WO2023024266A1 - Électrolyte solide au sulfure revêtu et son procédé de préparation et son utilisation - Google Patents

Électrolyte solide au sulfure revêtu et son procédé de préparation et son utilisation Download PDF

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WO2023024266A1
WO2023024266A1 PCT/CN2021/129082 CN2021129082W WO2023024266A1 WO 2023024266 A1 WO2023024266 A1 WO 2023024266A1 CN 2021129082 W CN2021129082 W CN 2021129082W WO 2023024266 A1 WO2023024266 A1 WO 2023024266A1
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solid electrolyte
sulfide solid
coated
preparation
sulfide
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PCT/CN2021/129082
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Chinese (zh)
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岳敏
陈杰
杨凯
王倩
钱超
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深圳市研一新材料有限责任公司
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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
    • 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

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  • the invention relates to the field of solid-state batteries, in particular to a coated sulfide solid-state electrolyte and a preparation method and application thereof.
  • lithium-ion batteries have become the main force of existing energy storage devices.
  • commercial lithium-ion batteries use ester or ether organic liquid electrolytes, which are volatile, easy to decompose, and prone to leakage during use, which seriously affects the service life of the battery.
  • organic The electrolyte is prone to side reactions with the electrode materials during the electrochemical cycle, resulting in flatulence, fire and explosion and other safety hazards.
  • metal lithium as the anode material of lithium-ion batteries has application prospects.
  • metal lithium is prone to grow lithium dendrites in the liquid electrolyte, and lithium dendrites may puncture the separator and cause short circuit, catch fire, or even explode.
  • solid electrolytes Compared with liquid electrolytes, solid electrolytes have the advantages of non-combustibility, non-flammability, non-corrosion, and high mechanical strength, which avoids electrolyte leakage and electrode short circuits in traditional liquid lithium-ion batteries, and reduces the sensitivity of the battery pack to temperature. Due to the high mechanical strength of the solid-state electrolyte, it can effectively prevent the growth of lithium dendrites, and has extremely high safety during use.
  • solid electrolytes mainly include oxides, sulfides, and polymer solid electrolytes.
  • oxide solid electrolytes are not sensitive to the environment, have excellent water and oxygen resistance, and have relatively stable physical and chemical properties, but low conductivity.
  • Polymer solid electrolyte is formed by the complexation of polar polymers and metal salts. It has good film-forming properties, flexibility and high safety performance, but has low conductivity, small migration number of lithium ions, and poor mechanical properties.
  • the sulfide solid electrolyte has an ionic conductivity comparable to that of a liquid electrolyte solution, the lithium ion migration number is close to 1, and the electrolyte and electrode materials have good wettability. It is suitable for high energy density energy storage devices and has become a very promising candidate for the development of all-solid-state batteries.
  • One of the technical routes One of the technical routes.
  • sulfide solid-state electrolytes are particularly sensitive to water and oxygen, and the environmental requirements during preparation and use are extremely harsh, which severely limits its large-scale application.
  • the electrochemical window of sulfide solid-state electrolytes and high-voltage cathode materials is not good. Matching, often produces a large impedance and a variety of decomposition products at the interface, forming a space charge layer; in addition, when the sulfide contacts with the lithium metal negative electrode, it reacts to form a substance with poor ion conductivity, which is not conducive to the migration of lithium ions , these problems faced by sulfide solid-state electrolytes greatly affect the performance of all-solid-state batteries.
  • Chinese patent CN111864256A discloses a sulfide solid electrolyte and an all-solid lithium secondary battery.
  • the sulfide solid electrolyte of the invention is a glass ceramic solid electrolyte in which a glass phase and a crystal phase are evenly mixed.
  • M x S 2 O 3 (M is selected from one or more of Na, K, Ba and Ca, 1 ⁇ x ⁇ 2) are mixed in proportion, and heat-treated at 150-450°C to obtain the invention Sulfide solid electrolyte.
  • the cathode membrane is obtained by mixing and pressing the cathode active material and the sulfide solid electrolyte of the invention into layers.
  • the sulfide solid electrolyte prepared by this process is still relatively sensitive to water, and the sulfide solid electrolyte is directly mixed with the high-voltage positive electrode active material in the positive electrode diaphragm. There are many side reactions; secondly, the preparation of the positive electrode membrane needs to be carried out under an inert atmosphere, which greatly increases its preparation cost and is not conducive to large-scale industrial production.
  • Chinese patent CN112203975A discloses a sulfide solid electrolyte and a battery.
  • the invention relates to a solid electrolyte that can be used as a lithium secondary battery, etc., which has the property of suppressing the generation of hydrogen sulfide gas even when exposed to moisture in the atmosphere.
  • the sulfide solid electrolyte prepared by this process cannot effectively isolate moisture, and is still sensitive to moisture during use and storage, and still produces a large amount of hydrogen sulfide gas in an environment with low humidity.
  • the interface problem between it and the high-voltage positive electrode material cannot be effectively suppressed.
  • Chinese patent CN111740152A discloses a high-performance sulfide solid-state electrolyte and its preparation method.
  • the invention provides a high-performance sulfide solid-state electrolyte with high ionic conductivity and low electronic conductivity, wherein two or three The two raw materials are mixed according to a certain molar ratio, ball milled and sintered, and the two processes are carried out under an inert atmosphere to obtain a sulfide solid with the general structure of (100-x)Li 2 P ⁇ xP 2 S 5 ⁇ yM Electrolyte, wherein M is zinc oxide, phosphorus pentoxide, lithium fluoride, lithium chloride.
  • the invention improves the chemical stability of the solid-state electrolyte by doping oxygen, fluorine or chlorine into the sulfide solid-state electrolyte.
  • the sulfide solid electrolyte obtained by this process still has high requirements on the atmosphere during use and storage, the oxygen content is not more than 0.1ppm, and the water content is not more than 0.1ppm.
