CN109378525A - A kind of preparation method of micron order carbuncle type inorganic solid electrolyte film - Google Patents

A kind of preparation method of micron order carbuncle type inorganic solid electrolyte film Download PDF

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CN109378525A
CN109378525A CN201811159924.0A CN201811159924A CN109378525A CN 109378525 A CN109378525 A CN 109378525A CN 201811159924 A CN201811159924 A CN 201811159924A CN 109378525 A CN109378525 A CN 109378525A
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solid electrolyte
ball milling
preparation
film
inorganic solid
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陈斐
曹诗雨
查文平
沈强
张联盟
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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Abstract

The present invention relates to a kind of preparation methods of micron order carbuncle type inorganic solid electrolyte film, first by the carbuncle type inorganic solid electrolyte of certain partial size and organic solvent, dispersant ball milling, it is subsequently added into plasticiser and binder carries out secondary ball milling, gained slurry forms the garnet-type solid electrolyte film with a thickness of (20-200) μm through de-bubble, casting film-forming, drying, hot pressing, dumping and sintering processes.Compared with the conventional method, the present invention has many advantages, such as that at low cost, equipment is simple, process stabilizing, is easy to industrialize, and gained film product ion conductivity is high, thickness is controllable.

Description

A kind of preparation method of micron order carbuncle type inorganic solid electrolyte film
Technical field
The present invention relates to membrane material and inorganic solid electrolyte field of material technology, and in particular to a kind of micron order garnet The preparation method of type inorganic solid electrolyte film.
Background technique
In recent years, with the rapid development of renewable energy, developing new and effective energy storage technology becomes raising using energy source Efficiency and power quality, the key for reducing the problems such as transport loss, promotion renewable energy extensive use.Common electric energy storage Technology mainly includes physics energy storage, chemical energy storage and Power Flow, wherein the chemical energy including lithium ion battery, lead-acid battery etc. Storage is considered as the energy storage technology of most industrial prospect.Lithium ion battery development is later, but because it is with light weight, ratio The advantages that energy/specific power is high, the service life is long, has been quickly become one of electrochemical energy storage technology of great competitiveness.
Lithium ion battery commercially use at present includes two classes: using the conventional lithium ion battery of liquid electrolyte With the lithium ion battery using gel state electrolyte.Due to used in these two types of lithium ion batteries it is inflammable, perishable, easily let out The organic liquid electrolytes of dew, so that there are potential security risks for lithium ion battery, and with ternary high-voltage anode material Large-scale application, more exacerbate the unstability of lithium ion battery.Turn admittedly in addition, liquid can occur at low temperature for liquid electrolyte Change, ionic conductivity is caused to significantly reduce, thus cryogenic applications requirement can not be met.
To solve safety and high/low temperature application problem existing for above-mentioned conventional lithium ion battery and further increasing energy Density is increasingly becoming current research hotspot with the all-solid lithium-ion battery that solid electrolyte replaces electrolyte and is formed.Nothing The advantages that machine solid electrolyte is highly-safe, energy density is big, have on New-energy electric vehicle and the following storage station compared with Good application prospect.Wherein garnet-type solid electrolyte has ionic conductivity height (10 at room temperature-4-10-3Scm-1), electrification It learns many significant advantages such as window wide (6V), good to lithium an- ode stabilization, electrochemical stability and receives significant attention.
The preparation method of garnet-type solid electrolyte sheet material or film mainly includes conventional solid reaction method, colloidal sol at present Gel method and field help sintering process etc., and the solid electrolyte thickness that these methods obtain is mostly grade or even Centimeter Level, are unfavorable for The raising of battery energy density and power density；And the methods of magnetron sputtering, pulse laser deposition or chemical vapor deposition are mostly suitable For 2D film lithium cell, it is less likely for bulk battery system, and higher cost, the characteristics of the device is complicated limit its work Industry application prospect.Pertinent literature referring to Chinese patent CN108155412A, CN104103873A, CN103113107A, CN106941190A and CN105914396A.
