CN103456984A - Preparation method of inorganic solid electrolyte membrane - Google Patents
Preparation method of inorganic solid electrolyte membrane Download PDFInfo
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- CN103456984A CN103456984A CN2013104183755A CN201310418375A CN103456984A CN 103456984 A CN103456984 A CN 103456984A CN 2013104183755 A CN2013104183755 A CN 2013104183755A CN 201310418375 A CN201310418375 A CN 201310418375A CN 103456984 A CN103456984 A CN 103456984A
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Abstract
The invention discloses a preparation method of an inorganic solid electrolyte membrane, which is used for preparing an inorganic solid electrolyte matrix in an electrode of a lithium battery. A material formulation of the matrix is as follows: a mass ratio of organopolysiloxane resin to lithium phosphate to kieselguhr is (25-30):(3-5):(72-65); the organic solid electrolyte membrane is prepared by inorganic electrolyte slice-slice superposing and polyphenylene sulfide membrane packaging. An inorganic lithium compound obtained by the method disclosed by the invention is uniform in distribution in a matrix membrane, so that charging and discharging performances of a full-solid lithium battery prepared by using the electrolyte are stable, and therefore, the charging and discharging times and the service life as well as the electric capacity are respectively improved by 80%-90% in comparison with the existing lithium battery, and the content of inorganic lithium in the solid electrolyte membrane is 18%-32%. A solid lithium battery prepared by using the electrolyte membrane has the characteristics of long service life, a plurality of charging and discharging times, and large battery capacity.
Description
Technical field
The invention relates to the manufacture method of inorganic solid electrolyte film, more particularly, the present invention relates to the manufacture method of inorganic solid electrolyte film in the electrode of lithium battery.
Background technology
Battery is the power supply as electrical equipment such as torch and phones by people very early, along with scientific and technological progress and the discovery of new material, people have developed Ni-MH battery and lithium battery, appearance along with portable electronics such as mobile phone and notebook computers, demand to the high performance of battery and miniaturization and etc. seems more and more stronger, for meeting this demand, the type lithium ion battery is high with energy density, the characteristics such as can charge rapidly progressively cause showing great attention to of people, with other the battery such as nickel-cadmium cell, compare, high and rapid these characteristics of charging based on energy content of battery density, the expectation that people benefit from long novel lithium battery polymer solid electrolyte film film of life-span to high-efficient high-capacity three amount high charge number of times strengthens day by day.
In-primary cell or the electrochemical elements such as secondary cell and capacitor, can use liquid electrolyte to be used as manufacturing the conduction raw material of new battery, but that the electrolyte of liquid have that liquid leaks is dangerous or lack the shortcoming of long stability.Because solid electrolyte film has overcome with liquid electrolyte battery leakage and unsettled shortcoming, polymer solid electrolyte film is applied to various electrochemical elements simultaneously, when realizing the simplification that element is manufactured, miniaturization or the lightweight of element self become a reality, the danger that does not only have liquid to leak, but also the cell device that reliability is high is provided.For this reason, in type lithium ion battery etc., in the research and development process of solid electrolyte film, the research and development of the polymer solid electrolyte film of light weight and softness, handling ease are carried out just actively.
