CN108258303B - Sulfide solid electrolyte, preparation method thereof and all-solid-state lithium secondary battery - Google Patents

Sulfide solid electrolyte, preparation method thereof and all-solid-state lithium secondary battery Download PDF

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CN108258303B
CN108258303B CN201810047984.7A CN201810047984A CN108258303B CN 108258303 B CN108258303 B CN 108258303B CN 201810047984 A CN201810047984 A CN 201810047984A CN 108258303 B CN108258303 B CN 108258303B
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solid electrolyte
lithium ion
sulfide
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ion solid
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CN108258303A (en
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陈少杰
刘高瞻
谢东九
许晓雄
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Ningbo Institute of Material Technology and Engineering of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G30/00—Compounds of antimony
    • C01G30/002—Compounds containing, besides antimony, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/006—Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
    • 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
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 provides a sulfide solid electrolyte, which has a chemical formula shown in a formula I or a formula II: li3+3xP1‑xZnxS4‑xOxFormula I; li3P1‑xSbxS4‑2.5xO2.5xFormula II; wherein x is more than or equal to 0.01 and less than or equal to 0.05. The application is realized by adding a certain amount of ZnO or Sb2O5For sulfide solid electrolyte material Li3PS4The double doping modification is carried out, so that the air stability of the modified sulfide solid electrolyte can be improved, and the improvement of the lithium ion conductivity is facilitated. The invention also provides a preparation method of the sulfide solid electrolyte and an all-solid-state lithium secondary battery.

Description

Sulfide solid electrolyte, preparation method thereof and all-solid-state lithium secondary battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a sulfide solid electrolyte, a preparation method of the sulfide solid electrolyte and an all-solid-state lithium secondary battery.
Background
Energy crisis and environmental pollution have increasingly become prominent problems restricting sustainable development of human society, and development and utilization of green clean energy are becoming more and more urgent. The electrochemical energy storage technology is very important for the utilization of intermittent clean renewable energy sources such as solar energy, wind energy and the like, and is also the core of a zero-emission pure electric vehicle. Therefore, the development of an energy storage device which is efficient, safe, large in capacity, long in service life and capable of stably releasing energy in use is of great significance. Lithium ion batteries are regarded as one of the most competitive electrochemical energy storage technologies due to their high energy density, long service life, and other characteristics.
However, the existing lithium ion battery adopts flammable organic liquid electrolyte, so that potential safety hazards such as leakage, corrosion, combustion and even explosion exist. At present, with the development of technologies such as power batteries and smart grid energy storage, the safety performance requirements of lithium ion batteries are further improved. The all-solid-state lithium battery which uses the inorganic solid electrolyte with good safety to replace the traditional organic liquid electrolyte is an effective way for solving the safety problem of the lithium ion battery. In addition, the lithium ion battery diaphragm can completely replace a diaphragm in a lithium battery, so that the structure of the battery is further simplified, the energy density of the battery is improved, the production and the use of the battery are facilitated, the limitation of the shape of the battery is broken through, the production cost of the battery is reduced, and the lithium ion battery diaphragm has great application potential.
Compared with other inorganic solid electrolyte materials, the sulfide solid electrolyte with the thio-LICION structure has relatively high room-temperature conductivity and wide electrochemical window, and can be applied to all-solid-state lithium secondary batteries. However, most sulfide solid electrolytes have poor air stability, and are easy to deliquesce after contacting with air to generate hydrogen sulfide gas, so the use process must be carried out under a closed condition, and the preparation and use costs of the battery are increased. In addition, at present, the conductivity of the inorganic sulfide electrolyte still needs to be further improved to meet the actual working requirement of the lithium battery, so that the preparation of the solid electrolyte with higher lithium ion conductivity and stable air is the key point for the practical application of the all-solid-state lithium secondary battery, the improvement of the air stability of the sulfide solid electrolyte material has practical value, and the method has important significance for the development of various high-energy-density long-cycle all-solid-state lithium secondary battery technologies.
Disclosure of Invention
The invention aims to provide a sulfide solid electrolyte, a preparation method thereof and an all-solid-state lithium secondary battery.
The invention provides a sulfide solid electrolyte, which has a chemical formula shown in a formula I or a formula II:
Li3+3xP1-xZnxS4-xOxformula I; li3P1-xSbxS4-2.5xO2.5xFormula II;
wherein x is more than or equal to 0.01 and less than or equal to 0.05.
Preferably, x is 0.01, 0.02, 0.03, 0.04 or 0.05.
The invention provides a preparation method of a sulfide solid electrolyte, which comprises the following steps:
A) mixing Li with a molar ratio of 3:12S and P2S5Mixing and grinding the mixture with metal oxide to obtain a primary material; the metal oxide is zinc oxide or antimony oxide;
the metal oxide is zinc oxide, Li2S、P2S5And zinc oxide in a molar ratio of (3+3 ×): (1-x): x;
the metal oxide is antimony oxide, Li2S、P2S5And antimony oxide in a molar ratio of 3 (1-x): (1-x): x.
B) Under the condition of inert gas, carrying out heat treatment on the primary material to obtain a sulfide lithium ion solid electrolyte shown as a formula (I) or (II);
Li3+3xP1-xZnxS4-xOxformula I; li3P1-xSbxS4-2.5xO2.5xFormula II;
wherein x is more than or equal to 0.01 and less than or equal to 0.05.
Preferably, the grinding is high-energy ball milling;
the rotating speed of the high-energy ball mill is 200-500 rpm;
the time of the high-energy ball milling is 9-18 hours.
