CN103456984B - A kind of manufacture method of inorganic solid electrolyte film - Google Patents
A kind of manufacture method of inorganic solid electrolyte film Download PDFInfo
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- CN103456984B CN103456984B CN201310418375.5A CN201310418375A CN103456984B CN 103456984 B CN103456984 B CN 103456984B CN 201310418375 A CN201310418375 A CN 201310418375A CN 103456984 B CN103456984 B CN 103456984B
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Abstract
The invention discloses the manufacture method of a kind of inorganic solid electrolyte film, the manufacture of inorganic solid electrolyte matrix in the electrode 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；Prepare after inorganic electrolyte thin slice thin slice superposition and PPS films are packed.The inventive method gained inorganic lithium compound being evenly distributed in base film, so that the charge-discharge performance of the all-solid lithium battery manufactured by this electrolyte is stable, its discharge and recharge number of times and service life and capacitance will be respectively increased 80～90% accordingly than current lithium battery, and in its solid electrolyte film, the content of inorganic lithium is 18～32%.The solid lithium battery being made up of this dielectric film, has service life long, discharge and recharge often, the features such as battery capacity is big.
Description
Technical field
The present invention is the manufacture method about inorganic solid electrolyte film, it is more particularly related to arrive
The manufacture method of inorganic solid electrolyte film in the electrode of lithium battery.
Background technology
Battery is used as the power supply of the electrical equipment such as torch and phone very early by people, along with progress and the green wood of science and technology
The discovery of material, it has been developed that Ni-MH battery and lithium battery, along with mobile phone and notebook computer etc. are portable
The appearance of electrical equipment, seems increasingly stronger to the demand of the high performance of battery and miniaturization etc., is full
This demand of foot, lithium-ion type battery is high with energy density, it is possible to the features such as rapid charging progressively cause people
Highest attention, compared with other the battery such as nickel-cadmium cell, and charging high based on battery energy density is rapidly
These features, high-efficient high-capacity three amount high charge number of times is benefited from the novel lithium battery polymer solids of life-span length by people
The expectation of dielectric film film strengthens day by day.
In-primary cell or the electrochemical element such as secondary cell and capacitor, it is possible to use liquid electrolyte comes
As the conduction raw material of the new battery of manufacture, but when the electrolyte of liquid has the danger of liquid leakage or lacks long
Between the shortcoming of stability.Owing to solid electrolyte film overcomes with liquid electrolyte battery leakage and instability
Shortcoming, polymer solid electrolyte film is applied to various electrochemical element simultaneously, is realizing element manufacture
Simplification while, miniaturization or the lightweight of element self become a reality, and not only do not have the danger that liquid leaks,
But also the cell device that reliability is high is provided.To this end, in lithium-ion type battery etc., at solid electrolyte
During the research and development of film, light weight and softness, the research of polymer solid electrolyte film of handling ease are opened
Send out and carry out the most actively.
Wright in 1973 et al. is found that polyethylene glycol oxide (PEO) and alkali metal lithium, sodium salt complexing first
There is the phenomenon of ion guide electronics, so that research one new stage of entrance of solid electrolyte film, but by
In being limited by material and technological means, the room-temperature conductivity of solid electrolyte film needs to go mutually with actual application
The most remote.In order to solve this problem, Feuillade etc. first proposed in 1975 a kind of elastomer of employing with
Inorganic lithium electrolyte is dissolved by the solvent that can volatilize and forms a kind of mixture solution, then will be containing inorganic
The surface being coated on a kind of solid of lithium salts, forms a kind of gel electrolyte membrane containing inorganic lithium salt, although
Further investigation had been made later by Abraham etc..Polymer gel is generally defined as one by solvent swell
Polymer network system, the network structure of its uniqueness makes gel have the cohesiveness of solid and dividing of liquid simultaneously
Dissipate conductibility.Nineteen ninety-five U.S. Bellcore, company disclosed a kind of new type gel polymer dielectric for grinding
Send out the technology of polymer Li-ion solid electrolyte battery.Since then, to polymer Li-ion battery with solid
The research of body dielectric film is the most more.Polymer Li-ion battery is to open on the basis of liquid lithium ionic cell
The latest generation lithium ion battery sent, it is constituted is to use have ionic conductivity and have barrier film effect concurrently
Polymer-Electrolyte replaces the electrolyte in liquid lithium ionic cell, and gel electrolyte is by polymer, plasticising
The gel polymeric network with appropriate microporous structure that agent and lithium salts are formed by certain method, utilizes solid
The liquid electrolyte molecule being scheduled in micro-structural realizes ionic conduction, and its room-temperature conductivity is typically 10-3S/cm
The order of magnitude.
