CN113097560A - High-air-stability nanocrystalline sulfide solid electrolyte, solid-state battery and preparation method of solid-state battery - Google Patents

High-air-stability nanocrystalline sulfide solid electrolyte, solid-state battery and preparation method of solid-state battery Download PDF

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CN113097560A
CN113097560A CN202110382390.3A CN202110382390A CN113097560A CN 113097560 A CN113097560 A CN 113097560A CN 202110382390 A CN202110382390 A CN 202110382390A CN 113097560 A CN113097560 A CN 113097560A
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solid electrolyte
solid
ball milling
air
stability
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涂江平
蒋朝
***
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Shandong Industrial Technology Research Institute of ZJU
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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 belongs to the technical field of solid-state batteries, and particularly relates to a high-air-stability nanocrystalline sulfide solid electrolyte, a solid-state battery and a preparation method of the solid-state battery. The invention provides a high air stability nanocrystalline sulfide solid electrolyte, the chemical composition of which is Li6+yPxM1‑xS5I, wherein x is 0-1, and y is 0-3; and M is a soft acid metal element. According to the invention, the soft acid metal is doped into the solid electrolyte, so that on one hand, the ionic conductivity of the solid electrolyte is improved; on the other hand, the bonding property with sulfur is improved, and further, the air stability of the solid electrolyte is improved.

Description

High-air-stability nanocrystalline sulfide solid electrolyte, solid-state battery and preparation method of solid-state battery
Technical Field
The invention belongs to the technical field of solid-state batteries, and particularly relates to a high-air-stability nanocrystalline sulfide solid electrolyte, a solid-state battery and a preparation method of the solid-state battery.
Background
With the continuous improvement of living standard, people put forward higher requirements on energy storage equipment. The lithium battery has the advantages of large output power, high energy density, long service life, high average output voltage, small self-discharge, no memory effect, quick charge and discharge, excellent cycle performance, no environmental pollution and the like, is widely applied in daily life, becomes a preferred object of rechargeable power supplies for portable electronic products at present, and is also considered as the most competitive power battery for vehicles. Lithium batteries are classified into liquid lithium batteries and solid lithium batteries. Among them, the liquid lithium battery contains a large amount of combustible and volatile organic electrolyte, and is liable to cause safety problems such as fire and the like under the conditions of overcharge, overdischarge, high temperature and the like, thereby causing concern of people. The solid lithium battery is a lithium battery which comprises all units of the battery, including a positive electrode, a negative electrode and electrolyte, is made of solid materials, has incomparable safety with liquid lithium batteries, is expected to thoroughly eliminate potential safety hazards in the use process, and meets the future development requirements of the fields of electric automobiles and scale energy storage. Therefore, all-solid-state lithium batteries using a solid electrolyte are candidates for next-generation high energy density batteries. The development of a high-performance solid electrolyte is the key to realizing the all-solid-state lithium battery.
At present, solid electrolytes can be mainly classified into two major categories, i.e., inorganic solid electrolytes and polymer solid electrolytes. The polymer electrolyte has the defects of low normal-temperature ionic conductivity, narrow electrochemical window, poor high-temperature stability and the like, and can not meet the use requirement. The inorganic solid electrolyte has the advantages of wide electrochemical stability window, wide working temperature range, nonflammability, high shear modulus and the like, and has the advantages of incomparable safety and service life compared with organic electrolyte. Among them, the inorganic solid electrolyte is further classified into an oxide electrolyte and a sulfide electrolyte. Sulfide electrolytes are most excellent in ionic conductivity, which is comparable to that of liquid electrolytes, and thus have received much attention. However, large scale application of sulfide solid electrolytes still presents certain problems. On one hand, the traditional preparation method of the sulfide electrolyte is complex and consumes time; on the other hand, the prepared vulcanized solid electrolytes cannot be stored and used in air because these electrolytes have low chemical stability to moisture in air.
Disclosure of Invention
The invention provides a high-air-stability nanocrystalline sulfide solid electrolyte, a solid-state battery and a preparation method thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a high air stability nanocrystalline sulfide solid electrolyte, the chemical composition of which is Li6+ yPxM1-xS5I, wherein x is 0-1, and y is 0-3;
and M is a soft acid metal element.
