrolyte particles to nano silicon was replaced with 3:1, and other parameters and conditions were exactly the same as in example 1.
Example 7
The present example is different from example 1 only in that the mass ratio of sulfide solid electrolyte particles to nano silicon was replaced with 20:1, and other parameters and conditions were completely the same as in example 1.
Example 8
The present example differs from example 1 only in that the mass ratio of sulfide solid electrolyte particles to nano silicon was replaced with 10:1, and other parameters and conditions were exactly the same as in example 1.
Example 9
This example is different from example 1 only in that D50 of powder M was 1 μ M, and other parameters and conditions were exactly the same as those in example 1.
Example 10
The present example is different from example 1 only in that D50 of powder M is 450nm, and other parameters and conditions are exactly the same as those in example 1.
Example 11
The present example is different from example 1 only in that D50 of powder M is 10nm, and other parameters and conditions are exactly the same as those in example 1.
Example 12
This example is different from example 1 only in that a halogen electrolyte (lithium chloroytridate) is substituted for sulfide solid electrolyte particles having a mass equivalent particle diameter, and other parameters and conditions are exactly the same as those in example 1.
Comparative example 1
This comparative example is different from example 1 in that the intermediate layer does not contain nano-silicon, and other parameters and conditions are exactly the same as those in example 1.
Comparative example 2
This comparative example is different from example 12 only in that the intermediate layer does not contain nano-silicon and other parameters and conditions are exactly the same as those in example 12.
And (3) performance testing:
the all-solid-state electrolyte layers obtained in the examples and the comparative examples are adopted, lithium metal is used as a working electrode and a reference electrode, and a symmetrical battery structure with the structure of Li/all-solid-state electrolyte layer/Li is obtained through assembly; at 0.6mAh/cm 2 Carrying out a cycle test under the current density;
the cycle performance test results of the symmetrical batteries assembled with the all-solid electrolyte layers in example 1 and comparative example 1 are shown in fig. 6 and 7, and it can be seen from fig. 6 that the symmetrical batteries assembled with the all-solid electrolyte layers prepared in the present invention do not suffer from short circuit after cycling for more than 300 hours, indicating that the all-solid electrolyte layers can well inhibit the growth of lithium dendrites; as can be seen from fig. 7, short circuit due to penetration of lithium dendrite occurred when the solid-state battery of comparative example 1 was cycled for not more than 6 hours.
A pouch cell (full cell) was assembled from a positive electrode sheet using lithium metal as a negative electrode and the all-solid electrolyte layers prepared in the examples of the present invention and the comparative examples as separators, with nickel cobalt lithium manganate as an active material. Carrying out a cycle test at a multiplying power of 0.1C, and recording time-voltage change;
cycle performance testing of the all-solid electrolyte layer-assembled all-cell of example 1 and comparative example 1 as shown in fig. 8 and 9, it can be seen from fig. 8 that no short circuit was observed for 10 cycles of the all-solid electrolyte layer-assembled all-cell obtained in example 1, whereas a micro short circuit due to lithium dendrite puncture occurred in the first cycle of the all-solid electrolyte layer-assembled all-cell of comparative example 1, as can be seen from fig. 9.
The results of the cycle performance test of the symmetrical batteries obtained by assembling all solid electrolyte layers in the examples and comparative examples are shown in table 1;
TABLE 1
Figure BDA0002697291600000131
Figure BDA0002697291600000141
Cycle life in the above table refers to the time during which a symmetrical cell exhibits overpotential that does not appreciably jitter, dip, and is capable of sustaining stability during a cycle with constant current.
As can be seen from the data in the above Table 1, the cycle life of the symmetrical batteries obtained by using the all-solid-state electrolyte layer of the present invention is long, and can reach more than 350 h.
As can be seen from comparative examples 1 to 4, the powder M of the present invention is preferably nanosilicon.
As can be seen from comparative examples 1 and 5 to 8, the intermediate layer has good cycle performance when the mass ratio of the solid electrolyte to the powder M is (2 to 20):1, and the mass ratio is preferably (3 to 10):1, and more preferably 3: 1.