In recent years, along with the progress of science and technology, the research to inorganic solid electrolyte film increasingly should towards reality
Direction develop, the lithium ion battery being made up of inorganic electrolyte plasma membrane is also to safety, high power capacity and long-life
Direction is developed, it is crucial that the optimization of inorganic electrolyte plastidome is with modified.But, due to organic liquid electricity
Solving matter and leakage easily occur, there is prominent potential safety hazard, and cost of material is high, packing charges costliness etc. is
Row problem, makes inorganic solid electrolyte film be applied to lithium and lithium ion battery has obtained swift and violent development in recent years.
Lithium inorganic solid electrolyte also known as lithium fast-ionic conductor, including crystalline state electrolyte (also known as ceramic electrolyte) and
Amorphous state electrolyte (also known as vitreous electrolyte), this inorganic electrolyte film material has higher Li+Conductance
Rate (> 10-3And Li S/cm)+Transport number (approximates 1), and the activation energy of conductance is low (E < 0.5eV), resistance to
High-temperature behavior and processability are good, easy to assembly, have in the large-sized power lithium ion battery of high-energy-density
Well application prospect, but, interface impedance when bad mechanical strength contact with electrode active material greatly and
Electrochemical window is the widest is the restriction lithium inorganic solid electrolyte major obstacle for lithium ion battery.Therefore,
Optimize inorganic solid electrolyte material the most further and becoming that of lithium ion battery electrolyte is important to grind
Study carefully direction.
From the point of view of the electrical conduction mechanism of inorganic solid electrolyte film, generally by matrix crystalline phase lithium salts formed crystallization
Compound Ion transfer under electric field action occurs mainly in amorphous phase region, due to matrix chemical constitution and
Constituent helps lend some impetus to polymer and Li+Between the destruction of coordinate bond and be formed as Li+Migration provide from
By volume, therefore increase its free volume density both contribute to obtain high conduction performance inorganic electrolyte and not
It is commonly considered as being conducted electricity by the directional migration to room with the anion of matrix generation association, another
The matrix of aspect low-k makes to there is strong interaction between ion and ion and result in without dynamo-electric
Xie Zhizhong there is also solvated ion to Tight ion pair in addition to the cation of anion and solvation freely
Three ion aggregations and other ion aggregation they determine the concentration of carrier and transfer ability is also impact
The key factor of the conductive capability of inorganic electrolyte.But, at the solid electrolyte formed by matrix and lithium salts
Among film, according to the electrical conduction mechanism of lithium salts, under certain voltage, lithium salts is made to be dissociated into zwitterion, these
Under the effect of voltage, there is directional migration in zwitterion, but, owing to matrix rises in solid electrolyte
Supporting role, limited by the structure of matrix meanwhile, if this matrix is crystal structure, can make
The zwitterion that lithium salts dissociation is formed hinders the motion of these zwitterions under the effect of voltage, therefore, for
The electric conduction quantity improving solid electrolyte and the capacity of the battery manufactured by this electrolyte, on the one hand, needs
It is amorphous form concrete dynamic modulus matrix, on the other hand, needs lithium salts to have good dissociating power, to this end,
Study the target that a kind of high-effect electrolyte is each researcher.
In Chinese patent application CN1359165A, describe a kind of production there is relatively high ionic conductivity
The method of inorganic solid electrolyte film, in the method, by vapour deposition process, in the substrate of heating
Forming the film being made up of inorganic solid electrolyte on element, this film obtained by heat treatment is had and is higher than
The ionic conductivity of the film formed on the most heated base members, this ionic conductivity is also by examination
Ask down or thin less than be formed with on the base members at a temperature of 40 DEG C that Pyatyi solid electrolyte makes on ground
Film, the step then heating this inorganic solid electrolyte film improves.This patent is by heating base members
Make inorganic electrolyte film, and this base members is lithium metal or lithium alloy, then pass through vapour deposition
Inorganic compound is deposited on substrate surface by method, although, the inorganic of certain conductance can be obtained by the method
Solid electrolyte film, but, under conditions of needs Large Copacity and high efficiency inorganic electrolyte plasma membrane, due to
Cathode of lithium is in charge and discharge process, and the lithium metal on negative pole can occur the danger of dendritic growth, and this dendrite
Bulk-growth can be formed and be short-circuited with positive pole, causes battery explosion.