The people such as Wright in 1973 have found that polyethylene glycol oxide (PEO) and alkali metal lithium, sodium salt complexing have the phenomenon of ion guide electronics first, thereby the research that makes solid electrolyte film enters a new stage, but, due to the restriction that is subject to material and technological means, the room-temperature conductivity of solid electrolyte film and practical application need to greatly differ from each other.In order to address this problem, at first Feuillade etc. have proposed to adopt a kind of elastomer and inorganic lithium electrolyte to form a kind of mixture solution by the dissolution with solvents that can volatilize in 1975, then the surface that is coated on a kind of solid that will contain inorganic lithium salt, form a kind of gel electrolyte membrane that contains inorganic lithium salt, although done further investigation by Abraham etc. afterwards.Polymer gel is generally defined as a system of the polymer network by solvent swell, and its unique network configuration makes gel have the dispersion conductibility of cohesiveness and the liquid of solid simultaneously.Nineteen ninety-five U.S. Bellcore company discloses a kind of new type gel polymer dielectric for researching and developing the technology of polymer Li-ion solid electrolyte battery.Since then, to polymer Li-ion battery with the research of solid electrolyte film just more.Polymer Li-ion battery is the latest generation lithium ion battery of developing on the basis of liquid lithium ionic cell, its formation is to adopt the polymer have ionic conductivity and to have the barrier film effect concurrently-electrolyte to replace the electrolyte in liquid lithium ionic cell, gel electrolyte is the gelatin polymer network with suitable microcellular structure formed by certain method by polymer, plasticizer and lithium salts, the liquid electrolyte molecule that utilization is fixed in micro-structural is realized ionic conduction, and its room-temperature conductivity is generally 10
-3the S/cm order of magnitude.
In recent years, along with scientific and technological progress, to the research of inorganic solid electrolyte film, more and more towards the future development of practical application, the lithium ion battery of being made by the inorganic electrolyte plasma membrane is also to safety, high power capacity and long-life future development, most critical be optimization and the modification of inorganic electrolyte plastidome.But, because leakage easily appears in liquid organic electrolyte, have outstanding potential safety hazard, and cost of material being high, the expensive series of problems that waits of packing charges, make the inorganic solid electrolyte film be applied to lithium and lithium ion battery has obtained swift and violent development in recent years.The lithium inorganic solid electrolyte claims again lithium fast-ionic conductor, comprises crystalline state electrolyte (claim not only ceramic electrolyte) and amorphous state electrolyte (but also claiming vitreous electrolyte), and this inorganic electrolyte film material has higher Li
+conductivity (>10
-3s/cm) and Li
+transport number (approximating 1), the activation energy that electricity is led low (E<0.5eV), resistance to elevated temperatures and processability are good, easy to assembly, in the large-sized power lithium ion battery of high-energy-density, good application prospect is arranged, yet the large and electrochemical window of bad mechanical strength, the interface impedance while contacting with electrode active material is wide not is the major obstacle of restriction lithium inorganic solid electrolyte for lithium ion battery.Therefore, how further to optimize the important research direction that the inorganic solid electrolyte material is becoming lithium ion battery electrolyte.
From the electrical conduction mechanism of inorganic solid electrolyte film, the crystalline compound usually formed by matrix crystalline phase lithium salts ion migration under electric field action mainly occurs in amorphous phase region, because chemical constitution and the constituent of matrix helps lend some impetus to polymer and Li
+between coordinate bond destruction and form Li
+migration free volume is provided, therefore increase its free volume density and all contribute to obtain the inorganic electrolyte of high conduction performance and be not commonly considered as conducting electricity by the directional migration to room with the anion of matrix generation association, the matrix of low-k makes between ion and ion to exist strong interaction and has caused in inorganic electrolyte also existing the tight ion pair three ion aggregations of solvation ion pair and other ion aggregation except the cation of anion and solvation freely they have determined that the concentration of charge carrier and transfer ability are also the key factors that affects the conductive capability of inorganic electrolyte on the other hand.But, among the solid electrolyte membrane formed by matrix and lithium salts, electrical conduction mechanism according to lithium salts, under certain voltage, make lithium salts be dissociated into zwitterion, these zwitterions are under the effect of voltage, directional migration occurs, but, play supporting role in solid electrolyte due to matrix, simultaneously, be subject to the restriction of the structure of matrix, if this matrix is crystal structure, can make lithium salts hinder the motion of these zwitterions from separating the zwitterion formed under the effect of voltage, therefore, capacity for the electric conduction quantity that improves solid electrolyte and the battery manufactured by this electrolyte, on the one hand, what need is amorphous form concrete dynamic modulus matrix, on the other hand, need lithium salts to there is good dissociating power, for this reason, study the target that a kind of high-effect electrolysis matter is each researcher.
