CN112687959B - Method for preparing solid electrolyte, solid electrolyte and solid battery - Google Patents

Method for preparing solid electrolyte, solid electrolyte and solid battery Download PDF

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CN112687959B
CN112687959B CN202011570705.9A CN202011570705A CN112687959B CN 112687959 B CN112687959 B CN 112687959B CN 202011570705 A CN202011570705 A CN 202011570705A CN 112687959 B CN112687959 B CN 112687959B
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solid electrolyte
solid
layer
composite
surface layer
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CN112687959A (en
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谭志
张艳芳
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Vitalink Industry Shenzhen Co ltd
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    • 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
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    • Y02E60/10—Energy storage using batteries
    • 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
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Abstract

The invention discloses a preparation method of a solid electrolyte, the solid electrolyte and a solid battery. The preparation method of the solid electrolyte comprises the following steps: mixing a base solid electrolyte material with the particle size of 1-50 mu m and a lithium conducting material with the particle size of 10-50 nm in a dry coating machine, and performing coating treatment to uniformly disperse the lithium conducting material and adsorb the lithium conducting material on the surface of the base solid electrolyte material to form a coating layer so as to prepare a composite material, wherein the lithium conducting material is a metal material; preparing the composite material into a film-shaped material to obtain a composite solid electrolyte base layer; depositing a first surface layer solid electrolyte material on the surface of one side of the composite solid electrolyte base layer to form a first solid electrolyte surface layer; and depositing a second surface layer solid electrolyte material on the surface of the other side opposite to the composite solid electrolyte base layer to form a second solid electrolyte surface layer. The ion conductivity of the solid electrolyte prepared by the preparation method of the solid electrolyte can be remarkably improved.

Description

Method for preparing solid electrolyte, solid electrolyte and solid battery
Technical Field
The invention relates to the technical field of batteries, in particular to a preparation method of a solid electrolyte, the solid electrolyte and a solid battery.
Background
With the development of science and technology, secondary batteries are widely used as typical energy storage devices in a variety of technical fields requiring energy storage, such as portable electronic devices, electric vehicles, smart grids, and the like. A conventional secondary battery has a basic structure including a positive electrode, a negative electrode, and an electrolyte disposed between the positive electrode and the negative electrode for conducting ions but blocking electrons. The traditional electrolyte is mostly organic liquid electrolyte, and is matched with a diaphragm to prevent direct contact of a positive electrode and a negative electrode. The organic liquid electrolyte has the hidden troubles of air inflation and liquid leakage in the use process, and lithium dendrites generated in the charging and discharging process of secondary batteries such as lithium ions or lithium metal and the like easily pierce through a diaphragm to cause short circuit of the batteries.
The all-solid-state battery is a novel battery, and all components in the all-solid-state battery are solid. The main difference between the electrolyte and the traditional battery is that the electrolyte in an all-solid state is adopted to replace the traditional liquid electrolyte and the diaphragm, so that the property of the electrolyte is fundamentally changed, and the problems can be better avoided. Although solid electrolytes greatly improve the safety of batteries, the ionic conductivity of solid electrolytes is generally about three orders of magnitude lower than that of liquid electrolytes. The ionic conductivity is an important index for measuring the electrical performance of the battery, reflects the migration rate of ions in the battery, and has an important influence on the charge and discharge rate of the battery. As a result, the internal resistance of the all-solid battery tends to be large, which becomes a bottleneck limiting the electrochemical performance of the all-solid battery.
Disclosure of Invention
Based on this, the primary object of the present invention is to provide a method for producing a solid electrolyte having higher ionic conductivity, further to provide a solid electrolyte and a solid battery.
According to an embodiment of the present invention, a method for preparing a solid electrolyte includes the steps of:
mixing a base layer solid electrolyte material with the particle size of 1-50 mu m and a lithium conducting material with the particle size of 10-50 nm in a dry coating machine, and performing coating treatment to uniformly disperse the lithium conducting material and adsorb the lithium conducting material on the surface of the base layer solid electrolyte material to form a coating layer so as to prepare a composite material, wherein the lithium conducting material is a metal material;
preparing the composite material into a film-shaped material to obtain a composite solid electrolyte base layer;
depositing a first surface layer solid electrolyte material on the surface of one side of the composite solid electrolyte base layer to form a first solid electrolyte surface layer; and depositing a second surface layer solid electrolyte material on the surface of the other side opposite to the composite solid electrolyte base layer to form a second solid electrolyte surface layer.
In one embodiment, the mass ratio of the metal material to the base solid electrolyte material is (1-10): 1.
In one embodiment, the method of depositing the first and/or second facing solid state electrolyte material is a physical vapor deposition method.
In one embodiment, the method further comprises the step of heating the first solid electrolyte surface layer and the second solid electrolyte surface layer, wherein the heating temperature is 80-140 ℃.
In one embodiment, the first facing solid state electrolyte material, the second facing solid state electrolyte material, and the base solid state electrolyte material are each independently selected from LiPON, La1-xLi0.15+xTiO2.45+x、Li1+xAlxTi2-x(PO4)3、Li3+xGexP1-xS4、Li2+2xZn1-xGeO4、Li2S-AyS2y+1、Li2S-Yy-1Sy、Li7La3Zr2O12、Li2S、Li3N、Li3PO4、LiPF6、Li14Zn(GeO4)4One or more of; wherein x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 1 and less than or equal to 3; a is selected from one or more of P, B and Al, and Y is selected from one or two of Si and Ge.
In one embodiment, the metal material is selected from one or more of lithium, copper and silver.
In one embodiment, the base layer solid state electrolyte material is LiPON and the metal material is metallic lithium.