Preferably, M is one or more of Ga, Sn, As, Sb, In, Bi, Cu and Pd.
The invention also provides a preparation method of the high-air-stability nanocrystalline sulfide solid electrolyte, which comprises the following steps:
mixing Li2S、LiI、P2S5And MmSnBall milling to obtain the high air stability nanocrystalline sulfide solid electrolyte;
the M ismSnWherein n is 1, 2, 3 or 5, and m is 1 or 2.
Preferably, said MmSnIs Ga2S3、SnS2、As2S5、Sb2S5、In2S3、Bi2S3One or more of CuS and PdS.
Preferably, in the ball milling process, Li2S、LiI、P2S5And MmSnThe molar ratio of (a) to (b) is 5.0-6.0: 2: 0.7-0.9: 0.1 to 0.9.
Preferably, the rotation speed of the ball milling is 1000-2000 rpm, and the ball milling time is 5-300 min.
Preferably, the ball-to-material ratio in the ball milling process is 20-50: 1.
preferably, the ball milling is performed in an argon atmosphere.
The invention also provides a solid-state battery which comprises a positive electrode, a solid electrolyte and a metal lithium negative electrode which are sequentially arranged, wherein the solid electrolyte is the high-air-stability nanocrystalline sulfide solid electrolyte prepared by the technical scheme or the high-air-stability nanocrystalline sulfide solid electrolyte prepared by the preparation method of the technical scheme.
The invention also provides a preparation method of the solid-state battery in the technical scheme, which comprises the following steps: and sequentially arranging the metal lithium cathode, the solid electrolyte and the anode, and compacting to obtain the solid battery.
The invention provides a high air stability nanocrystalline sulfide solid electrolyte, the chemical composition of which is Li6+ yPxM1-xS5I, wherein x is 0-1, and y is 0-3; and M is a soft acid metal element. According to the invention, the sulfide solid electrolyte is doped with the soft acid metal element, so that on one hand, the lithium ion transition activation energy can be greatly reduced by utilizing the larger ionic radius of the soft acid metal element, the lithium ion concentration is increased, and the ionic conductivity of the sulfide solid electrolyte is improved; on the other hand, on the basis of a soft and hard acid-base theory, the combination of the soft acid metal and the sulfur is adopted, so that the combination stability of the soft acid metal and the sulfur is improved, and the air stability of the sulfide solid electrolyte is further improved.
Secondly, the nanocrystalline sulfide solid electrolyte with high air stability is rich in element I, can form an interface rich in LiI, and improves the long-time cyclicity of lithium metal.
In addition, the preparation method of the high-air-stability nanocrystalline sulfide solid electrolyte provided by the invention is simple, and the high-air-stability nanocrystalline sulfide solid electrolyte can be obtained by performing ball milling on raw materials for one time.
Drawings
Fig. 1 is an assembly view of a solid-state battery prepared in example 1;
FIG. 2 is an SEM image of a high air stability nanocrystalline sulfide solid electrolyte prepared in example 1;
fig. 3 is a graph of ion conductivity before leaving the electrolytes prepared in example 1 and comparative example 1;
fig. 4 is a graph of ionic conductivity of the electrolytes prepared in example 1 and comparative example 1 after being left for 1 hour in an environment with a humidity of 30%;
fig. 5 is a graph of ion conductivity obtained in comparative example 2 before the electrolyte was left;
fig. 6 is a graph of ion conductivity obtained in comparative example 3 before the electrolyte was left;
FIG. 7 is a graph showing the ion conductivity before and after the electrolyte obtained in comparative example 4 was left;
FIG. 8 shows the electrolytes prepared in example 1 and comparative example 1 in air H2A time-varying curve of the S content;
fig. 9 is a lithium cycle deposition stripping diagram for a lithium/solid electrolyte/lithium symmetric battery employing the high air stability nanocrystalline sulfide solid electrolyte assembly prepared in example 1;
fig. 10 is a graph showing cycle characteristics of the solid-state battery prepared in example 1.