As can be seen from comparative examples 1 and 9 to 11, the particle size of the powder M of the present invention is preferably in the nanometer range, and more preferably the particle size D50 is 10 to 500 nm.
It can be seen from comparison of examples 1 and 12 and comparative examples 1 to 2 that when the solid electrolyte particles are sulfide solid electrolyte and halogen electrolyte, the intermediate layer doped with the powder M is beneficial to inhibiting the growth of lithium dendrite, thereby improving the cycle performance and safety of the battery.
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 (21)

1. An all-solid-state electrolyte layer is characterized by comprising a first solid-state electrolyte layer, a second solid-state electrolyte layer and an intermediate layer positioned between the first solid-state electrolyte layer and the second solid-state electrolyte layer, wherein the intermediate layer comprises solid-state electrolyte particles and powder M, the powder M is selected from substances capable of forming an alloy with lithium metal, the particle size of the solid-state electrolyte particles is larger than that of the powder M, the particle size of the solid-state electrolyte particles is micron-sized, the particle size of the powder M is nano-sized, and the mass ratio of the solid-state electrolyte particles to the powder M in the intermediate layer is (2-20): 1;
the powder M is selected from nano silicon and/or nano carbon;
the D50 of the solid electrolyte particles is 0.3-10 mu m; the D50 of the powder M is 10-1000 nm.
2. The all-solid-state electrolyte layer of claim 1 wherein the first solid-state electrolyte layer comprises solid-state electrolyte particles.
3. The all-solid electrolyte layer of claim 1 wherein the second solid electrolyte layer comprises solid electrolyte particles.
4. The all-solid electrolyte layer according to claim 1 wherein the solid electrolyte particles are selected from at least one of sulfide solid electrolytes, anti-perovskite electrolytes, halogen electrolytes, polymer electrolytes, and oxide electrolytes.
5. The all-solid electrolyte layer of claim 4 wherein the solid electrolyte particles are sulfide electrolytes.
6. The all-solid-state electrolyte layer according to claim 1, wherein D50 of the powder M is 50 to 500 nm.
7. The all-solid electrolyte layer according to claim 1 wherein the thickness of the first solid electrolyte layer is 2 to 50 μm.
8. The all-solid-state electrolyte layer of claim 7, wherein the first solid-state electrolyte layer has a thickness of 8 to 15 μm.
9. The all-solid-state electrolyte layer according to claim 1, wherein the thickness of the second solid-state electrolyte layer is 2 to 50 μm.
10. The all-solid electrolyte layer according to claim 9 wherein the thickness of the second solid electrolyte layer is 8 to 15 μm.
11. The all-solid electrolyte layer of claim 1 wherein the thickness of the intermediate layer is 5 to 30 μm.
12. The all-solid electrolyte layer of claim 11 wherein the thickness of the intermediate layer is 3 to 15 μm.
13. The all-solid-state electrolyte layer according to claim 1, wherein in the intermediate layer, the mass ratio of solid-state electrolyte particles to powder M is (3-10): 1.
14. The all-solid electrolyte layer according to claim 1, wherein in the intermediate layer, powder M is dispersed in the gaps of the solid electrolyte particles.
15. The all-solid-state electrolyte layer of claim 1 further comprising a binder.
16. The method for producing an all-solid electrolyte layer according to any one of claims 1 to 15, wherein the method comprises:
preparing a first solid electrolyte layer; and
forming an intermediate layer on the first solid electrolyte layer; and
and forming a second solid electrolyte layer on the intermediate layer to obtain the all-solid-state electrolyte layer.
17. The method of claim 16, wherein the first solid electrolyte layer is prepared by mixing solid electrolyte particles, a binder and a solvent, homogenizing, coating and drying.
18. The method of claim 16, wherein the step of forming the intermediate layer comprises mixing the solid electrolyte particles, the powder M, the binder and the solvent, homogenizing, coating, and drying.
19. The method of claim 16, wherein the step of forming the second solid electrolyte layer comprises mixing solid electrolyte particles, a binder and a solvent, homogenizing, coating and drying.
20. A solid-state battery employing the all-solid-state electrolyte layer according to any one of claims 1 to 15.
21. The solid-state battery of claim 20, wherein a negative electrode of the solid-state battery comprises lithium metal.
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