Preferably, the ball-to-material ratio of the high-energy ball mill is (1-60): 1.
preferably, the temperature of the heat treatment is 150-400 ℃;
the time of the heat treatment is 1-5 hours.
Preferably, the temperature of the heat treatment is realized by raising the temperature;
the rate of temperature rise is 1-10 ℃/min.
The invention provides an all-solid-state lithium secondary battery, which comprises a positive electrode, a negative electrode and an electrolyte;
the electrolyte is a sulfide solid electrolyte as described above.
The invention provides a sulfide solid electrolyte, which has a chemical formula shown in a formula I or a formula II: li3+3xP1- xZnxS4-xOxFormula I; li3P1-xSbxS4-2.5xO2.5xFormula II; it is composed ofIn the formula, x is more than or equal to 0.01 and less than or equal to 0.05. The lithium ion solid electrolyte material of the invention is characterized in that M is introduced into sulfide electrolyteyOzAnd (M ═ Zn and Sb), oxygen element is added into the sulfide solid electrolyte, and oxygen ions replace part of bridging sulfur which is easy to react with water in the solid electrolyte, namely P-O-P bond group replaces P-S-P bond group, so that the P-S-P bond group is prevented from reacting with water in the air to generate hydrogen sulfide gas, and the air stability of the sulfide solid electrolyte material is improved. Furthermore, MyOzThe P-O-P bond group formed by the introduction of (M ═ Zn, Sb) can increase the chain length of the network structure of the sulfide solid electrolyte material, leading to an increase in the content of S-Li bonds, while Li ion transport in the sulfide solid electrolyte material depends mainly on Li ions in the S-Li bonds, so M ═ Zn, Sb) is increasedyOzThe introduction of (M ═ Zn, Sb) can also improve the ionic conductivity of the sulfide solid electrolyte. The experimental result shows that the conductivity of the sulfide solid electrolyte in the invention exceeds 10-3S cm-1(25 ℃), the assembled all-solid-state lithium battery has no obvious attenuation after 100 cycles, and the battery capacity retention rate reaches 95.3 percent and 98.4 percent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a graph showing the air stability test of a sulfide electrolyte in example 2 of the present invention;
FIG. 2 is an air stability test of a sulfide electrolyte in example 7 of the present invention;
FIG. 3 is a test of the stability of the sulfide electrolyte to lithium in example 2 of the present invention;
FIG. 4 is a lithium stability test of a sulfide electrolyte at different amperages according to example 7 of the present invention;
FIG. 5 shows the conductivity of the sulfide electrolytes of examples 1 to 5 of the present invention at different temperatures;
FIG. 6 is a graph showing the conductivity of the sulfide electrolyte at different temperatures in examples 6 to 10 of the present invention;
fig. 7 is a first charge and discharge curve of the all solid-state lithium secondary battery in example 2 of the present invention;
fig. 8 is a first charge and discharge curve of the all solid-state lithium secondary battery in example 7 of the present invention;
FIG. 9 is an X-ray diffraction pattern of a sulfide electrolyte in examples 1 to 5 of the present invention and a comparative example;
FIG. 10 is an X-ray diffraction pattern of a sulfide electrolyte in examples 6 to 10 of the present invention;
FIG. 11 is an air stability test of a sulfide electrolyte in a comparative example of the present invention;
FIG. 12 is a graph showing the electrical conductivity of the sulfide electrolyte of comparative examples of the present invention at various temperatures.
Detailed Description
The invention provides a sulfide solid electrolyte, which has a chemical formula shown in a formula I or a formula II:
Li3+3xP1-xZnxS4-xOxformula I; li3P1-xSbxS4-2.5xO2.5xFormula II;
wherein x is more than or equal to 0.01 and less than or equal to 0.05.
The application is realized by adding a certain amount of ZnO or Sb2O5For sulfide solid electrolyte material Li3PS4The double doping modification is carried out, so that the air stability of the modified sulfide solid electrolyte can be improved, and the improvement of the lithium ion conductivity is facilitated.
In the invention, x is more than or equal to 0.02 and less than or equal to 0.04, and specifically, x is 0.01, 0.02, 0.03, 0.04 or 0.05.
The invention also provides a preparation method of the sulfide solid electrolyte, which comprises the following steps:
A) mixing Li2S and P2S5Mixing and grinding the mixture with metal oxide to obtain a primary material; the metal oxide is zinc oxide or antimony oxide;
B) under the condition of inert gas, carrying out heat treatment on the primary material to obtain a sulfide lithium ion solid electrolyte shown as a formula (I) or (II);
Li3+3xP1-xZnxS4-xOxformula I; li3P1-xSbxS4-2.5xO2.5xFormula II;
wherein x is more than or equal to 0.01 and less than or equal to 0.05.
The milling is preferably carried out under an inert gas, preferably nitrogen or argon.
In the present invention, since Zn and Sb have different valences, Li is doped in the case of doping2S and P2S5The amount of (a) is also varied, and in particular,
when the metal oxide is zinc oxide:
since Zn has a valence of +2, but the P element to be substituted by Zn has a valence of +5, the raw material composition is made according to the following formula for the ZnO-doped system.
(1-x) Li3PS4+3xLi2S+xZnO→Li3+3xP1-xZnxS4-xOxFormula III;
wherein Li3PS4The mixture ratio of: li2S:P2S5＝3:1；
Therefore, the raw material proportion is integrated to obtain the final raw material proportion of Li2S、P2S5And zinc oxide in a molar ratio of (3+3 ×): (1-x): x.