A kind of sulfide base inorganic solid electrolyte is described in Chinese patent application CN1465114A,
It can suppress the reaction between silicon sulfide and lithium metal, even when described electrolyte with state lithium metal and be in and connect
Also it is such during the state of touching, a kind of method forming described electrolyte, and a kind of lithium containing described electrolyte
Cell device and lithium secondary battery.Described electrolyte contains Li, P and S, but without Si.It is desirable that
1.33x10 can be kept below when having worn by one-9The XPS of the analysis room of the ultravacuum of hPa is analyzed
Time, the fringe region between following two elements, described oxygen content, from described electrolyte to described containing lithium
Material, gradually changes, and, described containing the oxygenous layer on lithium material surface, the most completely quilt
Remove.Described electrolyte can be formed by this way so that at least part of described forming step, with
Irradiate described surface with inert gas ion to carry out with the step etching described substrate surface simultaneously.When
When the sulfide base inorganic solid electrolyte thin layer in a kind of Containing Sulfur osmanthus contacts with lithium metal, at described silicon sulfide
In silicon, reduced by lithium metal, even if so that described inorganic solid electrolyte when room temperature as well as
Time and degenerate.A kind of compound layer with low ionic conductance is formed on the surface of described lithium metal
Such as a kind of oxide skin(coating).When described oxide skin(coating) is formed, between described lithium metal and described silicon sulfide
Reaction, can be suppressed.Therefore, if for the performance improving described battery, described oxide is removed
During layer, the most described inorganic solid electrolyte, it will anti-due between described lithium metal and described silicon sulfide
Should, and degenerate the most significantly.
The present invention, from the structure of lithium ceramic electrolyte, electrical conduction mechanism and the method for its electric conductivity of raising, elaborates
This electrolyte is used for lithium and the advantage of lithium ion battery and problem demanding prompt solution,
The present invention, in order to overcome the deficiency of current inorganic solid electrolyte film, uses good with diatomite compatibility
Polyorganosiloxane resin, its purpose is to improve lithium phosphate and polyorganosiloxane resin dispersion in diatomite
Property, and then improve the capacitance of solid electrolyte film and charge-discharge velocity, use this of base film simultaneously
The polysiloxane polymer that chain is relatively fewer and side chain is short, after High-Temperature Deoxygenation, hydrogen, fluorine, this gathers
It is high that silicone resin forms porosity in diatomite, and size is uniform, is to reduce lithium after lithium salts dissociates
Ion and the anion obstruction of movement under the effect of voltage, thus improve the conduction of this solid electrolyte film
Rate and be made up the capacity of battery of this electrolyte.
Summary of the invention
The present invention realizes the main technique of goal of the invention:
A kind of manufacture method of inorganic solid electrolyte film, inorganic solid electrolyte in the electrode of lithium battery
The manufacture of matrix, the composition of raw materials of matrix is: polyorganosiloxane resin: lithium phosphate: diatomaceous mass ratio is
25～30:3～5:72～65；Manufacturing process includes:
1), by formula polyorganosiloxane resin micropowder powder and nanoscale lithium phosphate powder and diatomite
After homogenizer is sufficiently mixed uniformly, it is hot pressed into the thin slice of 1～6 μ m-thick；
2), 1) gained thin slice inserts the polyorganosiloxane resin thin slice of high temperature furnace in high temperature furnace, in negative pressure be
0.096～0.098Mpa, under conditions of temperature 1200-1380 degree, process 150～188min, in anhydrous steaming
The normal temperature air room of gas is cooled to normal temperature；With the hydrogen on abjection polyorganosiloxane resin strand, oxygen, fluorine atom；
3), by 2) thin slice that obtains inserts the LiClO that concentration is 1.3～1.5mol/L4In the aqueous solution soak 30～
48min, at the air drying 45～60min that temperature is 20～30 DEG C after taking-up, then inserting temperature be
In the high temperature furnace of 280～300 DEG C, heat 45～60min, cool down through the normal temperature air room of anhydrous steam
To normal temperature, preparing porosity 60～78%, aperture is the target inorganic electrolyte of 3～5um structures；
4), by 3) after the inorganic electrolyte thin slice that obtains is superimposed as 2-8mm thickness, use correspondingly sized and thick
Degree is the PPS films packaging of 0.05～0.25mm, and the gap of PPS films therein uses swashs
Photocoagulator is welded into required inorganic solid electrolyte film.