Introduced a kind of method that production has the inorganic solid electrolyte film of relatively high ionic conductivity in Chinese patent application CN1359165A, in the method, pass through vapour deposition process, form the film of being made by inorganic solid electrolyte on the base members of heating, this film obtained by heat treatment has the ionic conductivity higher than the film formed on the base members without heating, this ionic conductivity also can be by may well ask down or being formed with the film that the Pyatyi solid electrolyte is made on ground on lower than the base members at the temperature of 40 ℃, the step that then heats this inorganic solid electrolyte film improves.This patent is made the inorganic electrolyte film by the heating base members, and this base members is lithium metal or lithium alloy, then by vapour deposition process, inorganic compound is deposited on to substrate surface, although, can obtain the inorganic solid electrolyte film of certain conductance by the method, but, under the condition of the large capacity of needs and high efficiency inorganic electrolyte plasma membrane, due to cathode of lithium in charge and discharge process, the danger of dendritic growth can occur in the lithium metal on negative pole, and this dendritic growth meeting formation and positive pole are short-circuited, and cause battery explosion.
Introduced a kind of sulfide base inorganic solid electrolyte in Chinese patent application CN1465114A, it can suppress reacting between silicon sulfide and lithium metal, even be also like this when described electrolyte when stating lithium metal in contact condition, a kind of described electrolytical method of formation, and a kind of described electrolytical lithium cell component and lithium secondary battery of containing.Described electrolyte contains Li, P and S, but not containing Si.Ideally, can keep below 1.33x10 with a kind of having worn as Bian
-9when the XPS of the analysis room of the ultravacuum of hPa is analyzed, the fringe region between following two elements, described oxygen content, from described electrolyte, to described, containing the lithium material, gradually change, and, described, containing the oxygenous layer on the lithium material surface, almost completely be removed.Described electrolyte can form by this way, makes at least part of described formation step, irradiates described surface with Bian with inert gas ion and carries out with the step of the described substrate surface of etching simultaneously.When the sulfide base inorganic solid electrolyte thin layer in a kind of Containing Sulfur osmanthus contacts with lithium metal, the silicon in described silicon sulfide, reduced by lithium metal, thereby even make described inorganic solid electrolyte also can degenerate along with the time when room temperature.On the surface of described lithium metal, formation is a kind of has the compound layer of low ionic conductance as a kind of oxide skin(coating).When described oxide skin(coating) forms, reacting between described lithium metal and described silicon sulfide, can be suppressed.Therefore, if in order to improve the performance of described battery, while removing described oxide skin(coating), described inorganic solid electrolyte, will be due to reacting between described lithium metal and described silicon sulfide, and As time goes on degenerate significantly.
The present invention, from the method for structure, electrical conduction mechanism and its conductivity of raising of lithium ceramic electrolyte, has set forth advantage and the problem demanding prompt solution of this electrolyte for lithium and lithium ion battery,
The present invention is in order to overcome the deficiency of current inorganic solid electrolyte film, adopt and the good polyorganosiloxane resin of diatomite compatibility, its objective is in order to improve lithium phosphate and the polyorganosiloxane resin dispersiveness in diatomite, and then capacitance and the charge-discharge velocity of raising solid electrolyte film, adopt the polysiloxane polymer that this side chain of base film is relatively less and side chain is short simultaneously, in the deoxidation of process high temperature, hydrogen, after fluorine, it is high that this polyorganosiloxane resin forms porosity in diatomite, and size evenly, in order to reduce lithium salts from the obstruction of separating rear lithium ion and anion movement under the effect of voltage, thereby improve the conductance of this solid electrolyte film and made the capacity of battery by this electrolyte.