When the metal oxide is an antimony oxide,
since Sb is +5 valent and is consistent with the valence state of P, the doping system of antimony oxide is carried out according to the following mixture ratio:
Li2S:P2S5＝3:1；Li2s and P2S5The molar ratio of the total moles of antimony oxide to antimony oxide is (1-x): x.
Among them, 0.01. ltoreq. x.ltoreq.0.05, preferably, 0.02. ltoreq. x.ltoreq.0.04, more preferably, x.ltoreq.0.02.
The invention is directed to said Li2S、P2S5And MyOzThe form of (M ═ Zn, Sb) mixed polishing is not particularly limited, and a method of mixed polishing known to those skilled in the art may be used. In the present invention, mechanical milling is preferably employed, and high energy ball milling is more preferred. The rotating speed of the high-energy ball mill is 200-500 rpm, preferably 300-500 rpm; the time of the high-energy ball milling is 9-18 h, preferably 12-15 h; the ball-to-material ratio of the high-energy ball mill is preferably (1-60): 1, and more preferably (40-55): 1.
And after grinding is finished, obtaining a primary material. And carrying out heat treatment on the primary material to obtain the lithium ion solid electrolyte material. The invention also comprises tabletting the initial material before the heat treatment to obtain a flaky initial material. The method of tableting is not particularly limited in the present invention, and tableting methods known to those skilled in the art may be used. In the present invention, the tableting is preferably performed as follows:
and tabletting the ground primary material under the pressure condition of 10-30 MPa to obtain a flaky primary material.
The obtained sheet-shaped primary material is placed in a sintering mold and is subjected to heat treatment under the condition of inert gas, so that the lithium ion solid electrolyte material shown in the formulas (I) and (II) is obtained. In the present invention, the inert gas is preferably nitrogen or argon. The temperature of the heat treatment is 150-400 ℃, and preferably 150-300 ℃; the time of the heat treatment is 1-5 h, preferably 2-5 h.
The specific method of heat treatment according to the present invention is preferably as follows:
heating the flaky primary material at a heating rate of 1-10 ℃/min to 150-400 ℃, preserving heat for 1-5 h, and cooling to room temperature along with the furnace to obtain the flaky lithium ion solid electrolyte material.
The invention also provides an all-solid-state lithium secondary battery which comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the lithium ion solid electrolyte material or the lithium ion solid electrolyte material prepared by the preparation method. In the present invention, the positive electrode is preferably lithium cobaltate, lithium manganate, lithium iron phosphate, more preferably lithium cobaltate; the negative electrode is preferably a carbon negative electrode, a metallic lithium negative electrode or a composite material thereof, and more preferably a metallic lithium negative electrode material.
The invention provides a sulfide solid electrolyte, which has a chemical formula shown in a formula I or a formula II: li3+3xP1- xZnxS4-xOxFormula I; li3P1-xSbxS4-2.5xO2.5xFormula II; wherein x is more than or equal to 0.01 and less than or equal to 0.05. The lithium ion solid electrolyte material of the invention is characterized in that M is introduced into sulfide electrolyteyOzAnd (M ═ Zn and Sb), oxygen element is added into the sulfide solid electrolyte, and oxygen ions replace part of bridging sulfur which is easy to react with water in the solid electrolyte, namely P-O-P bond group replaces P-S-P bond group, so that the P-S-P bond group is prevented from reacting with water in the air to generate hydrogen sulfide gas, and the air stability of the sulfide solid electrolyte material is improved. Furthermore, MyOzThe P-O-P bond group formed by the introduction of (M ═ Zn, Sb) can increase the chain length of the network structure of the sulfide solid electrolyte material, leading to an increase in the content of S-Li bonds, while Li ion transport in the sulfide solid electrolyte material depends mainly on Li ions in the S-Li bonds, so M ═ Zn, Sb) is increasedyOzThe introduction of (M ═ Zn, Sb) can also improve the ionic conductivity of the sulfide solid electrolyte. The experimental result shows that the conductivity of the sulfide solid electrolyte in the invention exceeds 10-3S cm-1(25 ℃), the assembled all-solid-state lithium battery has no obvious attenuation after 100 cycles, and the battery capacity retention rate reaches 95.3 percent and 98.4 percent.
In order to further illustrate the present invention, the sulfide solid electrolyte, the method for preparing the same, and the all solid-state lithium secondary battery according to the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Example 1
Under the protection of argon atmosphere, Li with the purity of more than 99 percent is respectively added2S、P2S5ZnO by molar ratio Li2S：P2S5ZnO is weighed as 303:99:2, and the water content is smallGrinding and mixing uniformly at the rotating speed of 200rpm under the condition of 10ppm, carrying out high-energy ball milling for 9 hours under the condition of a ball-to-material ratio of 10:1 to obtain a primary powder material, taking out the primary powder material, grinding uniformly, tabletting under the pressure of 10MPa to obtain a flaky primary material, and filling the flaky primary material into a sintering die. Heating the sintering mold filled with the sheet-shaped primary material to 150 ℃ at a heating rate of 1 ℃/min, preserving heat for 1h, cooling to room temperature along with the furnace, taking out the sheet-shaped sintering product under the condition that the water content is less than 100ppm, and uniformly grinding to obtain powder which is a lithium ion solid electrolyte material of the all-solid-state lithium secondary battery, namely Li3+3xP1-xZnxS4- xOx(x is 0.01) glass-ceramic.