To solve the above problems, the present invention gives full play to the advantages of casting molding processes, provide that a kind of equipment is simple, technique Stabilization, high production efficiency, micro inorganic solid electrolyte membrane preparation method easy to industrialized production, and thickness thereby is achieved The micron order garnet-type solid electrolyte membrane material that degree is controllable, chemical property is good.
Summary of the invention
It is an object of the invention to overcome the above problem of the existing technology, it is inorganic to provide a kind of micron order carbuncle type The preparation method of solid electrolyte film, method includes the following steps:
(a) ball milling will be carried out after carbuncle type inorganic solid electrolyte and solvent, dispersant, obtains first time ball milling Slurry；
(b) second of ball milling is carried out after mixing first time ball milling slurry with plasticiser, binder, obtains second of ball milling Slurry；
(c) pomegranate is obtained then through drying, hot pressing, dumping, sintering processes using second of ball milling slurry casting film-forming Stone-type inorganic solid electrolyte film.
Further, the carbuncle type inorganic solid electrolyte by conventional solid-state method, sol-gal process, coprecipitation, Microwave sintering method, plasma activated sintering method, field help any of them method such as sintering process to be prepared, and specifically include Li7La3Zr2O12、Li5La3Nb2O12Or its Al, Ta, Ga doped compound etc..Carbuncle type inorganic solid electrolyte is before use It needs to be ground up, sieved, the powder that average grain diameter is no more than 50 μm is made.
Further, the solvent is any one in ethyl alcohol, butanone, methyl ethyl ketone, trichloro ethylene, toluene, dimethylbenzene Kind is several (arbitrary proportion mixing), and the dispersing agent is selected from castor oil, phosphate ester, ethoxy compound, fish oil, KD-1 dispersion Any one in agent；The plasticiser is any one in polyethylene glycol, phthalic acid lipid compound, ethylene glycol Kind；Any one of the bonding agent in polyvinyl butyral, polyacrylic acid formicester and ethyl cellulose.
Further, carbuncle type inorganic solid electrolyte and the mass ratio of dispersing agent, solvent are when first time ball milling 100:0.5-5:50-200 the matter of the plasticiser being added when second of ball milling, binder and carbuncle type inorganic solid electrolyte Amount is than being 3-10:3-10:100.
Further, twice in mechanical milling process, the mass ratio of ball milling ball and carbuncle type inorganic solid electrolyte is 2-5: 1, drum's speed of rotation 100-600r/min, Ball-milling Time 6-48h.
Further, wet film is placed in 15-80 DEG C of environment through casting machine casting film-forming after second of ball milling removing bubbles from slurry Dry 6-48h.
Further, hot pressing temperature is 40-100 DEG C, hot pressing time 0.5-10h.
Further, the dumping detailed process are as follows: risen to film base from room temperature with the heating rate of 0.5-10 DEG C/min 500-1000 DEG C, then heat preservation 1-5h cools to room temperature with the furnace.
Further, the sintering detailed process are as follows: under protective atmosphere, with the heating rate of 3-20 DEG C/min by film base 1000-1200 DEG C is risen to from room temperature, then heat preservation 1-8h cools to room temperature with the furnace.
Further, micron order carbuncle type inorganic solid electrolyte film obtained is conductive at 300 DEG C or less, With a thickness of 20-200 μm, ionic conductivity is (1-16) × 10 at room temperature-4S/cm。
The present invention is specially added in two portions corresponding additive and has carried out ball milling twice.First time ball milling is only added organic molten Agent and dispersing agent prevent inorganic powder particle from settling or agglomerating the purpose is to form stable, uniform suspension；Second of ball Plasticiser is added in mill and bonding agent, the effect of bonding agent are coated powder particles, itself forms three-dimensional structure interconnected, and The interaction that plasticiser can then weaken binder molecule interchain is allowed to be separated from each other, and increases the work of binder molecule segment movement Dynamic space is conducive to the sub-chain motion for bonding agent molecule, so that it is guaranteed that slurry with good mobility and does not occur in room temperature Condensation.Comparative test shows for all raw materials to be added at one time and only the primary gained slurry of ball milling is not sufficiently stable easy flocculation, Dispersibility and stability are problematic in that, cannot be cast to obtain the uniform and relatively thin membrane material of thickness.