Summary of the invention
The present invention realizes that the main technique of goal of the invention is:
A kind of manufacture method of inorganic solid electrolyte film, for the manufacture of the electrode inorganic solid electrolyte matrix of lithium battery, the composition of raw materials of matrix is: polyorganosiloxane resin: lithium phosphate: diatomaceous mass ratio is 25～30:3～5:72～65; Manufacturing process comprises:
1), by formula polyorganosiloxane resin micro mist powder and nanoscale lithium phosphate powder and diatomite after homogenizer fully mixes, be hot pressed into the thick thin slice of 1～6 μ m;
2), 1) the gained thin slice insert high temperature furnace the polyorganosiloxane resin thin slice in high temperature furnace, in negative pressure, be 0.096～0.098Mpa, under the condition of temperature 1200-1380 degree, process 150～188min, be cooled to normal temperature in the normal temperature air chamber of anhydrous steam; To deviate from hydrogen, oxygen, the fluorine atom on the polyorganosiloxane resin strand;
3), by 2) thin slice that obtains inserts the LiClO that concentration is 1.3～1.5mol/L
4soak 30～48min in the aqueous solution, air drying 45～the 60min that is 20～30 ℃ in temperature after taking-up, then in inserting the high temperature furnace that temperature is 280～300 ℃, heat treated 45～60min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, make porosity 60～78%, the target inorganic electrolyte that aperture is 3～5um structure;
4), by 3) the inorganic electrolyte thin slice that obtains be superimposed as 2-8mm thick after, adopt the PPS (polyphenylene sulfide) films packing that corresponding size and thickness are 0.05～0.25mm, the gap of PPS (polyphenylene sulfide) films wherein adopts laser-beam welding machine to be welded into needed inorganic solid electrolyte film.
Adopt the inventive method gained inorganic lithium compound being evenly distributed in base film, thereby make the charge-discharge performance of the all-solid lithium battery manufactured by this electrolyte stable, it discharges and recharges number of times and useful life and capacitance will improve respectively 80～90% than current lithium battery is corresponding, and in its solid electrolyte film, the content of inorganic lithium is 18～32%.The characteristics such as the solid lithium battery of being made by this dielectric film, have long service life, discharges and recharges often, and battery capacity is large.
The accompanying drawing explanation
Fig. 1 process chart of the present invention
Fig. 2: the correlated performance table of solid electrolyte of the present invention.
Embodiment
Except special declaration, each chemical reagent related in the application is chemical pure.
The nanoscale lithium phosphate powder that the polyorganosiloxane resin micro mist powder that is 6um by the particle diameter in formula is 8nm with particle diameter and diatomite are after homogenizer fully mixes, then be hot pressed into the thick thin slice of 100 μ m, and to insert temperature be in 1200 ℃ of high temperature furnaces that are equipped with bleeding point, under the condition that is 0.096Mpa in negative pressure, process 150min, the metal tube connected at the end of bleeding point directly access is equipped with the cooling device of water, top exit at cooling device is connected with the air inlet of vacuum pump, the direct emptying in gas outlet; Then the normal temperature air chamber that by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam is cooled to normal temperature; The substrate foil porosity 78% after high-temperature process wherein, aperture is 5um; Hydrogen on the polyorganosiloxane resin strand, oxygen, fluorine atom, after high temperature vacuumizes treatment process, make its extrusion rate 98%.The diatomite thin slice obtained is inserted the LiClO that concentration is 1.3mol/L
4soak 30min in the aqueous solution, the air drying 60min that taking-up is 20 ℃ in temperature, then in inserting the high temperature furnace that temperature is 280 ℃, heat treated 45min, then the normal temperature air chamber that by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam is cooled to normal temperature, so just having made long is the inorganic electrolyte plasma membrane thin slice of 38mm for 66mm is wide, then adopt the PPS (polyphenylene sulfide) films packing that corresponding size and thickness are 0.05mm, the gap of wherein containing the 1nm carbon black micro mist PPS (polyphenylene sulfide) films of 6%wt adopts laser-beam welding machine to be welded into needed inorganic solid electrolyte film, the laser welding temperature is 268 ℃.
The correlation properties of this inorganic solid electrolyte film will show in accompanying drawing 2.