  • Such a harsh low dew point environment makes the sulfide solid electrolyte industrialization difficulty.
  • Chinese patent CN111908437A discloses a preparation method of a sulfide solid electrolyte.
  • the invention obtains a uniformly mixed precursor by mixing Li 2 S, P 2 S 5 and lithium salts of halides through stoichiometric ratio, grinding and sieving Then place the precursor in the ceramic vibrating tank in the microwave equipment, vibrate and turn over, microwave sintering at 150-400°C for 10min-1h, and after cooling, obtain argentite-type solid state containing elements lithium, phosphorus, sulfur and halogen electrolyte.
  • the sulfide solid electrolyte of the invention has high ion conductivity, it is extremely unstable in air, which limits the practical application of the solid electrolyte.
  • Chinese patent CN109509910A discloses a composite solid electrolyte and its preparation method.
  • the invention improves the interface problem between the sulfide solid electrolyte and the electrode material by compounding the amorphous oxide solid electrolyte on the surface of the sulfide solid electrolyte.
  • the composite solid electrolyte of the invention does not solve the problem of poor stability of the sulfide solid electrolyte to humidity and oxygen, and when the battery is assembled and tested, the voltage mismatch between the positive electrode material and the sulfide solid electrolyte cannot be avoided during the preparation of the positive electrode sheet. , seriously affecting the cycle stability.
  • the problem to be solved by the invention is to improve the stability of the sulfide solid electrolyte to water, and improve the matching degree of the electrochemical window when the sulfide solid electrolyte is mixed with positive electrode materials.
  • one of the objects of the present invention is to provide a highly stable coated sulfide solid electrolyte, which can effectively improve the water stability of the sulfide solid electrolyte and the compatibility with normal electrolytes. Electrochemical stability when negative electrode materials are mixed and used; the second object of the present invention is to provide the preparation method of the above-mentioned coated sulfide solid electrolyte; the third object of the present invention is to provide the above-mentioned coated sulfide solid electrolyte in a solid state Application in batteries; the fourth object of the present invention is to provide a solid-state battery containing the above-mentioned coated sulfide solid-state electrolyte.
  • a coated sulfide solid electrolyte which is a coated sulfide solid electrolyte in which an oxide solid electrolyte layer is coated on the surface of sulfide solid electrolyte particles;
  • the oxide solid electrolyte is at least one of LiNb x Ta 1-x O 3 (0.15 ⁇ x ⁇ 0.85) type, LiPON type and NASICON type.
  • the LiPON type is Li 3.3 PO 3.9 N 0.17
  • the NASICON type is Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 .
  • the DN 50 particle size of the sulfide solid electrolyte particles is 0.50-30.00 ⁇ m, preferably 0.50-3.00 ⁇ m; preferably, the DN 50 particle size of the coated sulfide solid electrolyte is 0.53 -3.08 ⁇ m.
  • the oxide solid electrolyte layer has a thickness of 8.00-100.00 nm, preferably 8.50-99.60 nm.
  • the initial ion conductivity of the coated sulfide solid electrolyte is 0.35-9.2 mS/cm, preferably, the initial ion conductivity of the sulfide solid electrolyte is 0.68-10.8 mS/cm.
  • the present invention also provides a preparation method for the above-mentioned coated sulfide solid electrolyte, comprising the following steps:
  • An oxide solid electrolyte layer is prepared on the surface of the sulfide solid electrolyte particles by a wet coating method or a physical vapor deposition method to obtain a coated sulfide solid electrolyte.
  • the pressing pressure of the tablet in step (1) is 100-1000 MPa, preferably, the sintering temperature is 350-600° C., further preferably, the sintering time is 2-15 h.
  • the above-mentioned preparation method, the wet coating method described in step (2) comprises the following steps:
  • step (B) spraying the precursor solution prepared in step (A) onto the surface of the sulfide solid electrolyte particles, pre-sintering in an inert atmosphere, and then sintering in a pure oxygen atmosphere to obtain a coated sulfide solid electrolyte.
  • the spraying rate in step (B) is 5-15g/min, preferably, the spraying time is 1-5min, further preferably, the sintering temperature is 200-600°C , More preferably, the sintering time is 1-3h.
  • the physical vapor deposition method is one of magnetron sputtering, atomic layer deposition and vacuum evaporation, preferably magnetron sputtering.
  • above-mentioned preparation method described magnetron sputtering method comprises the steps:
  • the sputtering power in step (b) is 50-400W, preferably 100-300W; preferably, the sputtering time is 100-300min; the sputtering pressure is 2.5 ⁇ 10 -1 -9.0 ⁇ 10 -1 Pa.
  • the present invention also provides the application of the above coated sulfide solid electrolyte or the coated sulfide solid electrolyte prepared by the above preparation method in a solid state battery.
  • the present invention also provides a solid-state battery, including a positive electrode, a solid electrolyte, and a negative electrode, wherein at least one of the positive electrode, solid electrolyte, and negative electrode includes the above-mentioned coated sulfide solid electrolyte or the coated sulfide prepared by the above-mentioned preparation method. Coated sulfide solid electrolyte.
  • a coated sulfide solid electrolyte is obtained by coating a specific oxide solid electrolyte on the surface of the sulfide solid electrolyte, and the oxide solid electrolyte layer has a relatively high ion conductivity, between 10 -4 -10 - 2 S/cm, has high chemical stability, is insensitive to moisture in the air, and has good electrochemical stability when mixed with high-voltage cathode materials, which inhibits the formation of space charges, thus successfully solving the problem of sulfide solid electrolytes. Poor water stability and electrochemical window mismatch problems when sulfide solid electrolytes are mixed with cathode materials.
  • the process conditions such as sintering temperature are strictly controlled, which significantly improves the chemical stability of the coated sulfide solid electrolyte, making industrial large-scale production possible.