Detailed Description
The invention provides a high air stability nanocrystalline sulfide solid electrolyte, the chemical composition of which is Li6+ yPxM1-xS5I, wherein x is 0-1, and y is 0-3;
and M is a soft acid metal element.
In the present invention, as the raw material, commercially available products known to those skilled in the art may be used unless otherwise specified.
The chemical composition of the high-air-stability nanocrystalline sulfide solid electrolyte provided by the invention is Li6+yPxM1- xS5I, wherein x is preferably 0-1, more preferably 0.1-0.9, and even more preferably 0.2-0.8; y is preferably 0 to 3, more preferably 0 to 2.4, and still more preferably 0 to 1.8. In the invention, M is a soft acid metal element. In the invention, M is preferably one or more of Ga, Sn, As, Sb, In, Bi, Cu and Pd. In the present invention, the chemical composition of the high air-stability nanocrystalline sulfide solid electrolyte is further preferableComprising Li6.5P0.75In0.25S5I、Li6.2P0.9In0.1S5I、Li6P0.8Sb0.2S5I、Li6.3P0.7Sn0.3S5I and Li6.6P0.7Bi0.3S5I. According to the soft and hard acid-base theory, the combination of the M element and the S element is more stable, and more stable MS can be formed4The tetrahedral structure further improves the air stability of the sulfide solid electrolyte.
The invention also provides a preparation method of the high-air-stability nanocrystalline sulfide solid electrolyte, which comprises the following steps:
mixing Li2S、LiI、P2S5And MmSnBall milling to obtain the high air stability nanocrystalline sulfide solid electrolyte;
the M ismSnWherein n is 1, 2, 3 or 5, and m is 1 or 2.
In the invention, Li2S、LiI、P2S5And MmSnBall milling to obtain the high air stability nanocrystalline sulfide solid electrolyte. In the present invention, said MmSnWherein n is 1, 2, 3 or 5, and m is 1 or 2. In the present invention, said MmSnPreferably Ga2S3、SnS2、As2S5、Sb2S5、In2S3、Bi2S3One or more of CuS and PdS.
In the present invention, the ball milling is preferably carried out in a zirconia milling jar. In the invention, the ball milling mode is preferably dry ball milling, in the ball milling process, the used grinding balls are preferably zirconia balls with the particle size of 10mm, and the ball-to-material ratio is preferably 20-50: 1, more preferably 25 to 45: 1, more preferably 30 to 40: 1; the rotation speed of the ball milling is preferably 1000-2000 rpm, more preferably 1200-1800 rpm, and even more preferably 1400-1600 rpm; the time for ball milling is preferably 5 to 300min, more preferably 10 to 200min, and still more preferably 20 to 120 min. In the present invention, the ball milling is preferably performed in an argon atmosphere. In the invention, the ball milling process is different from the traditional low-speed mechanical ball milling, only the glassy electrolyte can be obtained, and the ball milling process can realize uniform and rapid mixing, crushing, vitrification and crystallization of raw materials to obtain the high-performance sulfide solid electrolyte containing nano crystals.
In the present invention, in the ball milling process, Li2S、LiI、P2S5And MmSnThe molar ratio of (a) to (b) is preferably 5.0 to 6.0: 2: 0.7-0.9: 0.1 to 0.9, more preferably 5.2 to 5.9: 2: 0.7-0.9: 0.2 to 0.8, more preferably 5.3 to 5.8: 2: 0.75-0.85: 0.3 to 0.7; in the examples of the present invention, 5.5:2:0.75:0.25, 5.2:2:0.9:0.1, 5:2:0.8:0.2, 5.3:2:0.7:0.3 and 5.6:2:0.7:0.3 are specific.
The invention also provides a solid-state battery which comprises a positive electrode, a solid electrolyte and a metal lithium negative electrode which are sequentially arranged, wherein the solid electrolyte is the high-air-stability nanocrystalline sulfide solid electrolyte prepared by the technical scheme or the high-air-stability nanocrystalline sulfide solid electrolyte prepared by the preparation method of the technical scheme.