Correspondingly, another embodiment of the invention provides a solid-state electrolyte prepared by the method for preparing a solid-state electrolyte according to any one of the embodiments.
In yet another aspect, a solid state electrolyte includes: the composite solid electrolyte comprises a composite solid electrolyte base layer, a first solid electrolyte surface layer and a second solid electrolyte surface layer, wherein the first solid electrolyte surface layer is arranged on a first surface of the composite solid electrolyte base layer, and the second solid electrolyte surface layer is arranged on a second surface opposite to the first surface; the composite solid electrolyte base layer is of a core-shell structure, wherein a core material is a base layer solid electrolyte material, a shell material is a lithium conducting material, the particle size of the core material is 1-50 mu m, the particle size of the shell material is 10-50 nm, and the lithium conducting material is a metal material.
In one embodiment, the thickness of the first solid electrolyte surface layer is 1000nm to 3000 nm; and/or
The thickness of the second solid electrolyte surface layer is 1000 nm-3000 nm; and/or
The thickness of the composite solid electrolyte base layer is 10-100 mu m.
Further, a solid-state battery includes a positive electrode, a negative electrode, and a solid-state electrolyte disposed between the positive electrode and the negative electrode, the solid-state electrolyte being the solid-state electrolyte according to any of the embodiments described above.
In one embodiment, the solid-state battery is a solid-state thin-film battery, and the thickness of the whole solid-state thin-film battery is less than or equal to 500 micrometers.
The preparation method of the solid electrolyte has the following solid electrolyte structure: the composite solid electrolyte base layer simultaneously comprises a base layer solid electrolyte material and a metal material, wherein the solid electrolyte material is granular, and the metal material is coated on the surface of the solid electrolyte material. The solid electrolyte is a main body substance for ion diffusion, and the metal material coated on the surface of the base layer solid electrolyte material can assist ions to diffuse rapidly, so that the diffusion resistance of the ions in the base layer solid electrolyte material is reduced. The first solid electrolyte surface layer and the second solid electrolyte surface layer are used for preventing the composite solid electrolyte base layer from short-circuiting. Thus, the ion conductivity of the solid electrolyte can be effectively improved.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a solid electrolyte according to one embodiment;
FIG. 2 is a schematic structural view of a solid electrolyte according to an embodiment;
fig. 3 is a schematic view of the structure of an intermediate solid electrolyte layer in the solid electrolyte shown in fig. 1.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items, and as used herein, a "plurality" includes two or more items.
In the present invention, the sum of the parts of the components in the composition may be 100 parts by weight, if not indicated to the contrary. The percentages (including weight percentages) of the present invention are based on the total weight of the composition, unless otherwise specified, and "wt%" herein means mass percentages. As is not generally understood by those skilled in the art, "particle size" herein should be understood to mean the D50 particle size.
Herein, unless otherwise specified, the individual reaction steps may or may not be performed in the order indicated. For example, other steps may be included between the respective reaction steps, and the order may be appropriately changed between the reaction steps. As can be determined by the skilled person from routine knowledge and experience. Preferably, the reaction processes herein are carried out sequentially.
The solid electrolyte in the conventional art generally contains only one layer of the solid electrolyte material. The diffusion resistance of ions in solid substances is much greater than that in liquid substances, and thus the ionic conductivity of solid electrolyte materials is much lower than that of liquid electrolytes.
The solid-state thin-film battery is one of solid-state batteries, has the advantages of high capacity density, pure solid state, suitability for miniaturized preparation and the like, and is a battery system with great prospect. However, it is also difficult to satisfy the use of high performance scenarios due to the low ionic conductivity of the solid electrolyte in the solid-state thin film battery.
In order to solve the above-mentioned problems, according to an embodiment of the present invention, a method for preparing a solid electrolyte includes at least the steps of: mixing a base solid electrolyte material with the particle size of 1-50 mu m and a lithium conducting material with the particle size of 10-50 nm in a dry coating machine, and performing coating treatment to uniformly disperse the lithium conducting material and adsorb the lithium conducting material on the surface of the base solid electrolyte material to form a coating layer so as to prepare a composite material, wherein the lithium conducting material is a metal material;
preparing the composite material into a film-shaped material to obtain a composite solid electrolyte base layer;
depositing a first surface layer solid electrolyte material on the surface of one side of the composite solid electrolyte base layer to form a first solid electrolyte surface layer; and depositing a second surface layer solid electrolyte material on the surface of the other side opposite to the composite solid electrolyte base layer to form a second solid electrolyte surface layer.
More specifically, referring to fig. 1, the solid electrolyte can be prepared according to the following more detailed preparation method.
Step S1, obtaining a base layer solid electrolyte material with the grain diameter of 1-50 μm and a metal material with the grain diameter of 10-50 nm.
In one specific example, the base layer solid electrolyte material is spherical. On the one hand, a base solid electrolyte material in a spherical shape is easier to prepare, and can be obtained by subjecting the base solid electrolyte material to a high-speed ball milling treatment, for example. Moreover, the spherical base solid electrolyte material has better symmetry, and the metal material is easier to coat on the surface of the spherical base solid electrolyte material in the subsequent coating treatment process. On the other hand, the spherical base layer solid electrolyte material is easier to form close packing in the subsequent hot pressing process, and the defects in the prepared film are reduced.
In one specific example, the particle size of the base layer solid electrolyte material is 1 μm to 50 μm, alternatively, the particle size of the base layer solid electrolyte material is 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, or a range therebetween. More preferably, the D50 particle size of the base solid electrolyte material is 20 μm.