The nanoscale lithium phosphate powder that the polyorganosiloxane resin micro mist powder that is 12um by the particle diameter in formula is 12nm with particle diameter and diatomite are after homogenizer fully mixes, then be hot pressed into the thick thin slice of 600 μ m, and to insert temperature be in 1380 ℃ of high temperature furnaces that are equipped with bleeding point, under the condition that is 0.098Mpa in negative pressure, process 188min, the metal tube connected at the end of bleeding point directly access is equipped with the cooling device of water, top exit at cooling device is connected with the air inlet of vacuum pump, the direct emptying in gas outlet; Then the normal temperature air chamber that by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam is cooled to normal temperature; The substrate foil porosity 60% after high-temperature process wherein, aperture is 3um; Hydrogen on the polyorganosiloxane resin strand, oxygen, fluorine atom, after high temperature vacuumizes treatment process, make its extrusion rate 99%.The diatomite thin slice obtained is inserted the LiClO that concentration is 1.5mol/L
4soak 48min in the aqueous solution, taking-up is at the air drying 45min of 30 ℃ of temperature, then in inserting the high temperature furnace that temperature is 300 ℃, heat treated 60min, then the normal temperature air chamber that by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam is cooled to normal temperature, so just having made long is the inorganic electrolyte plasma membrane thin slice of 68mm for 132mm is wide, then adopt the PPS (polyphenylene sulfide) films packing that corresponding size and thickness are 0.25mm, the gap of wherein containing the 6nm carbon black micro mist PPS (polyphenylene sulfide) films of 8%wt adopts laser-beam welding machine to be welded into needed inorganic solid electrolyte film, the laser welding temperature is 288 ℃.
The correlation properties of this inorganic solid electrolyte film will show in accompanying drawing 2.
The nanoscale lithium phosphate powder that the polyorganosiloxane resin micro mist powder that is 7um by the particle diameter in formula is 9nm with particle diameter and diatomite are after homogenizer fully mixes, then be hot pressed into the thick thin slice of 200 μ m, and to insert temperature be in 1310 ℃ of high temperature furnaces that are equipped with bleeding point, under the condition that is 0.097Mpa in negative pressure, process 163min, the metal tube connected at the end of bleeding point directly access is equipped with the cooling device of water, top exit at cooling device is connected with the air inlet of vacuum pump, the direct emptying in gas outlet; Then the normal temperature air chamber that by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam is cooled to normal temperature; The substrate foil porosity 68% after high-temperature process wherein, aperture is 4.1um; Hydrogen on the polyorganosiloxane resin strand, oxygen, fluorine atom, after high temperature vacuumizes treatment process, make its extrusion rate 98.1%.The diatomite thin slice obtained is inserted the LiClO that concentration is 1.33mol/L
4soak 33min in the aqueous solution, the air drying 48min that taking-up is 26 ℃ in temperature, then in inserting the high temperature furnace that temperature is 283 ℃, heat treated 48min, then the normal temperature air chamber that by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam is cooled to normal temperature, so just having made long is the inorganic electrolyte plasma membrane thin slice of 48mm for 88mm is wide, then adopt the PPS (polyphenylene sulfide) films packing that corresponding size and thickness are 0.15mm, the gap of wherein containing the 3nm carbon black micro mist PPS (polyphenylene sulfide) films of 7%wt adopts laser-beam welding machine to be welded into needed inorganic solid electrolyte film, the laser welding temperature is 273 ℃.
The correlation properties of this inorganic solid electrolyte film will show in accompanying drawing 2.