For Li3+3xP1-xZnxS4-xOx(x ═ 0.01) the lithium ion solid electrolyte material was subjected to a crystal structure test and an electrochemical performance test. The lithium ion solid electrolyte powder material was used to prepare a sample in a glove box with a water content of less than 10ppm, and X-ray diffraction measurements were performed to obtain the crystal structure information of the sample as shown in fig. 9. Pressing the lithium ion solid electrolyte powder into sheet Li with the diameter of 10mm and the thickness of 1mm under the conditions that the water content is less than 10ppm and the pressure of 10MPa3+3xP1-xZnxS4- xOx(x ═ 0.01) glass ceramic lithium ion solid electrolyte. Then, carbon is used as a blocking electrode, EIS test is carried out at different temperatures to test the conductivity, FIG. 5 shows the conductivity of the lithium ion solid electrolyte material prepared in example 1 of the present invention at different temperatures (-40 ℃ to 100 ℃), and the room temperature conductivity is 8.82 × 10-4S cm-1。
Example 2
Under the protection of argon atmosphere, Li with the purity of more than 99 percent is respectively added2S、P2S5ZnO by molar ratio Li2S：P2S5Weighing ZnO 306:98:4, grinding and uniformly mixing at the rotating speed of 500rpm under the condition that the water content is less than 10ppm, carrying out high-energy ball milling for 13.5h under the condition of a ball-to-material ratio of 45:1 to obtain a primary powder material, taking out the primary powder material, uniformly grinding, tabletting under the pressure of 10MPa to obtain a flaky primary material, and filling the flaky primary material into a sintering die. Will be provided withHeating the sintering mold of the sheet-shaped primary material to 250 ℃ at a heating rate of 2 ℃/min, preserving heat for 2h, cooling to room temperature along with the furnace, taking out the sheet-shaped sintering product under the condition that the water content is less than 100ppm, and grinding uniformly to obtain the powder which is the lithium ion solid electrolyte material of the all-solid-state lithium secondary battery, namely Li3+3xP1- xZnxS4-xOx(x is 0.02) glass-ceramic.
For Li3+3xP1-xZnxS4-xOx(x ═ 0.02) the lithium ion solid electrolyte material was subjected to crystal structure characterization and electrochemical performance test. The lithium ion solid electrolyte powder material was used to prepare a sample in a glove box with a water content of less than 10ppm, and X-ray diffraction measurements were performed to obtain the crystal structure information of the sample as shown in fig. 9.
Pressing the lithium ion solid electrolyte powder material into a sheet Li with the diameter of 10mm and the thickness of 1mm under the conditions that the water content is less than 10ppm and the pressure of 10MPa3+3xP1-xZnxS4-xOx(x ═ 0.02) glass ceramic lithium ion solid electrolyte. Then, the conductivity of the lithium ion solid electrolyte was tested by EIS test using carbon as a blocking electrode at different temperatures, and the results are shown in fig. 5, where fig. 5 shows the conductivity of the lithium ion solid electrolyte prepared in example 2 of the present invention at different temperatures. As can be seen from FIG. 5, the system has ion conductivity of 1.12 × 10 at 25 deg.C-3S cm-1It is shown that the obtained lithium ion solid electrolyte material of the all-solid-state lithium secondary battery has good conductivity at room temperature, and fig. 5 shows that the lithium ion conduction of the material is facilitated along with the increase of the working temperature.
The obtained Li3+3xP1-xZnxS4-xOx(x ═ 0.02) lithium ion solid electrolyte exposed to H-bearing charge2S in the closed container of the gas detection equipment, the atmosphere of the container is air, and H is monitored2S gas content, results are shown in FIG. 1, in 180 minutes, H in the vessel2S gas content less than 1ppm, indicating Li3+3xP1-xZnxS4-xOx(x＝0.02)The lithium ion solid electrolyte material is stable to air.
The obtained Li3+3xP1-xZnxS4-xOx(x ═ 0.02) lithium ion solid electrolyte, sandwiched between two metallic lithium counter electrodes, was subjected to a lithium stability test, the results of which are shown in fig. 3. The results show that no obvious electrochemical reaction occurs between the prepared electrolyte and the lithium metal within 1500 hours, and the prepared electrolyte has good stability.
The lithium cobaltate is used as the positive electrode, the metallic lithium is used as the negative electrode, and the lithium ion solid electrolyte material and the lithium cobaltate are assembled together to form the all-solid-state lithium secondary battery, and the first charge-discharge curve chart is shown in figure 7. As can be seen from fig. 7, after 90 weeks of cycling, the all-solid-state battery did not undergo significant fading, and the battery still had very good capacity with a capacity retention of 98%.
Example 3
Under the protection of argon atmosphere, Li with the purity of more than 99 percent is respectively added2S、P2S5ZnO by molar ratio Li2S：P2S5Weighing ZnO 309:97:6, grinding and uniformly mixing at a rotating speed of 240rpm under the condition that the water content is less than 10ppm, carrying out high-energy ball milling for 10.5h under the condition of a ball-to-material ratio of 15:1 to obtain a primary powder material, taking out the primary powder material, uniformly grinding, tabletting under the pressure of 10MPa to obtain a flaky primary material, and filling the flaky primary material into a sintering die. Heating the sintering mold filled with the sheet-shaped primary material to 175 ℃ at a heating rate of 3 ℃/min, preserving heat for 1.5h, cooling to room temperature along with the furnace, taking out the sheet-shaped sintering product under the condition that the water content is less than 100ppm, and uniformly grinding to obtain the powder which is the lithium ion solid electrolyte material of the all-solid-state lithium secondary battery, namely Li3+3xP1- xZnxS4-xOx(x ═ 0.03) glass-ceramic.