In one specific example, the base layer solid electrolyte is selected from lithium-conducting solid electrolytes. For example, the base solid electrolyte material is selected from LiPON, La1-xLi0.15+xTiO2.45+x、Li1+xAlxTi2-x(PO4)3、Li3+xGexP1-xS4、Li2+2xZn1- xGeO4、Li2S-AyS2y+1、Li2S-Yy-1Sy、Li7La3Zr2O12、Li2S、Li3N、Li3PO4、LiPF6、Li14Zn(GeO4)4One or more of; wherein x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 1 and less than or equal to 3; a is selected from one or more of P, B and Al, and Y is selected from one or two of Si and Ge. More preferably, the base layer solid electrolyte material may be LiPON. Here, LiPON is lithium phosphate containing nitrogen, and the chemical formula of each of the other materials can be understood according to the general knowledge of those skilled in the art. The nitrogen-containing lithium phosphate is a material that can be obtained by sputtering a lithium phosphate target in nitrogen, and is very suitable for preparing a film-like material.
In one specific example, the metal material has a particle size of 10nm to 50nm, and optionally, the metal material has a particle size of 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50 nm. The particle size of the metal material is obviously lower than that of the base solid electrolyte material, and the metal material with extremely small particle size has higher surface energy and is easy to combine with the same material, so that the metal material can be coated on the surface of the base solid electrolyte material with larger particle size in the subsequent dry coating process.
In one specific example, the metal material may be selected from one or more of lithium, silver, or copper. More preferably, the metal material is lithium. The lithium metal material can be partially doped in the crystal lattice of the lithium-conducting solid electrolyte, has better compatibility with the lithium-conducting solid electrolyte, and avoids the influence on the conduction of lithium ions due to the generation of excessive interfaces.
In one specific example, the base layer solid electrolyte material is selected from LiPON and the metal material is lithium.
In one specific example, the manner of obtaining the base layer solid electrolyte material having a particle size of 1 μm to 50 μm may be mechanical milling, and the manner of mechanical milling may be high-speed ball milling. In other specific examples, the base layer solid state electrolyte material may also be commercially available.
And step S2, mixing the base layer solid electrolyte material and the metal material in a dry coating machine, and performing coating treatment.
In this step, the dry coating process enables the metal material to be uniformly dispersed and adsorbed on the surface of the base solid electrolyte material to form a coating layer, so as to prepare the composite material.
In one specific example, the dry coating may be performed in a dry coater. "dry coating" is a coating process that can be performed without the need for a liquid environment. Generally, a base material and a coating material are physically mixed, friction and collision occur in the mixing process, and the coating material can be uniformly dispersed and adsorbed on the surface of the base material to form a coating layer. The actual physical mixing process of dry coating may be high speed rotation, spiral up and down motion, etc. It is understood that dry coating does not mean complete removal of liquid, for example, some liquid additives may be added during dry coating to enhance adhesion between the coating material and the aggregate material and improve coating efficiency. In this particular example, the dry-coated raw material may only require the base solid electrolyte material and the metal material, since the metal material having a very small particle size has a very good binding force and adhesion property.
In this embodiment, the dry coating is performed in a dry coating machine. The dry-process coating machine is a NOBILTA NOB type dry-process coating machine of Mikrron corporation, thin Sichuan. The dry-method coating machine enables particles of two materials to be uniformly mixed through operations such as stirring, throwing and the like, and metal materials with small particles can be uniformly dispersed and adsorbed on the surface of a base solid electrolyte material with large particles to form a coating layer. Thus, the preparation of the composite material can be completed.
In some embodiments, the dry coating time is 1-5 hours.
In some embodiments, the rotating speed of the stirring paddle is 2000r/min to 5000r/min in the dry coating process.
In one specific example, a metal material is mixed with a base layer solid electrolyte material in an environment with a relative humidity of-35 degrees; further, the metal material is mixed with the base layer solid electrolyte material under a vacuum environment. The metal material with smaller grain diameter has higher surface energy, and can effectively avoid the introduction of excessive impurity elements when being operated under the anhydrous and anaerobic treatment condition.
In one specific example, the ratio of the amount of the metal material to the substance of the base solid electrolyte material is (1-10): 1. Specifically, the ratio of the amounts of the substances of the metal material and the base layer solid electrolyte material is 1:1, 2:1, 4:1, 6:1, 8:1, 10:1, or a range between the ratios of the amounts of the above substances.
And step S3, preparing the composite material obtained after the dry coating treatment into a film-shaped material to obtain the composite solid electrolyte base layer.
In one specific example, the method of preparing the composite material into a film-like material is hot press film formation. Specifically, the composite material which is coated by the dry method and originally in the powder state is pressed into a film layer under the heating treatment. In the hot pressing process, the original gaps among the composite materials can be removed by applying pressure to press the composite materials, so that the metal materials of the shell layer are contacted more tightly; in addition, the diffusion rate of atoms can be promoted by means of higher temperature, so that the materials of the coating layers are combined together to form a complete film layer. The purpose of the hot-press film-forming process is to compact the composite material, for example at a pressure of 10 to 50 tonnes.
In one specific example, the resulting composite is transferred to a mold and then autoclaved. The die can comprise an upper die and a lower die, wherein a groove is formed in the middle of the lower die, and a convex block matched with the groove is arranged in the middle of the upper die. And after the composite material is transferred into the groove, embedding the lug of the upper die into the groove of the lower die for hot pressing. The material of the mould can be graphite. More specifically, in one specific example, the pressure-bearing face area of the die is 100mm × 100 mm.
In one specific example, the hot-press film formation process is performed in a vacuum environment.
In one specific example, the hot pressing temperature is 100-150 ℃ in the process of hot pressing the composite material into a film; for example, the hot pressing temperature may be 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or a range between the above. In the case that the metal material is lithium, the hot pressing temperature is close to the melting temperature of lithium, and the diffusion rate of lithium atoms is greatly increased, so that the metal material on the surface of each base layer solid electrolyte material particle can generate lattice reconstruction in gaps among the particles, and the metal material in the metal material forms a complete metal channel, thereby effectively enhancing the diffusion rate of lithium ions.