The solid-state battery provided by the invention comprises a positive electrode, a solid electrolyte and a metallic lithium negative electrode which are sequentially arranged. In the present invention, the lithium metal negative electrode is preferably a lithium foil. The invention has no special requirement on the sizes of the anode and the cathode, and the sizes of the anode and the cathode of the lithium metal battery which are well known by the technical personnel in the field can be adopted.
The invention also provides a preparation method of the solid-state battery, which comprises the following steps: and sequentially arranging the metal lithium cathode, the solid electrolyte and the anode, and compacting to obtain the solid battery.
The invention preferably ball-mills elemental sulfur, cabo carbon, acetylene black and solid electrolyte to obtain the anode. In the invention, the solid electrolyte is preferably the nanocrystalline sulfide solid electrolyte with high air stability according to the technical scheme. In the present invention, the ball milling is preferably performed in a stainless steel ball milling jar. In the invention, the mass ratio of the elemental sulfur, the cabozon carbon, the acetylene black and the solid electrolyte is preferably 70-80: 5-10: 5-10: 10 to 15, and more preferably 72 to 78: 6-9: 6-9: 11-14, more preferably 74-76: 7-8: 7-8: 12 to 13. In the invention, the electronic conductivity of elemental sulfur can be further improved by adding carbon black; the solid electrolyte is added into the elemental sulfur, so that the utilization rate of the elemental sulfur active substances can be increased, and the ionic conductivity of the elemental sulfur can be further improved.
In the invention, preferably, elemental sulfur and cabozo carbon are ball-milled to obtain a primary material; and adding acetylene black and solid electrolyte into the primary material, and performing secondary ball milling to obtain the anode. In the invention, the ball milling process can increase the utilization rate of the elemental sulfur active substances and can effectively regulate and control the distribution of the elemental sulfur in the anode.
In the invention, elemental sulfur and Kabo carbon are preferably ball-milled to obtain a primary material. In the invention, the rotation speed of the ball mill is preferably 600-800 rpm, more preferably 650-750 rpm, and more preferably 700 rpm; the ball milling time is preferably 5 to 10 hours, more preferably 6 to 9 hours, and even more preferably 7 to 8 hours.
After the primary material is obtained, acetylene black and solid electrolyte are added into the primary material, and secondary ball milling is carried out to obtain the anode. In the invention, the rotation speed of the secondary ball milling is preferably 300-400 rpm, more preferably 320-380 rpm, and more preferably 340-360 rpm; the time for the secondary ball milling is preferably 1 to 2 hours, and more preferably 1.5 hours. In the invention, the low-speed ball milling process can prevent the crystal structure of the solid electrolyte from being damaged in the ball milling process, so that the ionic conductivity is reduced.
The lithium metal cathode, the solid electrolyte and the anode are sequentially arranged and compacted to obtain the solid battery. Preferably, the solid electrolyte is firstly placed in a polyether-ether-ketone tube with the diameter of 10mm and is pressed for the first time to obtain a solid electrolyte membrane; placing a positive electrode on one side of the solid electrolyte membrane, and performing secondary pressing; the metallic lithium negative electrode was placed on the other side of the solid electrolyte membrane, and third pressing was performed to obtain a solid-state battery. In the invention, the mass ratio of the positive electrode to the solid electrolyte is preferably 3-6: 50 to 100, and more preferably 4 to 5: 55 to 95. In the invention, the lithium metal negative electrode is preferably a lithium foil, and the thickness of the lithium foil is preferably 50-100 μm, more preferably 55-95 μm, and even more preferably 60-90 μm.
The solid electrolyte is preferably firstly placed in a polyether-ether-ketone tube with the diameter of 10mm and is pressed for the first time, so that the solid electrolyte membrane is obtained. In the invention, the pressure of the first pressing is 200-400 MPa, more preferably 250-350 MPa, and still more preferably 280-320 MPa; the time is preferably 4 to 8min, more preferably 5 to 7min, and still more preferably 6 min.