  • the coated sulfide solid electrolyte of the present invention is more compatible with high-voltage positive electrode materials, and the prepared solid-state battery has more excellent electrochemical performance and higher safety performance.
  • Fig. 1 is the schematic diagram of the coated sulfide solid state electrolyte of the embodiment of the present invention
  • Fig. 2 is a schematic diagram of a solid-state battery according to an embodiment of the present invention.
  • the particle size of the sulfide solid electrolyte is 0.5-30.0 ⁇ m means that the particle size of the solid electrolyte is 0.5 ⁇ m or more and 30.0 ⁇ m or less.
  • “at least one” means one or more, and “multiple” means two or more.
  • “one or more of a, b, or c”, or, “at least one of a, b, and c” can mean: a, b, c, a-b (that is, a and b ), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple.
  • DN 50 particle size refers to the particle size corresponding to when the cumulative particle size number distribution percentage of the sample reaches 50%.
  • the quality of the relevant components mentioned in the examples of the present invention can not only refer to the specific content of each component, but also represent the proportional relationship between the mass of each component. Therefore, as long as it is implemented according to the present invention
  • the proportional expansion or reduction of the content of the relevant components of the example is within the scope of the disclosure of the present invention.
  • the weight described in the embodiments of the present invention may be ⁇ g, mg, g, kg and other well-known mass units in the chemical industry.
  • the invention provides a coated sulfide solid electrolyte, which is a coated sulfide solid electrolyte with an oxide solid electrolyte layer coated on the surface of sulfide solid electrolyte particles;
  • the oxide solid electrolyte is at least one of LiNb x Ta 1-x O 3 (0.15 ⁇ x ⁇ 0.85), LiPON type and NASICON type.
  • the LiPON type is Li 3.3 PO 3.9 N 0.17
  • the NASICON type is Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 .
  • the above-mentioned sulfide solid electrolyte is extremely unstable in the air, and hydrogen sulfide will be generated when it meets water, which greatly affects the safety performance of use; moreover, there is a problem of voltage mismatch between the sulfide solid electrolyte and the high-voltage positive electrode material, which will generate space charge. A series of side reactions occur at the interface, which increases the interface impedance and seriously affects the electrochemical performance of the solid-state battery.
  • the surface of the sulfide solid electrolyte By coating the surface of the sulfide solid electrolyte with at least one oxide solid electrolyte layer among LiNb x Ta (1-x) O 3 (0.15 ⁇ x ⁇ 0.85) type, LiPON type and NASICON type, as shown in Figure 1,
  • the stability of the sulfide solid electrolyte to water is increased, which significantly suppresses the generation of hydrogen sulfide gas during storage and use of the sulfide solid electrolyte;
  • the direct contact between the positive electrode material and the sulfide solid electrolyte suppresses the formation of space charges between the sulfide solid electrolyte and the high-voltage positive electrode.
  • LiNb x Ta (1-x) O 3 is superior to LiNbO 3 and LiTaO 3 in terms of ionic conductivity and stability to water and oxygen due to the synergistic effect of niobium and tantalum.
  • Li 3.3 PO 3.9 N 0.17 has higher ionic conductivity and better mechanical properties, stable chemical and electrochemical properties, and can be matched with positive electrodes such as LiCoO 2 and LiMnO 4 and negative electrodes such as metal lithium and lithium alloys.
  • Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 not only has high ionic conductivity, but also has good chemical stability to water and oxygen, these characteristics make Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 can be used as a sulfide solid electrolyte of the cladding.
  • the D N 50 particle size of the sulfide solid electrolyte particles is 0.50-30.00 ⁇ m, preferably, the sulfide solid electrolyte particles
  • the DN 50 particle size of the coated sulfide solid electrolyte is 0.50-3.00 ⁇ m, and the DN 50 particle size of the coated sulfide solid electrolyte is 0.53-3.08 ⁇ m.
  • the DN 50 particle size of the sulfide solid electrolyte particles is preferably controlled at 0.50-3.00 ⁇ m.
  • the coated sulfide solid electrolyte is mixed with the positive and negative active materials to form a slurry, the coated sulfide solid electrolyte is more likely to be filled between the positive and negative active material particles, which requires the particle size of the sulfide solid electrolyte
  • the diameter is not easy to be too large.
  • the particle size is too large, the contact area between particles is small and the pores are large, resulting in large interface resistance.
  • the particle size is too low, it is not conducive to the process preparation, and the process is complicated.
  • the oxide solid electrolyte layer has a thickness of 8.00-100.00 nm, preferably 8.50-99.60 nm, and the oxide solid electrolyte layer
  • the thickness is too thin, it will affect the stability of water and oxygen, affect the safety performance of use, and cause the oxide electrolyte layer to be easily broken; when it is too thick, it will significantly reduce the ionic conductivity of the overall solid electrolyte, affecting ion transport performance.
  • the oxide solid electrolyte package The coating is not easy to be too thick or too thin.
  • the initial ion conductivity of the coated sulfide solid electrolyte is 0.35-9.2mS/cm, preferably, the sulfide The conductivity of the solid electrolyte is 0.68-10.8 mS/cm.
  • the present invention also provides a preparation method for the above-mentioned coated sulfide solid electrolyte, comprising the following steps:
  • An oxide solid electrolyte layer is prepared on the surface of the sulfide solid electrolyte particles by a wet coating method or a physical vapor deposition method to obtain a coated sulfide solid electrolyte.
  • the sulfide solid-state electrolyte raw material in step (1) includes one or more of metal sulfide, metal halide, and P 2 S 5 , wherein the metal sulfide includes Li 2 S, GeS 2 , SiS 2 , SnS One or more of 2 , the metal halides include one or more of LiCl, LiBr and LiI. Specifically, each raw material component is weighed according to the stoichiometric ratio of the sulfide solid electrolyte, without a certain excess.