Use the inventive method gained inorganic lithium compound being evenly distributed in base film, so that by this electricity
The charge-discharge performance solving the all-solid lithium battery that matter manufactures is stable, its discharge and recharge number of times and service life and electricity
Capacity will be respectively increased 80～90% accordingly than current lithium battery, and in its solid electrolyte film, inorganic lithium contains
Amount is 18～32%.The solid lithium battery being made up of this dielectric film, has service life long, discharge and recharge time
The features such as number is many, and battery capacity is big.
Accompanying drawing explanation
The process chart of Fig. 1 present invention
The correlated performance table of the solid electrolyte of Fig. 2: the present invention.
Detailed description of the invention
In addition to special declaration, each chemical reagent related in the application is chemical pure.
Embodiment 1
By the nanoscale phosphorus that the polyorganosiloxane resin micropowder powder that particle diameter is 6um in formula and particle diameter are 8nm
Acid lithium powder and diatomite, after homogenizer is sufficiently mixed uniformly, are then hot pressed into 100 μm
Thick thin slice, being placed into temperature is in 1200 DEG C of high temperature furnaces being equipped with bleeding point, is 0.096Mpa in negative pressure
Under conditions of, processing 150min, the metal tube that the end at bleeding point connects is directly accessed the cooling equipped with water
Device, is connected with the air inlet of vavuum pump at the top exit of cooling device, and gas outlet is directly vented；So
By conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to the normal of anhydrous steam afterwards
Warm air room is cooled to normal temperature；The wherein substrate foil porosity 78% after high-temperature process, aperture is 5um；
Hydrogen on polyorganosiloxane resin strand, oxygen, fluorine atom are after high temperature vacuumizes process technique so that it is de-
Go out rate 98%.The diatomite thin slice obtained inserts the LiClO that concentration is 1.3mol/L4The aqueous solution soaks
30min, takes out at the air drying 60min that temperature is 20 DEG C, is then inserting the height that temperature is 280 DEG C
In temperature stove, heat 45min, then by conveyer belt by the polyorganosiloxane resin handled well and lithium phosphate
Thin slice be transported to the normal temperature air room of anhydrous steam and be cooled to normal temperature, be thus made for a length of 66mm width
For the inorganic electrolyte plasma membrane thin slice of 38mm, then using correspondingly sized and thickness is the polyphenylene sulfide of 0.05mm
Film is packed, and the gap of the 1nm carbon black micro mist PPS films wherein containing 6%wt uses laser welding
Machine is welded into required inorganic solid electrolyte film；Laser welding temperature is 268 DEG C.
The correlation properties of this inorganic solid electrolyte film will show in fig 2.
Embodiment 2
It is the nanometer of 12nm by the polyorganosiloxane resin micropowder powder that particle diameter is 12um in formula and particle diameter
Level lithium phosphate powder and diatomite, after homogenizer is sufficiently mixed uniformly, are then hot pressed into
The thin slice of 600 μ m-thick, being placed into temperature is in 1380 DEG C of high temperature furnaces being equipped with bleeding point, in negative pressure is
Under conditions of 0.098Mpa, process 188min, bleeding point end connect metal tube be directly accessed equipped with
The cooling device of water, is connected with the air inlet of vavuum pump at the top exit of cooling device, and gas outlet is direct
Emptying；Then by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steaming
The normal temperature air room of gas is cooled to normal temperature；The wherein substrate foil porosity 60% after high-temperature process, hole
Footpath is 3um；Hydrogen on polyorganosiloxane resin strand, oxygen, fluorine atom vacuumize process technique through high temperature
After so that it is extrusion rate is 99%.The diatomite thin slice obtained inserts the LiClO that concentration is 1.5mol/L4Water
Solution soaks 48min, takes out at the air drying 45min of temperature 30 DEG C, then inserting temperature be
In the high temperature furnace of 300 DEG C, heat 60min, the polyorganosiloxane resin then will handled well by conveyer belt
The normal temperature air room being transported to anhydrous steam with the thin slice of lithium phosphate is cooled to normal temperature, is thus made for a length of
The inorganic electrolyte plasma membrane thin slice of a width of 68mm of 132mm, then using correspondingly sized and thickness is 0.25mm's
PPS films is packed, and the gap of the 6nm carbon black micro mist PPS films wherein containing 8%wt uses
Laser-beam welding machine is welded into required inorganic solid electrolyte film；Laser welding temperature is 288 DEG C.