After the solid electrolyte membrane is obtained, the present invention preferably places the positive electrode on one side of the solid electrolyte membrane and performs the second pressing. In the invention, the pressure of the second pressing is preferably 200-400 MPa, more preferably 250-350 MPa, and even more preferably 280-320 MPa; the time is preferably 4 to 8min, more preferably 5 to 7min, and still more preferably 6 min.
In the present invention, it is preferable that the metallic lithium negative electrode is placed on the other side of the solid electrolyte membrane and subjected to a third pressing to obtain a solid-state battery. In the invention, the pressure of the third pressing is preferably 40-80 MPa, more preferably 45-75 MPa, and more preferably 50-70 MPa; the time is preferably 2 to 4min, and more preferably 3 min.
For further illustration of the present invention, the following detailed description will be made of a high air stability nanocrystalline sulfide solid electrolyte and solid-state battery and the manufacturing method thereof, which are provided by the present invention, with reference to the drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparing the nanocrystalline sulfide solid electrolyte with high air stability:
mixing Li2S、LiI、P2S5And In2S3Mixing according to a molar ratio of 5.5:2:0.75:0.25, putting the mixture into a zirconia grinding tank under the protection of argon, wherein the rotation speed of ball milling is 1200rpm, and the ball milling time is 30min, so as to obtain the high-air-stability nanocrystalline sulfide solid electrolyte, wherein the chemical composition of the high-air-stability nanocrystalline sulfide solid electrolyte is Li6.5P0.75In0.25S5I；
Preparing a solid-state battery:
placing elemental sulfur and Kabo carbon in a stainless steel ball-milling tank for mechanical ball milling for 10 hours at the rotating speed of 600 rpm; after the ball milling is finished, acetylene black and solid electrolyte (Li) are added into a ball milling tank6.5P0.75In0.25S5I) Performing secondary mechanical ball milling for 1h at the rotating speed of 300rpm to obtain a positive electrode;
60mg of solid electrolyte (Li)6.5P0.75In0.25S5I) Placing in a polyether-ether-ketone tube (diameter 10mm), pressing at 300MPa for the first time, and maintaining the pressure for 5min to obtain a solid electrolyte membrane; uniformly spreading a 4mg positive electrode on one side of the solid electrolyte membrane, applying 300MPa pressure for secondary pressing, and keeping the pressure for 5 min; a lithium foil (thickness 60 μm) was placed on the other side of the solid electrolyte membrane and subjected to a third pressing with a pressure of 40MPa, and the pressure was maintained for 3min to obtain a solid-state battery.
Example 2
Preparing the nanocrystalline sulfide solid electrolyte with high air stability:
mixing Li2S、LiI、P2S5And In2S3Mixing according to a molar ratio of 5.2:2:0.9:0.1, putting the mixture into a zirconia grinding tank under the protection of argon, wherein the rotation speed of ball milling is 1200rpm, and the ball milling time is 30min, so as to obtain the high-air-stability nanocrystalline sulfide solid electrolyte, wherein the chemical composition of the high-air-stability nanocrystalline sulfide solid electrolyte is Li6.2P0.9In0.1S5I；
Preparing a solid-state battery:
placing elemental sulfur and Kabo carbon in a stainless steel ball-milling tank for mechanical ball milling for 10 hours at the rotating speed of 600 rpm; after the ball milling is finished, acetylene black and solid electrolyte (Li) are added into a ball milling tank6.2P0.9In0.1S5I) Performing secondary mechanical ball milling for 1h at the rotating speed of 300rpm to obtain a positive electrode;
60mg of solid electrolyte (Li)6.2P0.9In0.1S5I) Is placed in a polyetheretherketone pipe (diameter 10mm)Performing first pressing under the pressure of 300MPa, and maintaining the pressure for 5min to obtain a solid electrolyte membrane; uniformly spreading a 4mg positive electrode on one side of the solid electrolyte membrane, applying 300MPa pressure for secondary pressing, and keeping the pressure for 5 min; a lithium foil (thickness 60 μm) was placed on the other side of the solid electrolyte membrane and subjected to a third pressing with a pressure of 40MPa, and the pressure was maintained for 3min to obtain a solid-state battery.