In addition, since the base solid electrolyte material may deform to some extent during the hot-pressing film-forming process, the base solid electrolyte material does not necessarily maintain its original shape in the prepared composite solid electrolyte base layer, but generally, the metal material still covers the surface of the base solid electrolyte particles.
In addition, the thickness of the composite solid electrolyte base layer can be controlled to be 10 μm to 100 μm by controlling the amount of the composite material added to the mold.
Step S4, depositing a first surface layer solid electrolyte material on the first surface of the composite solid electrolyte base layer to prepare a first solid electrolyte surface layer.
In one specific example, the first facing solid state electrolyte material may be selected from lithium conducting electrolyte materials, such as: the first surface layer solid electrolyte material can be selected from LiPON and La1-xLi0.15+xTiO2.45+x、Li1+xAlxTi2-x(PO4)3、Li3+xGexP1-xS4、Li2+2xZn1-xGeO4、Li2S-AyS2y+1、Li2S-Yy-1Sy、Li7La3Zr2O12、Li2S、Li3N、Li3PO4、LiPF6、Li14Zn(GeO4)4One or more of; wherein x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 1 and less than or equal to 3; a is selected from one or more of P, B and Al, and Y is selected from one or two of Si and Ge.
In one specific example, the physical vapor deposition method is selected from radio frequency sputtering methods, and the sputtering power is 100W-1000W. Optionally, the sputtering power is 100W, 200W, 300W, 400W, 500W, 600W, 700W, 800W, 900W, 1000W, or a range therebetween. More preferably, the sputtering power is 500W.
The process of radio frequency sputtering can be completed in a vacuum chamber with a vacuum degree of less than 5 × 10-3Pa. The thickness of the first solid electrolyte surface layer can be controlled to be 1000 nm-3000 nm by controlling parameters such as deposition time and the like.
Step S5, depositing a second solid electrolyte surface layer material on the second surface of the composite solid electrolyte base layer to prepare a second solid electrolyte surface layer.
In one specific example, the second facing solid state electrolyte material may be selected from lithium conducting electrolyte materials, such as: the second surface layer solid electrolyte material can be selected from LiPON and La1-xLi0.15+xTiO2.45+x、Li1+xAlxTi2-x(PO4)3、Li3+xGexP1-xS4、Li2+2xZn1-xGeO4、Li2S-AyS2y+1、Li2S-Yy-1Sy、Li7La3Zr2O12、Li2S、Li3N、Li3PO4、LiPF6、Li14Zn(GeO4)4One or more of; wherein x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 1 and less than or equal to 3; a is selected from one or more of P, B and Al,y is selected from one or two of Si and Ge.
In one specific example, the physical vapor deposition method is selected from radio frequency sputtering methods, and the sputtering power is 100W-1000W. Optionally, the sputtering power is 100W, 200W, 300W, 400W, 500W, 600W, 700W, 800W, 900W, 1000W, or a range therebetween. More preferably, the sputtering power is 500W.
The process of radio frequency sputtering can be completed in a vacuum chamber with a vacuum degree of less than 5 × 10-3Pa. The thickness of the second solid electrolyte surface layer can be controlled to be 1000 nm-3000 nm by controlling parameters such as deposition time and the like.
It is to be understood that the deposition of the first and second facing solid state electrolyte materials may be performed simultaneously during the deposition of steps S4 and S5 described above.
In step S6, the solid electrolyte membrane layer is subjected to heat treatment.
Certain film defects often exist between the deposited first solid electrolyte surface layer and/or the deposited second solid electrolyte surface layer. Film defects not only lead to reduced ionic conductivity properties, but also may lead to local shorting of the solid electrolyte. In order to improve the preparation yield of the solid electrolyte, the heating treatment can be carried out when or after the first solid electrolyte surface layer and the second solid electrolyte surface layer are prepared, and the heating temperature is 80-140 ℃.
In one specific example, the heating temperature may be 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, or a range between the above temperatures.
In another specific example, the heating treatment may also be performed while the first solid electrolyte face layer and/or the second solid electrolyte face layer are prepared.
By the above-described preparation steps, the preparation of the solid electrolyte can be substantially completed. However, it is understood that the above preparation method may additionally add other preparation steps to impart more functions to the solid electrolyte.
Meanwhile, the embodiment of the invention also provides the solid electrolyte prepared by the preparation method of the solid electrolyte.
Referring to fig. 1, a solid electrolyte according to an embodiment of the present invention includes the following structure:
a composite solid electrolyte base layer 100, a first solid electrolyte face layer 110 disposed on a first surface 101 of the composite solid electrolyte base layer 100, and a second solid electrolyte face layer 120 disposed on a second surface 102, the first surface 101 and the second surface 102 being opposite. Referring to fig. 2, the composite solid electrolyte base layer 100 is a core-shell structure, wherein the core material is a base layer solid electrolyte material 103, the shell material is a lithium conducting material 104, the particle size of the core material is 1 μm to 50 μm, the particle size of the shell material is 10nm to 50nm, and the lithium conducting material 104 is a metal material.
The first solid electrolyte face layer 110 is made of a raw material comprising a first face layer solid electrolyte material. The second solid state electrolyte face layer 120 is made of a raw material that includes a second face layer solid state electrolyte material.
The materials of the respective layers in the solid electrolyte may refer to those used in the production methods of the above-described examples.