The correlation properties of this inorganic solid electrolyte film will show in fig 2.
Embodiment 3
It is the nanoscale of 9nm by the polyorganosiloxane resin micropowder powder that particle diameter is 7um in formula and particle diameter
Lithium phosphate powder and diatomite, after homogenizer is sufficiently mixed uniformly, are then hot pressed into 200 μm
Thick thin slice, being placed into temperature is in 1310 DEG C of high temperature furnaces being equipped with bleeding point, is 0.097Mpa in negative pressure
Under conditions of, processing 163min, the metal tube that the end at bleeding point connects is directly accessed the cooling equipped with water
Device, is connected with the air inlet of vavuum pump at the top exit of cooling device, and gas outlet is directly vented；So
By conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to the normal of anhydrous steam afterwards
Warm air room is cooled to normal temperature；The wherein substrate foil porosity 68% after high-temperature process, aperture is
4.1um；Hydrogen on polyorganosiloxane resin strand, oxygen, fluorine atom after high temperature vacuumizes process technique,
Make its extrusion rate 98.1%.The diatomite thin slice obtained inserts the LiClO that concentration is 1.33mol/L4Water-soluble
Liquid soaks 33min, takes out at the air drying 48min that temperature is 26 DEG C, then inserting temperature be
In the high temperature furnace of 283 DEG C, heat 48min, the polyorganosiloxane resin then will handled well by conveyer belt
The normal temperature air room being transported to anhydrous steam with the thin slice of lithium phosphate is cooled to normal temperature, is thus made for a length of
The inorganic electrolyte plasma membrane thin slice of a width of 48mm of 88mm, then using correspondingly sized and thickness is the poly-of 0.15mm
Diphenyl sulfide film is packed, and the gap of the 3nm carbon black micro mist PPS films wherein containing 7%wt uses swashs
Photocoagulator is welded into required inorganic solid electrolyte film；Laser welding temperature is 273 DEG C.
The correlation properties of this inorganic solid electrolyte film will show in fig 2.
Embodiment 4
By the nanoscale phosphoric acid that the polyorganosiloxane resin micropowder powder that particle diameter is 8um in formula and particle diameter are 9nm
Lithium powder and diatomite, after homogenizer is sufficiently mixed uniformly, are then hot pressed into 300 μ m-thick
Thin slice, being placed into temperature is in 1280 DEG C of high temperature furnaces being equipped with bleeding point, is 0.096Mpa's in negative pressure
Under the conditions of, processing 165min, the metal tube that the end at bleeding point connects is directly accessed the cooling equipped with water and fills
Putting, be connected with the air inlet of vavuum pump at the top exit of cooling device, gas outlet is directly vented；Then
By conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to the normal temperature of anhydrous steam
Air chamber is cooled to normal temperature；The wherein substrate foil porosity 66% after high-temperature process, aperture is 3.5um；
Hydrogen on polyorganosiloxane resin strand, oxygen, fluorine atom are after high temperature vacuumizes process technique so that it is de-
Go out rate 98.6%.The diatomite thin slice obtained inserts the LiClO that concentration is 1.41mol/L4The aqueous solution soaks
Bubble 38min, takes out at the air drying 50min that temperature is 23 DEG C, is then 291 DEG C inserting temperature
In high temperature furnace, heat 56min, then by conveyer belt by the polyorganosiloxane resin handled well and phosphoric acid
The thin slice of lithium is transported to the normal temperature air room of anhydrous steam and is cooled to normal temperature, is thus made for a length of 88mm
The inorganic electrolyte plasma membrane thin slice of a width of 58mm, then using correspondingly sized and thickness is the polyphenylene sulfide of 0.10mm
Ether film is packed, and the gap of the 2nm carbon black micro mist PPS films wherein containing 6.8%wt uses laser
Bonding machine is welded into required inorganic solid electrolyte film；Laser welding temperature is 271 DEG C.
The correlation properties of this inorganic solid electrolyte film will show in fig 2.