The nanoscale lithium phosphate powder that the polyorganosiloxane resin micro mist powder that is 8um by the particle diameter in formula is 9nm with particle diameter and diatomite are after homogenizer fully mixes, then be hot pressed into the thick thin slice of 300 μ m, and to insert temperature be in 1280 ℃ of high temperature furnaces that are equipped with bleeding point, under the condition that is 0.096Mpa in negative pressure, process 165min, the metal tube connected at the end of bleeding point directly access is equipped with the cooling device of water, top exit at cooling device is connected with the air inlet of vacuum pump, the direct emptying in gas outlet; Then the normal temperature air chamber that by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam is cooled to normal temperature; The substrate foil porosity 66% after high-temperature process wherein, aperture is 3.5um; Hydrogen on the polyorganosiloxane resin strand, oxygen, fluorine atom, after high temperature vacuumizes treatment process, make its extrusion rate 98.6%.The diatomite thin slice obtained is inserted the LiClO that concentration is 1.41mol/L
4soak 38min in the aqueous solution, the air drying 50min that taking-up is 23 ℃ in temperature, then in inserting the high temperature furnace that temperature is 291 ℃, heat treated 56min, then the normal temperature air chamber that by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam is cooled to normal temperature, so just having made long is the inorganic electrolyte plasma membrane thin slice of 58mm for 88mm is wide, then adopt the PPS (polyphenylene sulfide) films packing that corresponding size and thickness are 0.10mm, the gap of wherein containing the 2nm carbon black micro mist PPS (polyphenylene sulfide) films of 6.8%wt adopts laser-beam welding machine to be welded into needed inorganic solid electrolyte film, the laser welding temperature is 271 ℃.
The correlation properties of this inorganic solid electrolyte film will show in accompanying drawing 2.
The nanoscale lithium phosphate powder that the polyorganosiloxane resin micro mist powder that is 9um by the particle diameter in formula is 11nm with particle diameter and diatomite are after homogenizer fully mixes, then be hot pressed into the thick thin slice of 400 μ m, and to insert temperature be in 1350 ℃ of high temperature furnaces that are equipped with bleeding point, under the condition that is 0.098Mpa in negative pressure, process 178min, the metal tube connected at the end of bleeding point directly access is equipped with the cooling device of water, top exit at cooling device is connected with the air inlet of vacuum pump, the direct emptying in gas outlet; Then the normal temperature air chamber that by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam is cooled to normal temperature; The substrate foil porosity 72.4% after high-temperature process wherein, aperture is 4.6um; Hydrogen on the polyorganosiloxane resin strand, oxygen, fluorine atom, after high temperature vacuumizes treatment process, make its extrusion rate 98.4%.The diatomite thin slice obtained is inserted the LiClO that concentration is 1.48mol/L
4soak 42min in the aqueous solution, the air drying 53min that taking-up is 29 ℃ in temperature, then in inserting the high temperature furnace that temperature is 283 ℃, heat treated 58min, then the normal temperature air chamber that by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam is cooled to normal temperature, so just having made long is the inorganic electrolyte plasma membrane thin slice of 63mm for 108mm is wide, then adopt the PPS (polyphenylene sulfide) films packing that corresponding size and thickness are 0.20mm, the gap of wherein containing the 4nm carbon black micro mist PPS (polyphenylene sulfide) films of 7.3%wt adopts laser-beam welding machine to be welded into needed inorganic solid electrolyte film, the laser welding temperature is 281 ℃.
The correlation properties of this inorganic solid electrolyte film will show in accompanying drawing 2.
The nanoscale lithium phosphate powder that the polyorganosiloxane resin micro mist powder that is 11um by the particle diameter in formula is 11nm with particle diameter and diatomite are after homogenizer fully mixes, then be hot pressed into the thick thin slice of 500 μ m, and to insert temperature be in 1364 ℃ of high temperature furnaces that are equipped with bleeding point, under the condition that is 0.097Mpa in negative pressure, process 184min, the metal tube connected at the end of bleeding point directly access is equipped with the cooling device of water, top exit at cooling device is connected with the air inlet of vacuum pump, the direct emptying in gas outlet; Then the normal temperature air chamber that by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam is cooled to normal temperature; The substrate foil porosity 75.3% after high-temperature process wherein, aperture is 4.7um; Hydrogen on the polyorganosiloxane resin strand, oxygen, fluorine atom, after high temperature vacuumizes treatment process, make its extrusion rate 98.7%.The diatomite thin slice obtained is inserted the LiClO that concentration is 1.38mol/L
4soak 45min in the aqueous solution, the air drying 59min that taking-up is 30 ℃ in temperature, then in inserting the high temperature furnace that temperature is 297 ℃, heat treated 55min, then the normal temperature air chamber that by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam is cooled to normal temperature, so just having made long is the inorganic electrolyte plasma membrane thin slice of 72mm for 118mm is wide, then adopt the PPS (polyphenylene sulfide) films packing that corresponding size and thickness are 0.15mm, the gap of wherein containing the 5nm carbon black micro mist PPS (polyphenylene sulfide) films of 7.4%wt adopts laser-beam welding machine to be welded into needed inorganic solid electrolyte film, the laser welding temperature is 286 ℃.