Example 3
Preparing the nanocrystalline sulfide solid electrolyte with high air stability:
mixing Li2S、LiI、P2S5And Sb2S5Mixing according to a molar ratio of 5:2:0.8:0.2, putting the mixture into a zirconia grinding tank under the protection of argon, and carrying out ball milling at a rotating speed of 1200rpm for 30min to obtain the high-air-stability nanocrystalline sulfide solid electrolyte with a chemical composition of Li6P0.8Sb0.2S5I；
Preparing a solid-state battery:
placing elemental sulfur and Kabo carbon in a stainless steel ball-milling tank for mechanical ball milling for 10 hours at the rotating speed of 600 rpm; after the ball milling is finished, acetylene black and solid electrolyte (Li) are added into a ball milling tank6P0.8Sb0.2S5I) Performing secondary mechanical ball milling for 1h at the rotating speed of 300rpm to obtain a positive electrode;
60mg of solid electrolyte (Li)6P0.8Sb0.2S5I) Placing in a polyether-ether-ketone tube (diameter 10mm), pressing at 300MPa for the first time, and maintaining the pressure for 5min to obtain a solid electrolyte membrane; uniformly spreading a 4mg positive electrode on one side of the solid electrolyte membrane, applying 300MPa pressure for secondary pressing, and keeping the pressure for 5 min; a lithium foil (thickness 60 μm) was placed on the other side of the solid electrolyte membrane and subjected to a third pressing with a pressure of 40MPa, and the pressure was maintained for 3min to obtain a solid-state battery.
Example 4
Preparing the nanocrystalline sulfide solid electrolyte with high air stability:
mixing Li2S、LiI、P2S5And SnS2According to the molar ratio5.3:2:0.7:0.3, putting the mixture into a zirconia grinding tank under the protection of argon, and carrying out ball milling at the rotating speed of 1200rpm for 30min to obtain the high-air-stability nanocrystalline sulfide solid electrolyte with the chemical composition of Li6.3P0.7Sn0.3S5I；
Preparing a solid-state battery:
placing elemental sulfur and Kabo carbon in a stainless steel ball-milling tank for mechanical ball milling for 10 hours at the rotating speed of 600 rpm; after the ball milling is finished, acetylene black and solid electrolyte (Li) are added into a ball milling tank6.3P0.7Sn0.3S5I) Performing secondary mechanical ball milling for 1h at the rotating speed of 300rpm to obtain a positive electrode;
60mg of solid electrolyte (Li)6.3P0.7Sn0.3S5I) Placing in a polyether-ether-ketone tube (diameter 10mm), pressing at 300MPa for the first time, and maintaining the pressure for 5min to obtain a solid electrolyte membrane; uniformly spreading a 4mg positive electrode on one side of the solid electrolyte membrane, applying 300MPa pressure for secondary pressing, and keeping the pressure for 5 min; a lithium foil (thickness 60 μm) was placed on the other side of the solid electrolyte membrane and subjected to a third pressing with a pressure of 40MPa, and the pressure was maintained for 3min to obtain a solid-state battery.
Example 5
Preparing the nanocrystalline sulfide solid electrolyte with high air stability:
mixing Li2S、LiI、P2S5And Bi2S3Putting the mixture into a zirconia grinding tank under the protection of argon according to the molar ratio of 5.6:2:0.7:0.3, wherein the rotation speed of ball milling is 1200rpm, and the ball milling time is 100min to obtain the high-air-stability nanocrystalline sulfide solid electrolyte, wherein the chemical composition of the high-air-stability nanocrystalline sulfide solid electrolyte is Li6.6P0.7Bi0.3S5I；
Preparing a solid-state battery:
placing elemental sulfur and Kabo carbon in a stainless steel ball-milling tank for mechanical ball milling for 10 hours at the rotating speed of 600 rpm; after the ball milling is finished, acetylene black and solid electrolyte (Li) are added into a ball milling tank6.6P0.7Bi0.3S5I) Performing secondary mechanical ball milling for 1h, rotatingThe speed is 300rpm, and a positive electrode is obtained;
60mg of solid electrolyte (Li)6.3P0.7Sn0.3S5I) Placing in a polyether-ether-ketone tube (diameter 10mm), pressing at 300MPa for the first time, and maintaining the pressure for 5min to obtain a solid electrolyte membrane; uniformly spreading a 4mg positive electrode on one side of the solid electrolyte membrane, applying 300MPa pressure for secondary pressing, and keeping the pressure for 5 min; a lithium foil (thickness 60 μm) was placed on the other side of the solid electrolyte membrane and subjected to a third pressing with a pressure of 40MPa, and the pressure was maintained for 3min to obtain a solid-state battery.