For Li3+3xP1-xZnxS4-xOx(x ═ 0.03) the lithium ion solid electrolyte material was subjected to a crystal structure test and an electrochemical performance test. Preparing a sample from the lithium ion solid electrolyte powder material in a glove box with the water content of less than 10ppm, and carrying out X-ray diffraction test to obtain the sampleThe crystal structure information is shown in fig. 9. Pressing the lithium ion solid electrolyte powder material into a sheet Li with the diameter of 10mm and the thickness of 1mm under the conditions that the water content is less than 10ppm and the pressure of 10MPa3+3xP1- xZnxS4-xOx(x ═ 0.03) glass ceramic lithium ion solid electrolyte. Then EIS test was carried out at different temperatures using carbon as a blocking electrode to test the conductivity, and the results are shown in FIG. 5, where FIG. 5 shows the conductivity of the lithium ion solid electrolyte material prepared in example 3 of the present invention at different temperatures, and the room temperature conductivity is 1.12X 10-3S cm-1。
Example 4
Under the protection of argon atmosphere, Li with the purity of more than 99 percent is respectively added2S、P2S5ZnO by molar ratio Li2S：P2S5Weighing ZnO 312:96:8, grinding and uniformly mixing at a rotating speed of 200rpm under the condition that the water content is less than 10ppm, carrying out high-energy ball milling for 12 hours under the condition of a ball-to-material ratio of 20:1 to obtain a primary powder material, taking out the primary powder material, uniformly grinding, tabletting under the pressure of 10MPa to obtain a flaky primary material, and filling the flaky primary material into a sintering die. Heating the sintering mold filled with the sheet-shaped primary material to 200 ℃ at a heating rate of 4 ℃/min, preserving heat for 2.5h, cooling to room temperature along with the furnace, taking out the sheet-shaped sintering product under the condition that the water content is less than 100ppm, and uniformly grinding to obtain the powder which is the lithium ion solid electrolyte material of the all-solid-state lithium secondary battery, namely Li3+3xP1- xZnxS4-xOx(x is 0.04) glass-ceramic.
For Li3+3xP1-xZnxS4-xOx(x ═ 0.04) the lithium ion solid electrolyte material was subjected to crystal structure test and electrochemical performance test. The lithium ion solid electrolyte powder material was used to prepare a sample in a glove box with a water content of less than 10ppm, and X-ray diffraction measurements were performed to obtain the crystal structure information of the sample as shown in fig. 9. Pressing the lithium ion solid electrolyte powder material into a sheet Li with the diameter of 10mm and the thickness of 1mm under the conditions that the water content is less than 10ppm and the pressure of 10MPa3+3xP1- xZnxS4-xOx(x ═ 0.04) glass ceramic lithium ion solid electrolyte. Then EIS test was carried out at different temperatures using carbon as a blocking electrode to test the conductivity, and the results are shown in FIG. 5, where FIG. 5 shows the conductivity of the lithium ion solid electrolyte material prepared in example 4 of the present invention at different temperatures, and the room temperature conductivity was 8.41X 10-4S cm-1。
Example 5
Under the protection of argon atmosphere, Li with the purity of more than 99 percent is respectively added2S、P2S5ZnO by molar ratio Li2S：P2S5Weighing ZnO 315:95:10, grinding and uniformly mixing at a rotating speed of 300rpm under the condition that the water content is less than 10ppm, carrying out high-energy ball milling for 16.5h under the condition of a ball-to-material ratio of 25:1 to obtain a primary powder material, taking out the primary powder material, uniformly grinding, tabletting under the pressure of 10MPa to obtain a flaky primary material, and filling the flaky primary material into a sintering die. Heating the sintering mold filled with the sheet-shaped primary material to 225 ℃ at a heating rate of 5 ℃/min, preserving heat for 3h, cooling to room temperature along with the furnace, taking out the sheet-shaped sintering product under the condition that the water content is less than 100ppm, and grinding uniformly to obtain the powder which is the lithium ion solid electrolyte material of the all-solid-state lithium secondary battery, namely Li3+3xP1- xZnxS4-xOx(x is 0.05) glass-ceramic.
For Li3+3xP1-xZnxS4-xOx(x ═ 0.05) the lithium ion solid electrolyte material was subjected to a crystal structure test and an electrochemical performance test. The lithium ion solid electrolyte powder material was used to prepare a sample in a glove box with a water content of less than 10ppm, and X-ray diffraction measurements were performed to obtain the crystal structure information of the sample as shown in fig. 9. Pressing the lithium ion solid electrolyte powder material into a sheet Li with the diameter of 10mm and the thickness of 1mm under the conditions that the water content is less than 10ppm and the pressure of 10MPa3+3xP1- xZnxS4-xOx(x ═ 0.05) glass ceramic lithium ion solid electrolyte. EIS test was then performed at different temperatures using carbon as the blocking electrode to test the conductivity, and the results are shown in FIG. 5, which is a graph of the conductivity of the carbon-based conductive material prepared in example 5 of the present inventionThe lithium ion solid electrolyte material has a room temperature conductivity of 5.11X 10 at different temperatures-4S cm-1。
Example 6
Under the protection of argon atmosphere, Li with the purity of more than 99 percent is respectively added2S、P2S5、Sb2O5According to a molar ratio of Li2S：P2S5:Sb2O5Weighing 75:24:1, grinding and uniformly mixing at the rotating speed of 340rpm under the condition that the water content is less than 10ppm, carrying out high-energy ball milling for 18 hours under the condition of a ball-to-material ratio of 30:1 to obtain a primary powder material, taking out the primary powder material, uniformly grinding, tabletting under the pressure of 10MPa to obtain a primary flaky material, and filling the primary flaky material into a sintering die. Heating the sintering mold filled with the sheet-shaped primary material to 275 ℃ at the heating rate of 6 ℃/min, preserving the temperature for 3.5h, cooling the sintering mold to room temperature along with the furnace, taking out the sheet-shaped sintering product under the condition that the water content is less than 100ppm, and uniformly grinding to obtain the powder which is the lithium ion solid electrolyte material of the all-solid-state lithium secondary battery, namely Li3P1- xSbxS4-2.5xO2.5x(x is 0.01) glass-ceramic.