The correlation properties of this inorganic solid electrolyte film will show in accompanying drawing 2.
Comparative Examples 1
The nanoscale lithium phosphate powder that is 12nm by particle diameter and diatomite, after homogenizer fully mixes, then are hot pressed into the thick thin slice of 6 μ m and insert the LiClO that concentration is 1.3mol/L
4soak 48min in the aqueous solution, the air drying 60min that taking-up is 30 ℃ in temperature, then in inserting the high temperature furnace that temperature is 300 ℃, heat treated 45min, then the normal temperature air chamber that by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam is cooled to normal temperature, so just having made long is the inorganic electrolyte plasma membrane thin slice of 38mm for 66mm is wide, then adopt the PPS (polyphenylene sulfide) films packing that corresponding size and thickness are 0.05mm, the gap of wherein containing the 1nm carbon black micro mist PPS (polyphenylene sulfide) films of 6%wt adopts laser-beam welding machine to be welded into needed inorganic solid electrolyte film, the laser welding temperature is 268 ℃.
The correlation properties of this inorganic solid electrolyte film will show in accompanying drawing 2.
Comparative Examples 2
By the polyorganosiloxane resin micro mist powder that is 6～12um of the particle diameter in formula with diatomite after homogenizer fully mixes, then be hot pressed into the thick thin slice of 1 μ m, and to insert temperature be in 1000 ℃ of high temperature furnaces that are equipped with bleeding point, under the condition that is 0.098Mpa in negative pressure, process 188min, the metal tube connected at the end of bleeding point directly access is equipped with the cooling device of water, at the top exit of cooling device, with the air inlet of vacuum pump, is connected, and the direct emptying in gas outlet; Then the normal temperature air chamber that by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam is cooled to normal temperature; The substrate foil porosity 91% after high-temperature process wherein, aperture is 37um; Hydrogen on the polyorganosiloxane resin strand, oxygen, fluorine atom, after high temperature vacuumizes treatment process, make its extrusion rate 99.7%.The diatomite thin slice obtained is inserted the LiClO that concentration is 1.5mol/L
4soak 30min in the aqueous solution, the air drying 45min that taking-up is 20 ℃ in temperature, then in inserting the high temperature furnace that temperature is 280 ℃, heat treated 60min, then the normal temperature air chamber that by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam is cooled to normal temperature, so just having made long is the inorganic electrolyte plasma membrane thin slice of 68mm for 132mm is wide, then adopt the PPS (polyphenylene sulfide) films packing that corresponding size and thickness are 0.25mm, the gap of wherein containing the 6nm carbon black micro mist PPS (polyphenylene sulfide) films of 8%wt adopts laser-beam welding machine to be welded into needed inorganic solid electrolyte film, the laser welding temperature is 288 ℃.
The correlation properties of this inorganic solid electrolyte film will show in accompanying drawing 2.