Compared with prior art, the invention has the benefit that (1) garnet-type solid electrolyte is made up of ball milling Uniform and stable slurry, and tape casting obtains garnet-type solid electrolyte film, film with a thickness of micron order and be easy to control System；(2) ionic conductivity is high at room temperature for garnet-type solid electrolyte film made from, has in terms of all-solid-state battery and preferably answers With prospect, the energy density and power density of battery can be increased substantially；(3) simple process and low cost, equipment is simple, easily In realization industrialized production.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is micron order garnet-type solid electrolyte film material object photo made from the embodiment of the present invention 1；
Fig. 3 is micron order garnet-type solid electrolyte film X-ray diffractogram obtained under different sintering temperatures；
Fig. 4 is the section microscopic appearance figure of 1200 DEG C of sintering gained garnet-type solid electrolyte films in embodiment 4.
Specific embodiment
To make those of ordinary skill in the art fully understand technical solution of the present invention and beneficial effect, below in conjunction with specific Embodiment is further described.
Equipment used in ball milling of the present invention is ball grinder, and material is zirconium oxide；Equipment used in tape casting is Casting machine；The container that dumping process is used to hold sample is crucible, and material is one of zirconium oxide, aluminium oxide, lanthana； Sintering device therefor is one of Muffle furnace, tube furnace, van-type furnace, vacuum drying oven.Used raw material, reagent are common city It sells.
Embodiment 1
Process flow shown in referring to Fig.1, the carbuncle type solid electrolytic that will be prepared first using sol-gal process Matter Li6.25Al0.25La3Zr2O12Powder is put into agate mortar, hand-ground 30min, crosses 500 meshes.After weighing 6g sieving Powder is added in zirconia ball grinding jar, and zirconia ball and powder quality ratio are 4:1.Add ethyl alcohol and each 2.7g of butanone and Castor oil 0.15g, with the revolving speed ball milling 12h of 300r/min.Plasticiser phthalic acid two is added after the completion of first time ball milling Butyl ester (DBP) and bonding agent polyvinyl butyral (PVB) each 0.42g continue ball milling for 24 hours with the revolving speed of 300r/min, obtain Stable and finely dispersed casting slurry.Using casting slurry as raw material, the tape casting on casting machine, control scraper height are 500 μm, gained wet film is dried in vacuo for 24 hours at 45 DEG C, obtains the good curtain coating green body of processability.Green body is cast at 70 DEG C Hot pressing 0.5h is cut into the disk of diameter 16mm, is placed in alumina crucible and is transferred to Muffle furnace, with the heating speed of 2 DEG C/min Rate rises to 600 DEG C, and furnace cooling removes organic matter after keeping the temperature 2h.It, will using nitrogen as protective gas finally in vacuum tube furnace Green body rises to 1200 DEG C with the heating rate of 10 DEG C/min, keeps the temperature furnace cooling after 4h, and gained finished product is garnet of the present invention Type solid electrolyte film, photo in kind are as shown in Figure 1.