For Li3P1-xSbxS4-2.5xO2.5x(x ═ 0.01) the lithium ion solid electrolyte material was subjected to a crystal structure test and an electrochemical performance test. The lithium ion solid electrolyte powder material was used to prepare a sample in a glove box with a water content of less than 10ppm, and X-ray diffraction measurements were performed to obtain the crystal structure information of the sample as shown in fig. 10. Pressing the lithium ion solid electrolyte powder material into a sheet Li with the diameter of 10mm and the thickness of 1mm under the conditions that the water content is less than 10ppm and the pressure of 10MPa3P1- xSbxS4-2.5xO2.5x(x ═ 0.01) glass ceramic lithium ion solid electrolyte. Then EIS test was carried out at different temperatures using carbon as a blocking electrode to test the conductivity, and the results are shown in FIG. 6, where FIG. 6 is the conductivity of the lithium ion solid electrolyte material prepared in example 6 of the present invention at different temperatures, and the room temperature conductivity is 7.78X 10-4S cm-1。
Example 7
Under the protection of argon atmosphere, Li with the purity of more than 99 percent is respectively added2S、P2S5、Sb2O5According to a molar ratio of Li2S：P2S5:Sb2O5Weighing 75:23:2, grinding and uniformly mixing at the rotating speed of 500rpm under the condition that the water content is less than 10ppm, carrying out high-energy ball milling for 15 hours under the condition of a ball-to-material ratio of 45:1 to obtain a primary powder material, taking out the primary powder material, uniformly grinding, tabletting under the pressure of 10MPa to obtain a primary flaky material, and filling the primary flaky material into a sintering die. Heating the sintering mold filled with the sheet-shaped primary material to 250 ℃ at a heating rate of 2 ℃/min, preserving heat for 2h, cooling to room temperature along with the furnace, taking out the sheet-shaped sintering product under the condition that the water content is less than 100ppm, and grinding uniformly to obtain the powder which is the lithium ion solid electrolyte material of the all-solid-state lithium secondary battery, namely Li3P1-xSbxS4- 2.5xO2.5x(x is 0.02) glass-ceramic.
For Li3P1-xSbxS4-2.5xO2.5x(x ═ 0.02) the lithium ion solid electrolyte material was subjected to crystal structure characterization and electrochemical performance test. The lithium ion solid electrolyte powder material was used to prepare a sample in a glove box with a water content of less than 10ppm, and X-ray diffraction measurements were performed to obtain the crystal structure information of the sample as shown in fig. 10.
Pressing the lithium ion solid electrolyte powder material into a sheet Li with the diameter of 10mm and the thickness of 1mm under the conditions that the water content is less than 10ppm and the pressure of 10MPa3P1-xSbxS4-2.5xO2.5x(x ═ 0.02) glass ceramic lithium ion solid electrolyte. Then, the lithium metal is used as a symmetrical electrode to assemble the battery Li/electrolyte/Li, and the stability to lithium under different current intensities is tested, and the result is shown in FIG. 4. FIG. 4 shows the electrolyte Li3P1-xSbxS4-2.5xO2.5x(x ═ 0.02) at different current intensities (1mA cm)-2,0.5mA cm-2,0.1mA cm-2) All showed excellent stability to lithium. Using carbon as blocking electrode, EIS test is carried out at different temperatures, and conductivity and junction thereof are testedAs shown in fig. 6, fig. 6 shows the electrical conductivities of the lithium ion solid electrolyte material prepared in example 7 of the present invention at different temperatures. As can be seen from FIG. 6, the system has ion conductivity and lithium ion conductivity of 1.08X 10 at 25 deg.C-3S cm-1The obtained lithium ion solid electrolyte material of the all-solid-state lithium secondary battery has good conductivity at room temperature, and the fifth graph shows that the lithium ion solid electrolyte material is beneficial to the conduction of lithium ions along with the increase of the working temperature.
The obtained Li3P1-xSbxS4-2.5xO2.5x(x ═ 0.02) lithium ion solid electrolyte exposed to H-bearing charge2S in the closed container of the gas detection equipment, the atmosphere of the container is air, and H is monitored2S gas content, results are shown in FIG. 2, in 180 minutes, H in the vessel2S gas content less than 2.5ppm, indicating Li3P1-xSbxS4-2.5xO2.5x(x ═ 0.02) the lithium ion solid electrolyte material was stable to air.
The obtained Li3P1-xSbxS4-2.5xO2.5x(x ═ 0.02) lithium ion solid electrolyte, sandwiched between two metallic lithium counter electrodes, was subjected to a lithium stability test, the results of which are shown in fig. 3. The results show that no obvious electrochemical reaction occurs between the prepared electrolyte and the lithium metal within 900 hours, and the prepared electrolyte has good stability overall.