In one specific example, the thickness of the first solid electrolyte face layer 110 is 1000nm to 3000 nm. For example, the thickness of the first solid electrolyte face layer 110 may be 1000nm, 1200nm, 1500nm, 2000nm, 2200nm, 2500nm, 3000nm, or a range between any of the foregoing thicknesses.
In one specific example, the thickness of the second solid electrolyte surface layer 120 is 500nm to 1500 nm. For example, the thickness of the second solid electrolyte surface layer 120 may be 1000nm, 1200nm, 1500nm, 2000nm, 2200nm, 2500nm, 3000nm, or a range between any of the foregoing thicknesses.
In a specific example, the thickness of the composite solid electrolyte base layer 100 is 10 μm to 100 μm. For example, the thickness of the second solid electrolyte surface layer 120 may be 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, or a range between the above thicknesses.
It will be appreciated that the solid electrolyte may be a lithium battery solid electrolyte. In lithium battery solid-state electrolytes, lithium ions are transported in vacancies in the solid-state electrolyte lattice, but such transport rates tend to be slow. In the solid electrolyte described above, the first solid electrolyte surface layer 110 and the second solid electrolyte surface layer 120 serve as contact surfaces of the positive electrode and the negative electrode, and have a function of conducting lithium ions and isolating electrons. If lithium ions enter the second solid electrolyte surface layer 120 through the first solid electrolyte surface layer 110 and migrate to the second solid electrolyte surface layer 120 side, when the lithium ions migrate through the metal lithium in the composite solid electrolyte base layer, the metal lithium equivalently forms a rapid migration channel of the lithium ions, and the lithium ions in the metal lithium part do not need to be transferred by virtue of crystal lattice vacancies in the solid electrolyte, but directly realize the migration of the lithium ions by virtue of the potential difference between the positive electrode and the negative electrode, so that the extremely rapid migration can be realized, and the ion conductivity of the solid electrolyte is obviously improved. Similar principles apply to solid electrolytes of other systems.
In a specific example, in the composite solid electrolyte base layer 100, the ratio of the amount of the substance of the lithium conducting material 104 to the base layer solid electrolyte material 103 is (1-10): 1. Specifically, the ratio of the amounts of the substances of the lithium conductive material 104 and the base layer solid electrolyte material 103 is 1:1, 2:1, 4:1, 6:1, 8:1, 10:1, or ranges between the amounts of the above substances.
In another aspect, a solid-state battery includes a positive electrode, a negative electrode, and a solid-state electrolyte disposed between and in contact with the positive electrode and the negative electrode, respectively, the solid-state electrolyte being the solid-state electrolyte as in the above-described examples, or the solid-state electrolyte prepared by the method of preparing the solid-state electrolyte as in the above-described examples.
Specifically, the solid-state battery may be a lithium ion solid-state battery, wherein the positive electrode is a positive electrode of the lithium ion battery, the negative electrode is a negative electrode of the lithium ion battery, the base layer solid-state electrolyte material, the first surface layer solid-state electrolyte material and the second surface layer solid-state electrolyte material in the solid-state electrolyte are all selected from materials capable of conducting lithium ions, and the metal material is lithium. Optionally, the base layer solid state electrolyte material, the first face layer solid state electrolyte material, and the second face layer solid state electrolyte material are all nitrogen-containing lithium phosphate.
In order that the invention may be more readily understood and readily carried into effect, the following more specific and detailed test examples and comparative examples are provided below by reference. The embodiments of the present invention and their advantages will also be apparent from the description of specific test examples and comparative examples and performance results described below. In each of the following test examples and comparative examples,
the raw materials used in the following examples and comparative examples are all commercially available without specific indication.
The dry-process coating machines used in the following examples and comparative examples were NOBILTA NOB model dry-process coating machines from Mikrron corporation, thin Sichuan.
Example 1
(1) Grinding solid electrolyte particles LiPON to spherical particles with the particle size of D50 being about 20 mu m by using a ball mill, and then uniformly mixing lithium metal particles with the particle size of about 40nm with the LiPON particles in an environment with the relative humidity of-35 ℃, wherein the mass ratio of the lithium metal to the LiPON is 2: 1;
(2) putting the mixed material into a dry-method coating machine, stirring and mixing for 2 hours at the rotating speed of a stirring paddle of about 3000r/min to fully coat the lithium metal particles on the surfaces of the solid electrolyte particles to prepare a composite material;
(3) introducing the composite material into a graphite square shell clamp with the thickness of 100mm multiplied by 100mm, placing a graphite box into a vacuum heating furnace, setting the temperature at 120 ℃, heating for 2 hours, taking out, and compacting the graphite square shell clamp by using a graphite plate to obtain a composite solid electrolyte base layer with the thickness of about 50 mu m;
(4) placing the composite solid electrolyte base layer in a vacuum cavity, depositing LiPON materials on the top layer and the bottom layer simultaneously through radio frequency sputtering, wherein the sputtering power is 500W, and preparing a first solid electrolyte surface layer and a second solid electrolyte surface layer, wherein the thicknesses of the first solid electrolyte surface layer and the second solid electrolyte surface layer are about 1 mu m;
(5) and (3) introducing the solid electrolyte after deposition into a heating chamber, setting the temperature at 120 ℃, and the transmission speed at 1m/h, introducing dry argon to normal pressure after deposition, opening a vacuum cavity, and taking out the solid electrolyte.