Comparative example 1
A solid electrolyte and a solid-state battery were produced In the same manner as In example 1, except that In was not added to the solid electrolyte2S3Chemical composition of Li6PS5I。
Comparative example 2
A solid electrolyte and a solid-state battery were prepared in the same manner as in example 1, wherein Li2S、LiI、P2S5And In2S3Mixed according to the mol ratio of 6.2:2:0.4:0.6, and the chemical composition is Li7.2P0.4In0.6S5I。
Comparative example 3
A solid electrolyte and a solid-state battery were prepared according to the method of example 1, in which the ball milling time during the preparation of the solid electrolyte was 10 hours.
Comparative example 4
A solid electrolyte and a solid-state battery In which In was contained were produced In the same manner as In example 12S3Substitution to Al2S3Chemical composition of Li6.5P0.75Al0.25S5I。
Performance testing
SEM detection is carried out on the high air stability nanocrystalline sulfide solid electrolyte obtained in example 1, and the test result is shown in figure 2. As can be seen from FIG. 2, the nanocrystalline sulfide solid electrolyte with high air stability provided by the invention has irregular particles with the size of 1-10 μm.
Example 1 and comparative example 14 the obtained solid electrolyte is placed for 1h under an environment with the humidity of 30%, and the ion conductivity test is carried out before and after the placement. The test results before leaving as In example 1 and comparative example 1 are shown In FIG. 3, and the test results after leaving are shown In FIG. 4, and it can be seen from FIGS. 3 and 4 that In was added before and after leaving2S3The ionic conductivity of the electrolyte is improved, and In is not added after the electrolyte is placed2S3The ionic conductivity of the electrolyte was reduced from 0.79 to 0.005, and In was added2S31.82 of the electrolyte was changed to 1.08 and remained substantially unchanged, indicating that In was added2S3The electrolyte of (3) has excellent air stability.
Before the deposition, the test result of comparative example 2 is shown In FIG. 5, and it can be seen from FIG. 3 and FIG. 5 that In is increased2S3The doping amount may decrease the ionic conductivity of the electrolyte.
The test result of comparative example 3 before the standing is shown in fig. 6, and it can be understood from fig. 3 and 6 that the ion conductivity of the electrolyte is reduced by extending the time of ball milling during the preparation of the electrolyte.
The test results of comparative example 4 before and after the standing are shown in FIG. 7, and it can be seen from the combination of FIGS. 3 and 7 that the non-soft acid metal element (Al) is doped2S3) The sulfide of (a) does not effectively improve the air stability of the electrolyte.
The electrolytes obtained in example 1 and comparative example 1 were placed in air, and H generated in air was tested2The content of S, the test results are shown in FIG. 8. As can be seen from FIG. 8, Li obtained in example 16.5P0.75In0.25S5The electrolyte I has good stability to air.
The nanocrystalline sulfide solid electrolyte with high air stability obtained in example 1 was assembled into a lithium/solid electrolyte/lithium symmetric battery, and the cycle deposition performance of lithium during charge and discharge was tested, and the test results are shown in fig. 9. As can be seen from FIG. 9, example 1 gives Li6.5P0.75In0.25S5The electrolyte I has good stability to metal lithium and can be applied to solid-state batteries.
The solid-state batteries obtained in examples 1 to 5 and comparative examples 1 to 4 were subjected to constant-current charge and discharge tests under the following test conditions: the charging and discharging voltage range is 1.5-3.0V, the charging and discharging multiplying power is 0.1C, the testing temperature is 25 ℃, and the cycle is 200 circles. The test results are shown in table 1. Wherein fig. 10 is a graph showing the cycle stability performance of the solid-state battery obtained in example 1. As can be seen from fig. 10, the battery obtained in example 1 exhibited excellent cycle stability.