  • the pressure of the tablet pressing in step (1) is 100-1000 MPa, and the sintering is carried out under an inert atmosphere at a temperature of 350-600° C. for 2-15 hours. , wherein the temperature rising/falling rate is 2-5°C/min. If the pressure is too low during tablet compression, it will be difficult to form the tablet, and if it is too high, the mold may be damaged. If the sintering temperature is too high and the sintering time is too long, the solid electrolyte will melt and the impurity phase will increase; if the sintering temperature is too low and the sintering time is too short, the reaction will be insufficient.
  • the wet coating method described in step (2) includes the following steps:
  • step (B) spraying the precursor solution obtained in step (A) onto the surface of the sulfide solid electrolyte particles, pre-sintering in an inert atmosphere, and then sintering in a pure oxygen atmosphere to obtain a coating layer sulfide solid electrolyte.
  • metal lithium, niobium ethoxide and tantalum ethoxide are selected as raw materials for the oxide solid electrolyte in step (A).
  • the metal lithium is preferably battery-grade metal lithium with a purity of not less than 99.6 %.
  • metal lithium is dissolved in alcohol, and after the metal lithium is completely dissolved, a mixture of tantalum ethoxide and niobium ethoxide is added to form a precursor solution.
  • the spraying rate in step (B) is 5-15g/min, preferably, the spraying time is 1-5min, further preferably , after spraying, it also includes drying and sieving the sulfide solid electrolyte, wherein the drying temperature is 80°C.
  • the inventors have found through research that there is a positive correlation between the spraying rate and the spraying time and the thickness of the oxide solid electrolyte layer, and the thickness of the oxide solid electrolyte layer can be controlled by adjusting these two parameters.
  • the pre-sintering in step (B) is under an inert atmosphere, kept at 120°C for 2 hours, and the heating rate is 5°C/min; then Sintering, feed oxygen with a purity of 99.99%, raise the temperature to 200-600°C, preferably 500-600°C, keep the temperature at a constant temperature for 1-3h, and the heating rate is 5°C/min.
  • the coating is obtained type sulfide solid electrolyte.
  • pre-sintering is carried out under an inert atmosphere. The purpose is to form a dense layer on the surface of the sulfide solid electrolyte, and then raise the temperature and sinter in pure oxygen to remove the organic groups on the surface.
  • the physical vapor deposition method is one of magnetron sputtering, atomic layer deposition or vacuum evaporation, preferably magnetron sputtering.
  • the magnetron sputtering method includes the following steps:
  • the sputtering power in step (b) is 50-400W, preferably 100-300W; the sputtering time is 100-300min; The air pressure is 2.5 ⁇ 10 -1 -9.0 ⁇ 10 -1 Pa.
  • the present invention also provides the application of the above coated sulfide solid electrolyte or the coated sulfide solid electrolyte prepared by the above preparation method in a solid state battery.
  • the present invention also provides a solid-state battery, including a positive pole piece, a solid electrolyte and a negative pole piece, wherein at least one of the positive pole piece, the solid electrolyte and the negative pole piece comprises the above-mentioned coated sulfide solid electrolyte or The coated sulfide solid electrolyte prepared by the above preparation method.
  • the positive electrode piece is prepared by the following steps: under the environment of dew point -30°C, weigh the conductive agent, binder, positive electrode active The material and the coated sulfide solid electrolyte are added to the organic solvent, ground and mixed uniformly to obtain the positive active slurry; the positive active slurry is evenly coated on the surface of the positive current collector to form a positive active layer, and then rolled after drying , Cut to get the positive pole piece. A certain amount of coated solid electrolyte is added in the preparation process, so that lithium ions can be effectively conducted in the positive electrode. At the same time, the amount of coated solid electrolyte has a certain effect on the overall electrochemical performance of the solid-state battery. Impact.
  • the above positive electrode active materials include lithium cobaltate, lithium manganate, lithium iron phosphate, ternary materials and LiNi a Co b Mn 1-ab M c O 2 (0.3 ⁇ a ⁇ 0.75, 0.2 ⁇ b ⁇ 0.3, 0 ⁇ c ⁇ 0.1; M is at least one of Ti, Mg, Al, V, Cr, Zr, Ba, La, Ce, Sn).
  • the capacity of the solid-state battery provided by the invention is mainly contributed by the amount of positive electrode active material, and its mass proportion in the positive electrode active layer has a significant impact on the charge and discharge capacity of the positive electrode.
  • the electrochemical performance of the overall solid-state battery can be optimized by optimizing the amount of positive active material added.
  • the positive current collector is selected from at least one of aluminum foil, carbon-coated aluminum foil, foamed aluminum foil, and foamed nickel, preferably carbon-coated aluminum foil. This is because the positive electrode is at a relatively high potential during charging and discharging, while the negative electrode is at a low potential.
  • the current collector is prone to oxidation during the charging process, and the surface of the carbon-coated aluminum foil has a layer of dense alumina, which can resist this oxidation. Metals that are easily oxidized under high pressure such as copper foil cannot be used.
  • the conductive agent is at least one selected from SuperP, acetylene black, Ketjen black, carbon black, carbon nanotubes, graphene and carbon fibers.
  • the addition of the conductive agent plays a role in enhancing the overall electronic conductivity of the positive electrode, not as a source of capacity contribution. Therefore, the amount of conductive agent added will affect the overall capacity of the positive electrode to a certain extent. If the amount of conductive agent added is too low, there will be too few electronic conduction channels, which is not conducive to high-current charging and discharging; if the added amount of conductive agent is too high, the activity of the positive electrode will be reduced.
  • the relative content of substances affects the battery capacity, and the optimal electrochemical performance can be obtained by optimizing the mass proportion of the conductive agent in the positive active layer.