Example 2
(1) Grinding solid electrolyte particles LiPON to spherical particles with the particle size of D50 being about 20 mu m by using a ball mill, and then uniformly mixing lithium metal particles with the particle size of about 40nm with the LiPON particles in an environment with the relative humidity of-35 ℃, wherein the mass ratio of the lithium metal to the LiPON is 4: 1;
(2) putting the mixed material into a dry-method coating machine, stirring and mixing for 3 hours at the rotating speed of a stirring paddle of about 3000r/min to fully coat the lithium metal particles on the surfaces of the solid electrolyte particles to prepare a composite material;
(3) introducing the composite material into a graphite square shell clamp with the thickness of 100mm multiplied by 100mm, placing a graphite box into a vacuum heating furnace, setting the temperature at 120 ℃, heating for 2 hours, taking out, and compacting the graphite square shell clamp by using a graphite plate to obtain a composite solid electrolyte base layer with the thickness of about 50 mu m;
(4) placing the composite solid electrolyte base layer in a vacuum cavity, depositing LiPON materials on the top layer and the bottom layer simultaneously through radio frequency sputtering, wherein the sputtering power is 500W, and preparing a first solid electrolyte surface layer and a second solid electrolyte surface layer, wherein the thicknesses of the first solid electrolyte surface layer and the second solid electrolyte surface layer are about 1 mu m;
(5) and (3) introducing the solid electrolyte after deposition into a heating chamber, setting the temperature at 120 ℃, and the transmission speed at 1m/h, introducing dry argon to normal pressure after deposition, opening a vacuum cavity, and taking out the solid electrolyte.
Example 3
(1) Grinding solid electrolyte particles LiPON to spherical particles with the particle size of D50 being about 20 mu m by using a ball mill, and then uniformly mixing lithium metal particles with the particle size of about 40nm with the LiPON particles in an environment with the relative humidity of-35 ℃, wherein the mass ratio of the lithium metal to the LiPON is 8: 1;
(2) putting the mixed material into a dry-method coating machine, stirring and mixing for 4 hours at the rotating speed of a stirring paddle of about 3000r/min to fully coat the lithium metal particles on the surfaces of the solid electrolyte particles to prepare a composite material;
(3) introducing the composite material into a graphite square shell clamp with the thickness of 100mm multiplied by 100mm, placing a graphite box into a vacuum heating furnace, setting the temperature at 120 ℃, heating for 2 hours, taking out, and compacting the graphite square shell clamp by using a graphite plate to obtain a composite solid electrolyte base layer with the thickness of about 50 mu m;
(4) placing the composite solid electrolyte base layer in a vacuum cavity, depositing LiPON materials on the top layer and the bottom layer simultaneously through radio frequency sputtering, wherein the sputtering power is 500W, and preparing a first solid electrolyte surface layer and a second solid electrolyte surface layer, wherein the thicknesses of the first solid electrolyte surface layer and the second solid electrolyte surface layer are about 1 mu m;
(5) and (3) introducing the solid electrolyte after deposition into a heating chamber, setting the temperature at 120 ℃, and the transmission speed at 1m/h, introducing dry argon to normal pressure after deposition, opening a vacuum cavity, and taking out the solid electrolyte.
Example 4
(1) Grinding solid electrolyte particles LiPON to spherical particles with the particle size of D50 being about 20 mu m by using a ball mill, and then uniformly mixing lithium metal particles with the particle size of about 40nm with the LiPON particles in an environment with the relative humidity of-35 ℃, wherein the mass ratio of the lithium metal to the LiPON is 8: 1;
(2) putting the mixed material into a dry-method coating machine, stirring and mixing for 5 hours at the rotating speed of a stirring paddle of about 3000r/min to fully coat the lithium metal particles on the surfaces of the solid electrolyte particles to prepare a composite material;
(3) introducing the composite material into a graphite square shell clamp with the thickness of 100mm multiplied by 100mm, placing a graphite box into a vacuum heating furnace, setting the temperature at 120 ℃, heating for 2 hours, taking out, and compacting the graphite square shell clamp by using a graphite plate to obtain a composite solid electrolyte base layer with the thickness of about 50 mu m;
(4) placing the composite solid electrolyte base layer in a vacuum cavity, depositing LiPON materials on the top layer and the bottom layer simultaneously through radio frequency sputtering, wherein the sputtering power is 500W, and preparing a first solid electrolyte surface layer and a second solid electrolyte surface layer, wherein the thicknesses of the first solid electrolyte surface layer and the second solid electrolyte surface layer are about 1 mu m;
(5) and (3) introducing the solid electrolyte after deposition into a heating chamber, setting the temperature at 60 ℃, and the transmission speed at 1m/h, introducing dry argon to normal pressure after deposition, opening a vacuum cavity, and taking out the solid electrolyte.
Example 5
(1) Grinding solid electrolyte particles LiPON to spherical particles with the particle size of D50 being about 20 mu m by using a ball mill, and then uniformly mixing lithium metal particles with the particle size of about 40nm with the LiPON particles in an environment with the relative humidity of-35 ℃, wherein the mass ratio of the lithium metal to the LiPON is 2: 1;
(2) putting the mixed material into a dry-method coating machine, stirring and mixing for 2 hours at the rotating speed of a stirring paddle of about 3000r/min to fully coat the lithium metal particles on the surfaces of the solid electrolyte particles to prepare a composite material;
(3) introducing the composite material into a graphite square shell clamp with the thickness of 100mm multiplied by 100mm, placing a graphite box into a vacuum heating furnace, setting the temperature at 120 ℃, heating for 2 hours, taking out, and compacting the graphite square shell clamp by using a graphite plate to obtain a composite solid electrolyte base layer with the thickness of about 50 mu m;
(4) placing the composite solid electrolyte base layer in a vacuum cavity, depositing LiPON materials on the top layer and the bottom layer simultaneously through radio frequency sputtering, wherein the sputtering power is 500W, and preparing a first solid electrolyte surface layer and a second solid electrolyte surface layer, wherein the thicknesses of the first solid electrolyte surface layer and the second solid electrolyte surface layer are about 3 mu m;
(5) and (3) introducing the solid electrolyte after deposition into a heating chamber, setting the temperature at 120 ℃, and the transmission speed at 1m/h, introducing dry argon to normal pressure after deposition, opening a vacuum cavity, and taking out the solid electrolyte.