The lithium cobaltate is used as the positive electrode, the metallic lithium is used as the negative electrode, and the lithium ion solid electrolyte material and the lithium cobaltate are assembled together to form the all-solid-state lithium secondary battery, and the first charge-discharge curve chart is shown in figure 8. As can be seen from fig. 8, no significant fading occurred after 100 cycles of the all-solid-state battery, and the battery still had very good capacity with a capacity retention rate of 98%.
Example 8
Under the protection of argon atmosphere, Li with the purity of more than 99 percent is respectively added2S、P2S5、Sb2O5According to a molar ratio of Li2S：P2S5:Sb2O5Weighing the raw materials in a ratio of 75:22:3,grinding and mixing uniformly at the rotating speed of 360rpm under the condition that the water content is less than 10ppm, carrying out high-energy ball milling for 9 hours under the condition of a ball-to-material ratio of 35:1 to obtain a primary powder material, taking out the primary powder material, grinding uniformly, tabletting under the pressure of 10MPa to obtain a flaky primary material, and filling the flaky primary material into a sintering die. Heating the sintering mold filled with the sheet-shaped primary material to 300 ℃ at a heating rate of 7 ℃/min, preserving heat for 4h, cooling to room temperature along with the furnace, taking out the sheet-shaped sintering product under the condition that the water content is less than 100ppm, and uniformly grinding to obtain the powder which is the lithium ion solid electrolyte material of the all-solid-state lithium secondary battery, namely Li3P1-xSbxS4- 2.5xO2.5x(x ═ 0.03) glass-ceramic.
For Li3P1-xSbxS4-2.5xO2.5x(x ═ 0.03) the lithium ion solid electrolyte material was subjected to a crystal structure test and an electrochemical performance test. The lithium ion solid electrolyte powder material was used to prepare a sample in a glove box with a water content of less than 10ppm, and X-ray diffraction measurements were performed to obtain the crystal structure information of the sample as shown in fig. 10. Pressing the lithium ion solid electrolyte powder material into a sheet Li with the diameter of 10mm and the thickness of 1mm under the conditions that the water content is less than 10ppm and the pressure of 10MPa3P1- xSbxS4-2.5xO2.5x(x ═ 0.03) glass ceramic lithium ion solid electrolyte. Then EIS test was carried out at different temperatures using carbon as a blocking electrode to test the conductivity, and the results are shown in FIG. six 6. FIG. 6 shows the conductivity of the lithium ion solid electrolyte material prepared in example 8 of the present invention at different temperatures, and the room temperature conductivity was 7.71X 10-4S cm-1。
Example 9
Under the protection of argon atmosphere, Li with the purity of more than 99 percent is respectively added2S、P2S5、Sb2O5According to a molar ratio of Li2S：P2S5:Sb2O5Weighing 75:21:4, grinding and mixing uniformly at the rotating speed of 400rpm under the condition that the water content is less than 10ppm, carrying out high-energy ball milling for 13.5 hours under the condition of 40:1 ball-to-material ratio to obtain a powder initial material, taking out the powder initial material, grinding uniformly, and then collectingTabletting under 10MPa pressure to obtain a flaky primary material, and loading the flaky primary material into a sintering die. Heating the sintering mold filled with the sheet-shaped primary material to 350 ℃ at a heating rate of 8 ℃/min, preserving heat for 4.5h, cooling to room temperature along with the furnace, taking out the sheet-shaped sintering product under the condition that the water content is less than 100ppm, and uniformly grinding to obtain the powder which is the lithium ion solid electrolyte material of the all-solid-state lithium secondary battery, namely Li3P1- xSbxS4-2.5xO2.5x(x is 0.04) glass-ceramic.
For Li3P1-xSbxS4-2.5xO2.5x(x ═ 0.04) the lithium ion solid electrolyte material was subjected to crystal structure test and electrochemical performance test. The lithium ion solid electrolyte powder material was used to prepare a sample in a glove box with a water content of less than 10ppm, and X-ray diffraction measurements were performed to obtain the crystal structure information of the sample as shown in fig. 10. Pressing the lithium ion solid electrolyte powder material into a sheet Li with the diameter of 10mm and the thickness of 1mm under the conditions that the water content is less than 10ppm and the pressure of 10MPa3P1- xSbxS4-2.5xO2.5x(x ═ 0.04) glass ceramic lithium ion solid electrolyte. Then EIS test was carried out at different temperatures using carbon as a blocking electrode to test the conductivity, and the results are shown in FIG. 6. FIG. 6 shows the conductivity of the lithium ion solid electrolyte material prepared in example 6 of the present invention at different temperatures, and the room temperature conductivity was 5.84X 10-4S cm-1。
Example 10
Under the protection of argon atmosphere, Li with the purity of more than 99 percent is respectively added2S、P2S5、Sb2O5According to a molar ratio of Li2S：P2S5:Sb2O5Weighing 75:20:5, grinding and uniformly mixing at the rotating speed of 460rpm under the condition that the water content is less than 10ppm, carrying out high-energy ball milling for 10.5h under the condition of a ball-to-material ratio of 5:1 to obtain a primary powder material, taking out the primary powder material, uniformly grinding, tabletting under the pressure of 10MPa to obtain a primary flaky material, and filling the primary flaky material into a sintering die. Heating the sintering mold filled with the sheet-shaped primary material to 400 ℃ at a heating rate of 10 ℃/min, and preserving heat5h, cooling to room temperature along with the furnace, taking out the sheet-shaped sintering product under the condition that the water content is less than 100ppm, and uniformly grinding to obtain the powder which is the lithium ion solid electrolyte material of the all-solid-state lithium secondary battery, namely Li3P1- xSbxS4-2.5xO2.5x(x is 0.05) glass-ceramic.