Embodiment 5
It is the nanometer of 11nm by the polyorganosiloxane resin micropowder powder that particle diameter is 9um in formula and particle diameter
Level lithium phosphate powder and diatomite, after homogenizer is sufficiently mixed uniformly, are then hot pressed into
The thin slice of 400 μ m-thick, being placed into temperature is in 1350 DEG C of high temperature furnaces being equipped with bleeding point, in negative pressure is
Under conditions of 0.098Mpa, process 178min, bleeding point end connect metal tube be directly accessed equipped with
The cooling device of water, is connected with the air inlet of vavuum pump at the top exit of cooling device, and gas outlet is direct
Emptying；Then by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steaming
The normal temperature air room of gas is cooled to normal temperature；The wherein substrate foil porosity 72.4% after high-temperature process,
Aperture is 4.6um；Hydrogen on polyorganosiloxane resin strand, oxygen, fluorine atom vacuumize process through high temperature
After technique so that it is extrusion rate is 98.4%.It is 1.48mol/L's that the diatomite thin slice obtained inserts concentration
LiClO4The aqueous solution soaks 42min, takes out at the air drying 53min that temperature is 29 DEG C, then putting
Enter in the high temperature furnace that temperature is 283 DEG C, heat 58min, then poly-by handle well by conveyer belt
The thin slice of silicone resin and lithium phosphate is transported to the normal temperature air room of anhydrous steam and is cooled to normal temperature, thus
It is made for the inorganic electrolyte plasma membrane thin slice of a width of 63mm of a length of 108mm, then uses correspondingly sized and thickness
PPS films for 0.20mm is packed, and the 4nm carbon black micro mist polyphenylene sulfide wherein containing 7.3%wt is thin
The gap of film uses laser-beam welding machine to be welded into required inorganic solid electrolyte film；Laser welding temperature
It it is 281 DEG C.
The correlation properties of this inorganic solid electrolyte film will show in fig 2.
Embodiment 6
It is the nanometer of 11nm by the polyorganosiloxane resin micropowder powder that particle diameter is 11um in formula and particle diameter
Level lithium phosphate powder and diatomite, after homogenizer is sufficiently mixed uniformly, are then hot pressed into
The thin slice of 500 μ m-thick, being placed into temperature is in 1364 DEG C of high temperature furnaces being equipped with bleeding point, in negative pressure is
Under conditions of 0.097Mpa, process 184min, bleeding point end connect metal tube be directly accessed equipped with
The cooling device of water, is connected with the air inlet of vavuum pump at the top exit of cooling device, and gas outlet is direct
Emptying；Then by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steaming
The normal temperature air room of gas is cooled to normal temperature；The wherein substrate foil porosity 75.3% after high-temperature process,
Aperture is 4.7um；Hydrogen on polyorganosiloxane resin strand, oxygen, fluorine atom vacuumize process through high temperature
After technique so that it is extrusion rate is 98.7%.It is 1.38mol/L's that the diatomite thin slice obtained inserts concentration
LiClO4The aqueous solution soaks 45min, takes out at the air drying 59min that temperature is 30 DEG C, then putting
Enter in the high temperature furnace that temperature is 297 DEG C, heat 55min, then poly-by handle well by conveyer belt
The thin slice of silicone resin and lithium phosphate is transported to the normal temperature air room of anhydrous steam and is cooled to normal temperature, thus
It is made for the inorganic electrolyte plasma membrane thin slice of a width of 72mm of a length of 118mm, then uses correspondingly sized and thickness
PPS films for 0.15mm is packed, and the 5nm carbon black micro mist polyphenylene sulfide wherein containing 7.4%wt is thin
The gap of film uses laser-beam welding machine to be welded into required inorganic solid electrolyte film；Laser welding temperature
It it is 286 DEG C.
The correlation properties of this inorganic solid electrolyte film will show in fig 2.
Comparative example 1
Nanoscale lithium phosphate powder and diatomite that particle diameter is 12nm are sufficiently mixed through homogenizer
After Jun Yun, the thin slice being then hot pressed into 6 μ m-thick inserts the LiClO that concentration is 1.3mol/L4In the aqueous solution
Soak 48min, take out at the air drying 60min that temperature is 30 DEG C, be then 300 DEG C inserting temperature
High temperature furnace in, heat 45min, then by conveyer belt by the polyorganosiloxane resin handled well and phosphorus
The thin slice of acid lithium is transported to the normal temperature air room of anhydrous steam and is cooled to normal temperature, is thus made for a length of 66mm
The inorganic electrolyte plasma membrane thin slice of a width of 38mm, then using correspondingly sized and thickness is the polyphenylene sulfide of 0.05mm
Ether film is packed, and the gap of the 1nm carbon black micro mist PPS films wherein containing 6%wt uses Laser Welding
Pick and be welded into required inorganic solid electrolyte film；Laser welding temperature is 268 DEG C.