Example 6
(1) Grinding solid electrolyte particles LiPON to spherical particles with the particle size of D50 being about 20 mu m by using a ball mill, and then uniformly mixing lithium metal particles with the particle size of about 40nm with the LiPON particles in an environment with the relative humidity of-35 ℃, wherein the mass ratio of the lithium metal to the LiPON is 2: 1;
(2) putting the mixed material into a dry-method coating machine, stirring and mixing for 2 hours at the rotating speed of a stirring paddle of about 3000r/min to fully coat the lithium metal particles on the surfaces of the solid electrolyte particles to prepare a composite material;
(3) introducing the uniformly mixed materials into a graphite square shell clamp with the thickness of 100mm multiplied by 100mm, then placing a graphite box into a vacuum heating furnace, keeping the temperature at normal temperature, pressing for 2 hours, taking out, and compacting the graphite square shell clamp by using a graphite plate to prepare a composite solid electrolyte base layer with the thickness of about 50 mu m;
(4) placing the composite solid electrolyte base layer in a vacuum cavity, depositing LiPON materials on the top layer and the bottom layer simultaneously through radio frequency sputtering, wherein the sputtering power is 500W, and preparing a first solid electrolyte surface layer and a second solid electrolyte surface layer, wherein the thicknesses of the first solid electrolyte surface layer and the second solid electrolyte surface layer are about 1 mu m;
(5) and (3) introducing the solid electrolyte after deposition into a heating chamber, setting the temperature at 120 ℃, and the transmission speed at 1m/h, introducing dry argon to normal pressure after deposition, opening a vacuum cavity, and taking out the solid electrolyte.
Comparative example 1
(1) Grinding solid electrolyte particles LiPON to spherical particles having a D50 particle size of about 20 μm using a ball mill;
(2) introducing solid electrolyte particles LiPON into a graphite square shell clamp with the thickness of 100mm multiplied by 100mm, then placing a graphite box into a vacuum heating furnace, setting the temperature at 120 ℃, heating for 2 hours, taking out, and compacting the graphite square shell clamp by using a graphite plate to prepare a composite solid electrolyte base layer with the thickness of about 52 mu m;
comparative example 2
(1) Grinding solid electrolyte particles LiPON to spherical particles having a D50 particle size of about 20 μm using a ball mill;
(2) putting lithium metal particles with the particle size of about 40nm and the LiPON particles in a ball mill in an environment with the relative humidity of-35 ℃, wherein the rotating speed of the ball mill is 500r/min, the ball milling time is 2 hours, so that the lithium metal particles and the LiPON particles are fully mixed, and the mass ratio of the lithium metal to the LiPON particles is 2: 1;
(3) introducing the uniformly mixed materials into a graphite square shell clamp with the thickness of 100mm multiplied by 100mm, placing a graphite box into a vacuum heating furnace, setting the temperature at 120 ℃, heating for 2 hours, taking out, and compacting the graphite square shell clamp by using a graphite plate to prepare a composite solid electrolyte base layer with the thickness of about 50 mu m;
(4) placing the composite solid electrolyte base layer in a vacuum cavity, depositing LiPON materials on the top layer and the bottom layer simultaneously through radio frequency sputtering, wherein the sputtering power is 500W, and preparing a first solid electrolyte surface layer and a second solid electrolyte surface layer, wherein the thicknesses of the first solid electrolyte surface layer and the second solid electrolyte surface layer are about 1 mu m;
(5) and (3) introducing the solid electrolyte after deposition into a heating chamber, setting the temperature at 120 ℃, and the transmission speed at 1m/h, introducing dry argon to normal pressure after deposition, opening a vacuum cavity, and taking out the solid electrolyte.
Comparative example 3
(1) Grinding solid electrolyte particles LiPON to spherical particles with the particle size of D50 being about 20 mu m by using a ball mill, and then uniformly mixing lithium metal particles with the particle size of about 40nm with the LiPON particles in an environment with the relative humidity of-35 ℃, wherein the mass ratio of the lithium metal to the LiPON is 2: 1;
(2) and (3) introducing the uniformly mixed materials into a graphite square shell clamp with the thickness of 100mm multiplied by 100mm, placing a graphite box into a vacuum heating furnace, keeping the temperature at normal temperature, pressing for 2 hours, taking out, and compacting the graphite square shell clamp by using a graphite plate to obtain the composite solid electrolyte base layer with the thickness of about 50 mu m.
The solid electrolytes obtained in examples 1 to 5 and comparative examples 1 to 3 were respectively tested for ionic conductivity and internal resistance of batteries assembled therefrom, and the results are shown in table 1.
The method for testing the ionic conductivity comprises the following steps:
the ionic conductivity sigma of the electrolyte film can be obtained through the following formula according to the volume resistance R in the electrolyte alternating-current impedance spectrum, the area A of the electrolyte film opposite to the contact pole piece and the thickness d of the electrolyte film.