For Li3P1-xSbxS4-2.5xO2.5x(x ═ 0.05) the lithium ion solid electrolyte material was subjected to a crystal structure test and an electrochemical performance test. The lithium ion solid electrolyte powder material was used to prepare a sample in a glove box with a water content of less than 10ppm, and X-ray diffraction measurements were performed to obtain the crystal structure information of the sample as shown in fig. 10. Pressing the lithium ion solid electrolyte powder material into a sheet Li with the diameter of 10mm and the thickness of 1mm under the conditions that the water content is less than 10ppm and the pressure of 10MPa3P1- xSbxS4-2.5xO2.5x(x ═ 0.05) glass ceramic lithium ion solid electrolyte. Then EIS test was carried out at different temperatures using carbon as a blocking electrode to test the conductivity, and the results are shown in FIG. 6, where FIG. 6 is the conductivity of the lithium ion solid electrolyte material prepared in example 6 of the present invention at different temperatures, and the room temperature conductivity is 4.67X 10-4S cm-1。
Comparative example
Under the protection of argon atmosphere, Li with the purity of more than 99 percent is respectively added2S、P2S5Weighing according to a molar ratio of 75:25, grinding and uniformly mixing at a rotating speed of 500rpm under the condition that the water content is less than 10ppm, carrying out high-energy ball milling for 12 hours under the condition of a ball-to-material ratio of 45:1 to obtain a primary powder material, taking out the primary powder material, uniformly grinding, tabletting under a pressure of 10MPa to obtain a flaky primary material, and filling the flaky primary material into a sintering die. Heating the sintering mold filled with the sheet-shaped primary material to 270 ℃ at a heating rate of 2 ℃/min, preserving heat for 2h, cooling to room temperature along with the furnace, taking out the sheet-shaped sintering product under the condition that the water content is less than 100ppm, and grinding uniformly to obtain the powder which is the lithium ion solid electrolyte material of the all-solid-state lithium secondary battery, namely Li3PS4A glass-ceramic.
For Li3PS4And (3) carrying out crystal structure characterization and electrochemical performance test on the lithium ion solid electrolyte material. The lithium ion solid electrolyte powder material was used to prepare a sample in a glove box with a water content of less than 10ppm, and X-ray diffraction measurements were performed to obtain the crystal structure information of the sample as shown in fig. 9.
The obtained Li3PS4Lithium ion solid electrolyte exposed to H-bearing gas2S in the closed container of the gas detection equipment, the atmosphere of the container is air, and H is monitored2S gas content, results are shown in FIG. 11, in 180 minutes, H in the vessel2The S gas content reached 90ppm, indicating Li3+3xP1-xZnxS4-xOx,Li3P1-xSbxS4-2.5xO2.5xWherein x is 0.01-0.05 of Li-ion solid electrolyte material compared with Li3PS4The lithium ion solid electrolyte is more stable to air. Simultaneously shows higher lithium ion conductivity, Li3PS4The lithium ion solid electrolyte has a room temperature conductivity of 4.1X 10 as shown in FIG. 12-4S cm-1。
The above examples and test results show that no significant chemical reaction occurs between the lithium ion solid electrolyte prepared by the present invention and air within 180 minutes, and the lithium ion solid electrolyte has good stability (see fig. 1 and 2). The lithium ion solid conductor material prepared by the invention has no obvious reaction with metallic lithium within 900 hours, and has excellent stability to lithium (see fig. 3 and fig. 4). The conductivity of the lithium ion solid conductor material prepared by the invention exceeds 10-3S cm-1(25 ℃) the conductivity increased with increasing temperature (see fig. 5, 6). The lithium ion solid conductor material is assembled to prepare the all-solid-state lithium battery, no obvious attenuation occurs after 100 cycles, and the capacity retention rate of the battery reaches 95.3% and 98.4% (see fig. 7 and 8).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (3)

1. A sulfide solid electrolyte is prepared according to the following steps:
A) mixing Li2S and P2S5Mixing with antimony oxide, and performing high-energy ball milling to obtain a primary material;
Li2S、P2S5and antimony oxide in a molar ratio of 3(1-x）：（1-x）：x；
The rotating speed of the high-energy ball mill is 200-500 rpm; the time of the high-energy ball milling is 9-18 hours; the ball-material ratio of the high-energy ball mill is (1-60): 1;
B) under the condition of inert gas, carrying out heat treatment on the primary material to obtain a sulfide lithium ion solid electrolyte shown in a formula (II);
the temperature of the heat treatment is 150-400 ℃; the heat treatment time is 1-5 hours; the temperature of the heat treatment is realized by raising the temperature; the heating rate is 1-10 ℃/min;
Li3P x1-Sb x S x4-2.5O x2.5formula (II);
wherein, 0.01 is less than or equal tox≤0.05。
2. The sulfide solid electrolyte according to claim 1, wherein the sulfide solid electrolyte is characterized byx0.01, 0.02, 0.03, 0.04 or 0.05.
3. An all-solid-state lithium secondary battery includes a positive electrode, a negative electrode, and an electrolyte;
the electrolyte is the sulfide solid electrolyte according to any one of claims 1 to 2.
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