The correlation properties of this inorganic solid electrolyte film will show in fig 2.
Comparative example 2
By the polyorganosiloxane resin micropowder powder that particle diameter is 6～12um in formula with diatomite through too high
After speed mixer is sufficiently mixed uniformly, being then hot pressed into the thin slice of 1 μ m-thick, being placed into temperature is 1000
DEG C it is equipped with in the high temperature furnace of bleeding point, under conditions of negative pressure is 0.098Mpa, processes 188min, taking out
The metal tube that the end of gas port connects is directly accessed the cooling device equipped with water, at the top exit of cooling device
Being connected with the air inlet of vavuum pump, gas outlet is directly vented；Then the poly-silicon will handled well by conveyer belt
The thin slice of oxygen alkane resin and lithium phosphate is transported to the normal temperature air room of anhydrous steam and is cooled to normal temperature；Wherein pass through
Substrate foil porosity 91% after high-temperature process, aperture is 37um；Hydrogen on polyorganosiloxane resin strand,
Oxygen, fluorine atom are after high temperature vacuumizes process technique so that it is extrusion rate is 99.7%.The diatomite obtained
Thin slice inserts the LiClO that concentration is 1.5mol/L4Soaking 30min in the aqueous solution, taking out in temperature is 20 DEG C
Air drying 45min, then in inserting the high temperature furnace that temperature is 280 DEG C, heat 60min,
Then by conveyer belt, the thin slice of the polyorganosiloxane resin handled well and lithium phosphate is transported to anhydrous steam
Normal temperature air room is cooled to normal temperature, is thus made for the inorganic electrolyte plasma membrane of a width of 68mm of a length of 132mm
Thin slice, then uses correspondingly sized and that thickness is 0.25mm PPS films to pack, wherein contains 8%wt
6nm carbon black micro mist PPS films gap use laser-beam welding machine be welded into required inoganic solids
Electrolytic thin-membrane；Laser welding temperature is 288 DEG C.
The correlation properties of this inorganic solid electrolyte film will show in fig 2.
Claims (3)
1. a manufacture method for inorganic solid electrolyte film, the manufacture of inorganic solid electrolyte matrix in the electrode 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 includes:
1), by formula polyorganosiloxane resin micropowder powder and nanoscale lithium phosphate powder and diatomite after homogenizer is sufficiently mixed uniformly, be hot pressed into the thin slice of 1～6 μ m-thick；
2), by 1) gained polyorganosiloxane resin thin slice is inserted in high temperature furnace, is 0.096～0.098Mpa in negative pressure, and under conditions of temperature 1200-1380 DEG C, process 150～188min, be cooled to normal temperature in the normal temperature air room of anhydrous steam；With the hydrogen on abjection polyorganosiloxane resin strand, oxygen, fluorine atom；
3), by 2) thin slice that obtains inserts the LiClO that concentration is 1.3～1.5mol/L4The aqueous solution soaks 30～48min, at the air drying 45～60min that temperature is 20～30 DEG C after taking-up, then in inserting the high temperature furnace that temperature is 280～300 DEG C, heat 45～60min, it is cooled to normal temperature through the normal temperature air room of anhydrous steam, preparing porosity 60～78%, aperture is the target inorganic electrolyte of 3～5 μm structures；
4), by 3) after the inorganic electrolyte thin slice that obtains is superimposed as 2-8mm thickness, using correspondingly sized and that thickness is 0.05～0.25mm PPS films to pack, the gap of PPS films therein uses laser-beam welding machine to be welded into required inorganic solid electrolyte film.
The manufacture method of a kind of inorganic solid electrolyte film the most according to claim 1, it is characterised in that the particle diameter of polyorganosiloxane resin micro mist therein is 6～12 μm, the particle diameter of lithium phosphate powder is 8～12nm.
The manufacture method of a kind of inorganic solid electrolyte film the most according to claim 1, it is characterised in that in described PPS films containing 6～8%wt 1～6nm carbon black, laser welding temperature is 268～288 DEG C.
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