  • the above binder is selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene, CMC, SBR, NBR, PVC, Polysiloxane, SEBS and SBS. If the amount of binder added is too low, it will be difficult to stabilize the electrode structure; if the amount of binder added is too high, it will cause an increase in resistance, resulting in a decrease in the relative content of the conductive agent or positive electrode active material and a decrease in the resulting positive electrode conductivity. performance degradation.
  • the organic solvent is at least one selected from N-methylpyrrolidone, dimethyl carbonate, ethyl acetate, absolute ethanol, acetone, diethyl carbonate and methyl propionate. These organic solvents do not react to positive electrode active materials, conductive agents, binders, and coated sulfide solid electrolytes, and have a relatively low vaporization temperature.
  • the solid-state electrolyte sheet is prepared by the following method: compressing the coated sulfide solid-state electrolyte under a pressure of 100MPa-1000MPa. Since the solid electrolyte sheet is too thick, the lithium ion transmission rate will be slow, so the solid electrolyte should be made as thin as possible.
  • the negative electrode of the solid-state battery of the present invention can preferably be one of lithium metal sheet, indium sheet, lithium-indium alloy, aluminum foil, tin foil, lithium aluminum alloy or lithium silicon alloy, or the negative electrode can be prepared by the following method: In an environment with a dew point of -30°C, weigh the conductive agent, binder, negative electrode active material and coated sulfide solid electrolyte according to a certain proportion, add them to the organic solvent, grind and mix evenly to obtain the negative electrode active slurry; The negative electrode active slurry is uniformly coated on the surface of the negative electrode current collector to form a negative electrode active layer, and after drying, the negative electrode is obtained by rolling and cutting.
  • the anode active material includes one of silicon carbon, lithium titanate or graphite, and the anode current collector is selected from one of copper foil and stainless steel foil.
  • the above-mentioned solid-state battery is prepared by the following method: the positive electrode sheet, the solid-state electrolyte sheet and the negative electrode are sequentially laminated and subjected to cold pressing under a pressure of 500MPa-1000MPa to obtain a solid-state battery.
  • the solid-state battery includes but is not limited to one of a button battery, a flat battery, a cylindrical battery and a pouch battery.
  • the raw materials or reagents used in the present invention are all purchased from mainstream manufacturers in the market, and those who do not indicate the manufacturer or the concentration are all analytically pure grade raw materials or reagents that can be routinely obtained. As long as they can play the expected role, There are no particular restrictions.
  • the instruments and equipment used in this example are all purchased from major manufacturers in the market, and there are no special limitations as long as they can play the expected role. If no specific technique or condition is indicated in this example, the technique or condition described in the literature in this field or the product manual shall be followed.
  • the magnetron sputtering apparatus was purchased from Shenyang Jingyi Research Technology Co., Ltd., model: high vacuum multifunctional magnetron sputtering equipment (101A-1B).
  • Laser particle size analyzer purchased from Zhubai Zhenzhen Optical Instrument Co., Ltd., model: LT3600.
  • the tube furnace with three temperature zones was purchased from Shanghai Hanjun Experimental Equipment Co., Ltd., model: HTF-1200III.
  • the isostatic press was purchased from Hefei Kejing Material Technology Co., Ltd., model: YLJ-CIP-15; the tableting die was purchased from Hefei Kejing Material Technology Co., Ltd., model: Die-SP20; the conductivity test kit was purchased from Hefei Kejing Material Technology Co., Ltd., model: EQ-PSC.
  • a high-energy ball mill was purchased from Changsha Deco Instrument Equipment Co., Ltd., model DECO-PBM-V-0.4L.
  • BTS-5V10mA battery testing equipment was purchased from Shenzhen Newwell Electronics Co., Ltd.
  • a transmission electron microscope was purchased from Zeiss, Germany.
  • Li 2 S, GeS 2 , SiS 2 , SnS 2 , LiCl, LiBr, LiI, P 2 S 5 were all purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.
  • Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 was purchased from Hefei Kejing Technology Materials Co., Ltd.
  • step 2 pour the powder obtained in step 1 into a tableting mold, and use an isostatic press to perform tableting with a pressure of 200 MPa and a holding time of 1 min to obtain a disc with a diameter of 16 mm.
  • step (1) Spray the above precursor solution evenly on the surface of the Li 6 PS 5 Cl sulfide solid electrolyte particles prepared in step (1), the spraying rate is 5g/min, and the spraying time is 1.5min.
  • the thickness of the oxide solid electrolyte layer was measured by transmission electron microscope TEM to be 10.5 nm, and the particle size of the coated sulfide solid electrolyte DN 50 was measured by a laser particle size analyzer to be 0.53 ⁇ m.
  • step (1) Spray the above precursor solution evenly on the surface of the Li 3 PS 4 sulfide solid electrolyte particles prepared in step (1), the spraying rate is 10g/min, and the spraying time is 2.6min.
  • the thickness of the oxide solid electrolyte layer was measured to be 38.6 nm.
  • the DN 50 particle size of the coated sulfide solid electrolyte was measured by a laser particle size analyzer to be 3.08 ⁇ m.
  • the DN 50 particle size measured by a laser particle size analyzer is 1.0 ⁇ m.
  • the thickness of the oxide solid electrolyte layer was measured to be 8.5 nm.
  • the DN 50 particle size of the coated sulfide solid electrolyte was measured by a laser particle size analyzer to be 1.01 ⁇ m.
  • Li 2 S, P 2 S 5 , and LiBr were thoroughly mixed in a molar ratio of 4:1:3 to obtain 6.0 g of mixed powder.
  • Zirconia balls with a diameter of 10 mm were used for ball milling, the ball milling speed was set at 300 rpm, the ball milling time was 20 hours, and the mass ratio of balls to materials was 30:1.
  • the ball-milled powder is ground in a mortar to make the powder fine.