Claims (3)
1. the manufacture method of an inorganic solid electrolyte film, for the manufacture of the electrode inorganic solid electrolyte matrix of lithium battery, the composition of raw materials of matrix is: polyorganosiloxane resin: lithium phosphate: diatomaceous mass ratio is 25～30:3～5:72～65; Manufacturing process comprises:
1), by formula polyorganosiloxane resin micro mist powder and nanoscale lithium phosphate powder and diatomite after homogenizer fully mixes, be hot pressed into the thick thin slice of 1～6 μ m;
2), 1) the gained thin slice insert high temperature furnace the polyorganosiloxane resin thin slice in high temperature furnace, in negative pressure, be 0.096～0.098Mpa, under the condition of temperature 1200-1380 degree, process 150～188min, be cooled to normal temperature in the normal temperature air chamber of anhydrous steam; To deviate from hydrogen, oxygen, the fluorine atom on the polyorganosiloxane resin strand;
3), by 2) thin slice that obtains inserts the LiClO that concentration is 1.3～1.5mol/L
4soak 30～48min in the aqueous solution, air drying 45～the 60min that is 20～30 ℃ in temperature after taking-up, then in inserting the high temperature furnace that temperature is 280～300 ℃, heat treated 45～60min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, make porosity 60～78%, the target inorganic electrolyte that aperture is 3～5um structure;
4), by 3) the inorganic electrolyte thin slice that obtains be superimposed as 2-8mm thick after, adopt the PPS (polyphenylene sulfide) films packing that corresponding size and thickness are 0.05～0.25mm, the gap of PPS (polyphenylene sulfide) films wherein adopts laser-beam welding machine to be welded into needed inorganic solid electrolyte film.
2. a kind of manufacture method of inorganic solid electrolyte film according to claim 1, the particle diameter that it is characterized in that polyorganosiloxane resin micro mist wherein is 6～12um, the particle diameter of lithium phosphate powder is 8～12nm.
3. a kind of manufacture method of inorganic solid electrolyte film according to claim 1, the carbon black of the 1～6nm that it is characterized in that containing 6～8%wt in described PPS (polyphenylene sulfide) films, the laser welding temperature is 268～288 ℃.
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Cited By (5)
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| CN103985910A (en) * | 2014-05-16 | 2014-08-13 | 宋大余 | Method for preparing all-solid-state electrolyte of lithium sulfur battery |
| CN104538577A (en) * | 2015-01-28 | 2015-04-22 | 中国科学院宁波材料技术与工程研究所 | Composite diaphragm and preparation method thereof |
| CN108232290A (en) * | 2016-12-09 | 2018-06-29 | 丰田自动车株式会社 | The manufacturing method of sulfide solid electrolyte |
| RU2716278C1 (en) * | 2017-02-08 | 2020-03-11 | ЭЛКЕМ СИЛИКОНС ЮЭсЭй КОРП. | Storage battery unit with improved thermal control |
| JP2020038775A (en) * | 2018-09-03 | 2020-03-12 | トヨタ自動車株式会社 | Composite solid electrolyte layer, method for producing the same, and method for producing all-solid-state battery |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985910A (en) * | 2014-05-16 | 2014-08-13 | 宋大余 | Method for preparing all-solid-state electrolyte of lithium sulfur battery |
| CN103985910B (en) * | 2014-05-16 | 2016-06-08 | 宋大余 | A kind of manufacture method of lithium-sulfur cell all solid state electrolyte |
| CN104538577A (en) * | 2015-01-28 | 2015-04-22 | 中国科学院宁波材料技术与工程研究所 | Composite diaphragm and preparation method thereof |
| CN108232290A (en) * | 2016-12-09 | 2018-06-29 | 丰田自动车株式会社 | The manufacturing method of sulfide solid electrolyte |
| RU2716278C1 (en) * | 2017-02-08 | 2020-03-11 | ЭЛКЕМ СИЛИКОНС ЮЭсЭй КОРП. | Storage battery unit with improved thermal control |
| US11780983B2 (en) | 2017-02-08 | 2023-10-10 | Elkem Silicones USA Corp. | Secondary battery pack with improved thermal management |
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| JP2020038775A (en) * | 2018-09-03 | 2020-03-12 | トヨタ自動車株式会社 | Composite solid electrolyte layer, method for producing the same, and method for producing all-solid-state battery |
| JP6992710B2 (en) | 2018-09-03 | 2022-01-13 | トヨタ自動車株式会社 | A composite solid electrolyte layer, a method for manufacturing the same, and a method for manufacturing an all-solid-state battery. |
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| CN103456984B (en) | 2016-08-17 |
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