Figure BDA0002862526940000181
The solid electrolytes obtained in examples 1 to 5 and comparative examples 1 to 3 were used to prepare batteries by using a copper foil 8 μm thick coated with graphite 50 μm thick as a negative electrode and a lithium cobaltate film prepared by sputtering as a positive electrode, and internal resistances of the batteries were measured. The method for testing the internal resistance of the battery comprises the following steps: measuring the open circuit voltage U of a battery1Connecting a resistor with resistance R in parallel at two ends of the batteryDischarging, measuring the voltage U across the battery during the discharge period2And calculating the internal resistance of the battery: r ═ U (U)1-U2)/(U2/R)。
TABLE 1
Item Ion conductivity (S.cm)-1) Internal resistance of battery (omega)
Example 1 2.7×10-6 370
Example 2 3.0×10-6 350
Example 3 3.6×10-6 300
Example 4 1.9×10-6 440
Example 5 0.8×10-6 510
Example 6 0.3×10-6 592
Comparative example 1 1.5×10-7 621
Comparative example 2 2.5×10-7 650
Comparative example 3 -- 0.015
Where "- -" indicates no valid result.
As shown in Table 1, the ionic conductivities of examples 1 to 3 were as high as 2.7X 10-6And more than S/cm. Example 4 the subsequent heating process at a lower temperature resulted in a lower ionic conductivity of only 1.9X 10 compared to example 1-6S/cm。
Comparative example 1 no metal additive material was added to the solid electrolyte membrane. Comparative example 1 in comparison with example 1, a solid electrolyte thin film was directly prepared by ball-milling an electrolyte material and then hot-pressing, and the obtained ionic conductivity was 1.5 × 10- 7S/cm. Comparative example 2 in comparison with example 1, lithium metal particles were simply ball-milled and mixed with LiPON solid electrolyte particles, in which lithium metal was not coated or sufficiently coated on the surfaces of the LiPON solid electrolyte particles, and thus the resulting ionic conductivity was low, only 2.5 × 10-7S/cm. The solid electrolyte prepared in comparative example 3 does not have a surface coating layer, and thus cannot effectively separate the positive electrode and the negative electrode of the battery, so that the internal resistance is extremely low, and the electrolyte is in a short circuit state, wherein the electrolyte in the short circuit state is mainly in electron conduction. Ionic conductivity is difficult to detect effectively and has no practical significance.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (11)

1. A method for preparing a solid electrolyte, comprising the steps of:
mixing a base layer solid electrolyte material with the particle size of 1-50 mu m and a lithium conducting material with the particle size of 10-50 nm in a dry coating machine, and performing coating treatment to uniformly disperse the lithium conducting material and adsorb the lithium conducting material on the surface of the base layer solid electrolyte material to form a coating layer so as to prepare a composite material, wherein the lithium conducting material is a metal material;
preparing the composite material into a film-shaped material to obtain a composite solid electrolyte base layer;
depositing a first surface layer solid electrolyte material on the surface of one side of the composite solid electrolyte base layer to form a first solid electrolyte surface layer; and depositing a second surface layer solid electrolyte material on the surface of the other side opposite to the composite solid electrolyte base layer to form a second solid electrolyte surface layer.
2. The method for producing a solid electrolyte according to claim 1, wherein the ratio of the amounts of the metal material and the base solid electrolyte material is (1-10): 1.
3. The method of producing a solid electrolyte according to claim 1, characterized in that the method of depositing the first-facing solid electrolyte material and/or the second-facing solid electrolyte material is a physical vapor deposition method.
4. The method for producing a solid electrolyte according to any one of claims 1 to 3,
the method also comprises a step of heating the first solid electrolyte surface layer and the second solid electrolyte surface layer, wherein the heating temperature is 80-140 ℃.
5. The method for producing a solid electrolyte according to any one of claims 1 to 3, wherein the first surface layer solid electrolyte material, the second surface layer solid electrolyte material, and the base layer solid electrolyte material are each independently selected from LiPON, La, and La1-xLi0.15+xTiO2.45+x、Li1+xAlxTi2-x(PO4)3、Li3+xGexP1-xS4、Li2+2xZn1-xGeO4、Li2S-AyS2y+1、Li2S-Yy-1Sy、Li7La3Zr2O12、Li2S、Li3N、Li3PO4、LiPF6、Li14Zn(GeO4)4One or more of; wherein x is more than or equal to 0 and less than or equal to 0.5, and y is more than or equal to 1 and less than or equal to 3; a is selected from one or more of P, B and Al, and Y is selected from one or two of Si and Ge.
6. A method of producing a solid state electrolyte as claimed in any one of claims 1 to 3 wherein the metallic material comprises one or more of lithium, copper and silver.
7. The method for producing a solid electrolyte according to any one of claims 1 to 3, wherein the base layer solid electrolyte material is LiPON and the metal material is metallic lithium.
8. A solid state electrolyte, comprising: the composite solid electrolyte comprises a composite solid electrolyte base layer, a first solid electrolyte surface layer and a second solid electrolyte surface layer, wherein the first solid electrolyte surface layer is arranged on a first surface of the composite solid electrolyte base layer, and the second solid electrolyte surface layer is arranged on a second surface opposite to the first surface; the composite solid electrolyte base layer is of a core-shell structure, wherein a core material is a base layer solid electrolyte material, a shell material is a lithium conducting material, the particle size of the core material is 1-50 mu m, the particle size of the shell material is 10-50 nm, and the lithium conducting material is a metal material.
9. The solid state electrolyte of claim 8, wherein the first solid state electrolyte face layer has a thickness of 1000nm to 3000 nm; and/or
The thickness of the second solid electrolyte surface layer is 1000 nm-3000 nm; and/or
The thickness of the composite solid electrolyte base layer is 10-100 mu m.
10. A solid-state battery comprising a positive electrode, a negative electrode, and a solid-state electrolyte provided between and in contact with the positive electrode and the negative electrode, respectively, wherein the solid-state electrolyte is prepared by the preparation method according to any one of claims 1 to 7 or the solid-state electrolyte according to claim 8 or 9.
11. The solid-state battery according to claim 10, wherein the solid-state battery is a solid-state thin-film battery having an overall thickness of 500 μm or less.
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