  • step 2 pour the powder obtained in step 1 into a tableting mold, and use an isostatic press to perform tableting with a pressure of 350 MPa and a holding time of 1 min to obtain a disc with a diameter of 16 mm.
  • the thickness of the oxide solid electrolyte layer was measured to be 68.7 nm.
  • the particle size D N 50 of the coated sulfide solid electrolyte was measured by a laser particle size analyzer to be 1.63 ⁇ m.
  • Li 2 S, P 2 S 5 , and SnS 2 were thoroughly mixed in a molar ratio of 5.25:0.75:1.5 to obtain 6.0 g of mixed powder.
  • Zirconia balls with a diameter of 10 mm were used for ball milling, the ball milling speed was set at 450 rpm, the ball milling time was 15 hours, and the ball-to-material mass ratio was 10:1.
  • the ball-milled powder is ground in a mortar to make the powder fine.
  • step 2 pour the powder obtained in step 1 into a tableting mold, and use an isostatic press to perform tableting with a pressure of 350 MPa and a holding time of 1 min to obtain a disc with a diameter of 16 mm.
  • the thickness of the oxide solid electrolyte layer was measured to be 50.6 nm.
  • the DN 50 particle size of the coated sulfide solid electrolyte was measured by a laser particle size analyzer to be 1.60 ⁇ m.
  • Li 2 S, P 2 S 5 , and SiS 2 were thoroughly mixed in a molar ratio of 9.5:2.5:1.0 to obtain 6.0 g of mixed powder.
  • Zirconia balls with a diameter of 10 mm were used for ball milling, the ball milling speed was set at 450 rpm, the ball milling time was 10 hours, and the ball-to-material mass ratio was 10:1.
  • the ball-milled powder is ground in a mortar to make the powder fine.
  • step 2 pour the powder obtained in step 1 into a tableting mold, and use an isostatic press to perform tableting with a pressure of 300 MPa and a holding time of 1 min to obtain a disc with a diameter of 16 mm.
  • target material Grind 15g of Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 solid electrolyte powder and 1% binder (PVA) to make them evenly mixed, and use a tablet press at 300kg/cm The pressure of 2 presses the powder into a copper mold with a diameter of 50mm to make a copper back target with a thickness of 2.5mm.
  • PVA binder
  • cladding layer adopt radio frequency magnetron sputtering method, the parameters of magnetron sputtering are: chamber vacuum degree is 1.0 ⁇ 10 -4 Pa, working atmosphere is argon, target distance is 7cm, gas flow rate is 35sccm, working pressure 0.25Pa, sputtering time 100min, sputtering power 100W, substrate temperature at room temperature, build Li 1.4 Al 0.4 Ti 1.6 on the surface of Li 9.5 Si 0.5 P 2.5 S 12 (LSiPS) sulfide solid electrolyte (PO 4 ) 3 (LATP) cladding layer to obtain the cladding sulfide solid electrolyte LATP-LSiPS.
  • LSiPS sulfide solid electrolyte
  • LATP LATP
  • the thickness of the oxide solid electrolyte layer was measured to be 9.8 nm.
  • the DN 50 particle size of the coated sulfide solid electrolyte was measured by a laser particle size analyzer to be 1.28 ⁇ m.
  • target material Grind 15g of Li 3 PO 4 and 1% binder (PVA) to make them evenly mixed, and use a tablet press to press the powder on a surface with a diameter of 50mm at a pressure of 300kg/cm 2 A copper back target with a thickness of 2.5 mm was made in a copper mold.
  • PVA binder
  • LGPS Li 10 GeP 2 S 12
  • the thickness of the oxide solid electrolyte layer was measured to be 95.3 nm.
  • Energy dispersive X-ray fluorescence spectrometer (test conditions) was used to test the elemental composition content of the oxide solid electrolyte layer, and the molecular formula of LiPON was Li 3.3 PO 3.9 N 0.17 .
  • the DN 50 particle size of the coated sulfide solid electrolyte was measured by a laser particle size analyzer to be 1.25 ⁇ m.
  • step 2 pour the powder obtained in step 1 into a tableting mold, and use an isostatic press to perform tableting, the pressure is kept at 100 MPa, and the holding time is 1 minute to obtain a disc with a diameter of 16 mm.
  • step (1) Spray the above precursor solution evenly on the surface of the Li 6 PS 5 Cl sulfide solid electrolyte particles prepared in step (1), the spraying rate is 5g/min, and the spraying time is 2min.
  • the thickness of the oxide solid electrolyte layer was measured to be 17.5 nm by transmission electron microscope TEM, and the particle size of the coated sulfide solid electrolyte DN 50 was measured to be 2.04 ⁇ m by a laser particle size analyzer.
  • step 2 pour the powder obtained in step 1 into a tableting mold, and use an isostatic press to perform tableting.
  • the pressure is maintained at 1000 MPa, and the holding time is 1 minute to obtain a disc with a diameter of 16 mm.
  • step (1) Spray the above precursor solution evenly on the surface of the Li 6 PS 5 Cl sulfide solid electrolyte particles prepared in step (1), the spraying rate is 15g/min, and the spraying time is 5min.
  • the thickness of the oxide solid electrolyte layer was measured to be 99.6 nm, and the particle size of the coated sulfide solid electrolyte DN 50 was measured to be 3.0 ⁇ m by a laser particle size analyzer.
  • the preparation method of Li 6 PS 5 Cl (LPSC) sulfide solid electrolyte particles is the same as the preparation method of step (1) in Example 1.
  • the preparation method is the same as the preparation method in step (1) in Example 2.
  • the preparation method of Li 10 GeP 2 S 12 (LGPS) sulfide solid electrolyte particles is the same as the preparation method of step (1) in Example 3.
  • the thickness of the oxide solid electrolyte layer was measured to be 11.5 nm.
  • the DN 50 particle size of the coated sulfide solid electrolyte was measured by a laser particle size analyzer to be 0.55 ⁇ m.