Table 1 examples 1 to 4 and comparative examples 1 to 4 obtained results of cycle stability test of solid-state batteries
Capacity retention rate Capacity retention rate
Example 1 95％ Comparative example 1 55％
Example 2 86％ Comparative example 2 65％
Example 3 90％ Comparative example 3 79％
Example 4 88％ Comparative example 4 61％
Example 5 90％
As can be seen from table 1, the solid-state battery obtained by using the high air stability nanocrystalline sulfide solid electrolyte assembly provided by the invention has excellent cyclicity, and the capacity retention rate can reach over 86% after 200 cycles at 0.1C rate. From the results of comparative example 1, on the other hand, no soft metal element was added, and the obtained electrolyte assembly had poor cycle stability of the solid-state battery, and the capacity retention rate was only 55% after 200 cycles.
In conclusion, the soft acid metal element is introduced into the sulfide solid electrolyte, so that the lithium ion concentration is increased, and the ionic conductivity of the sulfide solid electrolyte is improved; meanwhile, on the basis of a soft and hard acid-base theory, the combination of soft acid metal and sulfur is adopted, so that the combination stability of the soft acid metal and the sulfur is improved, and the air stability of the sulfide solid electrolyte is further improved.
The air stability nanocrystalline sulfide solid electrolyte provided by the invention is applied to a solid battery, can effectively inhibit the growth of lithium dendrites, and improves the cycle stability of the solid battery.
The preparation method of the high-air-stability nanocrystalline sulfide solid electrolyte provided by the invention is simple, and the high-air-stability nanocrystalline sulfide solid electrolyte can be obtained by performing ball milling on raw materials once, so that the production efficiency is further improved.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.

Claims (10)

1. A high-air-stability nanocrystalline sulfide solid electrolyte contains Li as chemical component6+yPxM1-xS5I, wherein x is 0-1, and y is 0-3;
and M is a soft acid metal element.
2. The high air stability nanocrystalline sulfide solid electrolyte according to claim 1, wherein M is one or more of Ga, Sn, As, Sb, In, Bi, Cu and Pd.
3. The method for preparing the high air stability nanocrystalline sulfide solid electrolyte according to claim 1 or 2, comprising the steps of:
mixing Li2S、LiI、P2S5And MmSnBall milling to obtain the high air stability nanocrystalline sulfide solid electrolyte;
the M ismSnWherein n is 1, 2, 3 or 5, and m is 1 or 2.
4. The method of claim 3, wherein M ismSnIs Ga2S3、SnS2、As2S5、Sb2S5、In2S3、Bi2S3One or more of CuS and PdS.
5. The method of claim 3, wherein during the ball milling, Li2S、LiI、P2S5And MmSnThe molar ratio of (a) to (b) is 5.0-6.0: 2: 0.7-0.9: 0.1 to 0.9.
6. The preparation method of claim 3, wherein the rotation speed of the ball mill is 1000-2000 rpm, and the ball milling time is 5-300 min.
7. The preparation method according to claim 3, wherein the ball-to-material ratio in the ball milling process is 20-50: 1.
8. the method of claim 3, wherein the ball milling is performed in an argon atmosphere.
9. A solid-state battery comprises a positive electrode, a solid electrolyte and a metallic lithium negative electrode which are sequentially arranged, wherein the solid electrolyte is the high-air-stability nanocrystalline sulfide solid electrolyte disclosed by claim 1 or 2 or the high-air-stability nanocrystalline sulfide solid electrolyte prepared by the preparation method disclosed by any one of claims 3-8.
10. A method for producing the solid-state battery of claim 9, comprising: and sequentially arranging the metal lithium cathode, the solid electrolyte and the anode, and compacting to obtain the solid battery.
CN202110382390.3A 2021-04-09 2021-04-09 High-air-stability nanocrystalline sulfide solid electrolyte, solid-state battery and preparation method of solid-state battery Pending CN113097560A (en)

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