  • the thickness of the oxide solid electrolyte layer was measured to be 12.0 nm.
  • the DN 50 particle size of the coated sulfide solid electrolyte was measured by a laser particle size analyzer to be 0.54 ⁇ m.
  • step (2) in Example 1 The difference from step (2) in Example 1 is that the spraying time is 0.5min; the powdery interior is Li 6 PS 5 Cl sulfide solid electrolyte and the surface is coated with LiNb 0.5 Ta 0.5 O 3 coating layer Type sulfide solid electrolyte LiNb 0.5 Ta 0.5 O 3 -LPSC; using a transmission electron microscope TEM, the thickness of the oxide solid electrolyte layer was measured to be 3.4nm, and the coated sulfide solid electrolyte D was measured by a laser particle size analyzer. The N 50 particle size is 0.51 ⁇ m.
  • step (1) preparation method in the embodiment 2.
  • step (2) in Example 2 The difference from step (2) in Example 2 is that the spraying rate is 10g/min, and the spraying time is 10min; the obtained powdery interior is Li 3 PS 4 sulfide solid electrolyte and the surface is LiNb 0.15 Ta 0.85 O 3 Coated sulfide solid electrolyte LiNb 0.15 Ta 0.85 O 3 -LPS for the coating layer; the thickness of the oxide solid electrolyte layer was measured to be 140.6 nm by using a transmission electron microscope (TEM). The DN 50 particle size of the coated sulfide solid electrolyte was measured by a laser particle size analyzer to be 3.26 ⁇ m.
  • TEM transmission electron microscope
  • Lithium metal negative pole piece In a vacuum glove box, cut a metal lithium negative pole disc with a diameter of 12mm, which is the negative active material and negative current collector.
  • Lithium-indium alloy negative pole piece In a vacuum glove box, cut a lithium-indium alloy negative pole disc with a diameter of 12mm, which is the negative active material and negative current collector.
  • the solid-state electrolyte is mixed in N-methylpyrrolidone (NMP) solvent according to the mass ratio of 0.5:0.5:7.5:1.5 to prepare negative electrode active slurry.
  • NMP N-methylpyrrolidone
  • the negative electrode active slurry was coated on the copper foil, and after vacuum drying at 80°C, it was rolled and sliced to obtain a negative electrode sheet with a diameter of 12 mm, which was designated as CE-S3.
  • Example 1-9 and Comparative Examples 1-7 were respectively placed in a mold, and a solid electrolyte sheet with a thickness of 100 ⁇ m and a diameter of 16 mm was prepared by applying a pressure of 100 MPa, respectively denoted as SSE-S1 and SSE-S2 , SSE-S3, SSE-S4, SSE-S5, SSE-S6, SSE-S7, SSE-S8, SSE-S9, SSE-C1, SSE-C2, SSE-C3, SSE-C4, SSE-C5, SSE -C6 and SSE-C7.
  • SSE-S1 and SSE-S2 SSE-S3, SSE-S4, SSE-S5, SSE-S6, SSE-S7, SSE-S8, SSE-S9, SSE-C1, SSE-C2, SSE-C3, SSE-C4, SSE-C5, SSE -C6 and SSE-C7.
  • the coated sulfide solid electrolytes prepared in Examples 1-9 compared with the uncoated sulfide solid electrolytes in Comparative Examples 1-3, it can be seen from Table 1 that the coated sulfide solid electrolytes of the present invention The amount of hydrogen sulfide gas produced by the electrolyte is much lower than that of the uncoated sulfide solid electrolyte, and the attenuation of the ion conductivity after exposure to dry air for 4 hours is significantly lower than that of Comparative Examples 1-3; it can be seen from Table 3 that the battery The test results show that, compared with the uncoated sulfide solid electrolyte battery, the battery containing the coated sulfide solid electrolyte of the present invention has the first cycle charge specific capacity, the first cycle discharge specific capacity, and the discharge capacity after 100 cycles. The specific capacity and rate performance are significantly increased.
  • LiNb x Ta 1-x O 3 (0.15 ⁇ x ⁇ 0.85) is superior to LiNbO 3 and LiTaO 3 in ensuring the stability of the solid electrolyte to water and oxygen, It can improve the electrochemical stability of the sulfide solid electrolyte, and is significantly better than LiNbO 3 and LiTaO 3 in improving the cycle performance and rate performance of the battery.
  • the amount of hydrogen sulfide gas generated is too large, and the attenuation of ionic conductivity after 4 hours of exposure in dry air becomes significantly larger, which indicates that the electrochemical stability of the sulfide solid electrolyte cannot be improved at this time; it can be seen from Table 3 , the battery test results show that the thickness of the oxide solid electrolyte layer of the coated sulfide solid electrolyte is too low, and its first cycle charge specific capacity, first cycle discharge specific capacity, discharge specific capacity and rate performance after 100 cycles are significantly reduced .
  • the thickness of the oxide solid electrolyte layer is too thick, and the ionic conductivity of the oxide solid electrolyte is lower than that of the sulfide solid electrolyte, thus significantly reducing the ionic conductivity of the overall solid electrolyte, resulting in an increase in internal resistance and affecting ion transport performance. , is not conducive to the cycle performance, resulting in a decrease in the charge-discharge specific capacity and cycle performance, and seriously reduces the rate discharge performance.

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Abstract

La présente invention concerne le domaine des batteries solides, et spécifiquement un électrolyte solide à base de sulfure revêtu et son procédé de préparation et son utilisation. L'invention concerne un électrolyte solide de sulfure revêtu, qui est un électrolyte solide de sulfure revêtu ayant une couche d'électrolyte solide d'oxyde recouvrant les surfaces de particules d'électrolyte solide de sulfure. Un électrolyte solide d'oxyde spécifique est revêtu sur la surface d'un électrolyte solide de sulfure pour obtenir l'électrolyte solide de sulfure revêtu. La couche d'électrolyte solide d'oxyde de celui-ci présente une conductivité ionique relativement élevée et une stabilité chimique élevée, et est insensible à l'humidité dans l'air, et a une bonne stabilité électrochimique et inhibe la formation de charges d'espace lorsqu'il est mélangé avec des matériaux d'anode à haute tension, ce qui résout avec succès les problèmes de mauvaise stabilité à l'eau des électrolytes solides de sulfure et de la désadaptation de fenêtres électrochimiques lorsque des électrolytes solides de sulfure sont mélangés avec des matériaux d'anode.
PCT/CN2021/129082 2021-08-27 2021-11-05 Électrolyte solide au sulfure revêtu et son procédé de préparation et son utilisation WO2023024266A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117352856A (zh) * 2023-11-14 2024-01-05 深圳汇能储能材料工程研究中心有限公司 一种锂二次电池及其制备方法
CN117594869A (zh) * 2024-01-17 2024-02-23 中国第一汽车股份有限公司 一种硫化物及其制备方法、固态电解质、全固态电池和用电设备
CN118425805A (zh) * 2024-06-26 2024-08-02 浙江久功新能源科技有限公司 一种快速评估固态电池复合正极锂离子传输能力的方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114243099B (zh) * 2022-01-24 2023-09-19 蜂巢能源科技(无锡)有限公司 硫化物型电解质及其制备方法和应用
CN114914422B (zh) * 2022-05-19 2024-03-15 武汉理工大学 适用于硫化物全固态电池的复合负极、制备方法及锂电池
CN115000502A (zh) * 2022-07-21 2022-09-02 惠州亿纬锂能股份有限公司 一种具有核壳结构的固态电解质复合材料及其制备方法和应用
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CN117613369A (zh) * 2023-12-20 2024-02-27 高能时代(珠海)新能源科技有限公司 一种硫化物固态电解质材料及其制备方法和应用
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101114718A (zh) * 2007-08-31 2008-01-30 中国科学院上海硅酸盐研究所 锂离子无机复合固体电解质材料的设计准则与制备方法
CN103943880A (zh) * 2013-01-22 2014-07-23 华为技术有限公司 一种硫基玻璃陶瓷电解质及其制备方法、全固态锂电池及其制备方法
US20160322666A1 (en) * 2015-04-29 2016-11-03 Hyundai Motor Company Solid electrolyte and all-solid state battery comprising the same
CN107851840A (zh) * 2015-06-01 2018-03-27 气动覆层科技有责任限公司 用于阳极活性材料、阴极活性材料和固态电解质的纳米工程涂层及包含纳米工程涂层的电池的制造方法
CN108736069A (zh) * 2017-04-24 2018-11-02 通用汽车环球科技运作有限责任公司 锂金属电池的硫化物、氧化物和硫氧化物玻璃电解质膜的钝化
CN109244547A (zh) * 2018-08-23 2019-01-18 武汉艾特米克超能新材料科技有限公司 一种复合固态电解质隔膜及其制备方法和锂离子电池

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6090249B2 (ja) * 2014-07-10 2017-03-08 トヨタ自動車株式会社 複合活物質及びその製造方法
JP6347268B2 (ja) * 2016-02-26 2018-06-27 トヨタ自動車株式会社 複合活物質の製造方法
JP2017220318A (ja) * 2016-06-06 2017-12-14 トヨタ自動車株式会社 複合活物質
CN109509910A (zh) * 2018-12-12 2019-03-22 宁波容百新能源科技股份有限公司 一种复合型固态电解质及其制备方法
CN111864256B (zh) * 2019-04-25 2021-07-13 宁德时代新能源科技股份有限公司 硫化物固态电解质及全固态锂二次电池
CN111082132B (zh) * 2019-12-11 2023-05-09 天津巴莫科技有限责任公司 一种硫化物固态电解质及其制备方法
CN111785974B (zh) * 2020-08-25 2022-03-08 中南大学 用于硫化物固态锂离子电池的正极包覆方法、正极及电池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101114718A (zh) * 2007-08-31 2008-01-30 中国科学院上海硅酸盐研究所 锂离子无机复合固体电解质材料的设计准则与制备方法
CN103943880A (zh) * 2013-01-22 2014-07-23 华为技术有限公司 一种硫基玻璃陶瓷电解质及其制备方法、全固态锂电池及其制备方法
US20160322666A1 (en) * 2015-04-29 2016-11-03 Hyundai Motor Company Solid electrolyte and all-solid state battery comprising the same
CN107851840A (zh) * 2015-06-01 2018-03-27 气动覆层科技有责任限公司 用于阳极活性材料、阴极活性材料和固态电解质的纳米工程涂层及包含纳米工程涂层的电池的制造方法
CN108736069A (zh) * 2017-04-24 2018-11-02 通用汽车环球科技运作有限责任公司 锂金属电池的硫化物、氧化物和硫氧化物玻璃电解质膜的钝化
CN109244547A (zh) * 2018-08-23 2019-01-18 武汉艾特米克超能新材料科技有限公司 一种复合固态电解质隔膜及其制备方法和锂离子电池

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117352856A (zh) * 2023-11-14 2024-01-05 深圳汇能储能材料工程研究中心有限公司 一种锂二次电池及其制备方法
CN117594869A (zh) * 2024-01-17 2024-02-23 中国第一汽车股份有限公司 一种硫化物及其制备方法、固态电解质、全固态电池和用电设备
CN117594869B (zh) * 2024-01-17 2024-05-14 中国第一汽车股份有限公司 一种硫化物及其制备方法、固态电解质、全固态电池和用电设备
CN118425805A (zh) * 2024-06-26 2024-08-02 浙江久功新能源科技有限公司 一种快速评估固态电池复合正极锂离子传输能力的方法

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