Embodiment 2
The garnet-type solid electrolyte Li that will be prepared using conventional solid-state method5La3Nb2O12Powder is put into agate and grinds In alms bowl, hand-ground 60min crosses 300 meshes.Weigh 6g sieving after powder, be added zirconia ball grinding jar in, zirconia ball with Powder quality ratio is 3:1.Ethyl alcohol and each 3.2g and KD-1 dispersing agent 0.18g of toluene are added, with the revolving speed ball of 400r/min Grind 18h.Plasticiser butyl benzyl phthalate (BBP) and each 0.45g of bonding agent PVB are added after the completion of first time ball milling, Continue ball milling 18h with the revolving speed of 400r/min, is stablized and finely dispersed casting slurry.It is being flowed by raw material of casting slurry Prolong tape casting on machine, control scraper height is 300 μm, and gained wet film is dried in vacuo 36h at 60 DEG C, obtains processability Good curtain coating green body.It is cast green body hot pressing 0.5h at 80 DEG C, the disk of diameter 18mm is cut into, is placed in alumina crucible And be transferred in batch-type furnace, 700 DEG C are risen to the heating rate of 3 DEG C/min, furnace cooling removes organic matter after keeping the temperature 1h.Finally exist In vacuum tube furnace, using nitrogen as protective gas, green body is risen to 1150 DEG C with the heating rate of 20 DEG C/min, keep the temperature after 6h with Furnace is cooling, and gained finished product is garnet-type solid electrolyte film of the present invention.
Embodiment 3
The garnet-type solid electrolyte Li that will be prepared using plasma activated sintering6.4La3Zr1.4Ta0.6O12Powder It is put into agate mortar, hand-ground 45min, crosses 300 meshes.Powder after weighing 6g sieving, is added in zirconia ball grinding jar, Zirconia ball and powder quality ratio are 2.5:1.Trichloro ethylene 9.0g and fish oil 0.12g is added, with the revolving speed of 200r/min Ball milling is for 24 hours.Plasticiser ethylene glycol 0.45g, bonding agent polymethyl acrylate 0.36g are added after the completion of first time ball milling, with The revolving speed of 300r/min continues ball milling for 24 hours, is stablized and finely dispersed casting slurry.It is being cast by raw material of casting slurry Tape casting on machine, control scraper height are 400 μm, and gained wet film is dried in vacuo for 24 hours at 80 DEG C, and it is good to obtain processability Good curtain coating green body.It is cast green body hot pressing 1h at 60 DEG C, is cut into the disk of diameter 16mm, be placed in alumina crucible and is turned Enter Muffle furnace, rise to 800 DEG C by the heating rate of 4 DEG C/min, furnace cooling removes organic matter after keeping the temperature 1h.Finally in vacuum tube In formula furnace, using argon gas as protective gas, green body is risen to 1100 DEG C with the heating rate of 10 DEG C/min, is kept the temperature cold with furnace after 5h But, gained finished product is garnet-type solid electrolyte film of the present invention.
Embodiment 4
The garnet-type solid electrolyte Li that will be prepared using solid-phase synthesis6.4Ga0.2La3Zr2O12Powder is put into In agate mortar, hand-ground 40min crosses 500 meshes.Powder after weighing 6g sieving, is added in zirconia ball grinding jar, oxidation Zirconium ball and powder quality ratio are 5:1.Butanone 4.5g, dimethylbenzene 2.5g, fish oil 0.15g are added, with the revolving speed ball of 300r/min Grind 12h.Plasticiser polyethylene glycol 0.45g, bonding agent ethyl cellulose 0.45g are added after the completion of first time ball milling, with 300r/ The revolving speed of min continues ball milling for 24 hours, is stablized and finely dispersed casting slurry.It is raw material on casting machine using casting slurry Tape casting, control scraper height are 500 μm, and gained wet film is dried in vacuo for 24 hours at 70 DEG C, and it is good to obtain processability It is cast green body.It is cast green body hot pressing 0.5h at 70 DEG C, the disk of diameter 16mm is cut into, is placed in alumina crucible and is transferred to Muffle furnace rises to 600 DEG C with the heating rate of 3 DEG C/min, and furnace cooling removes organic matter after keeping the temperature 2h.Finally in electron tubes type In furnace, using argon gas as protective gas, green body is risen to 1200 DEG C with the heating rate of 10 DEG C/min, keeps the temperature furnace cooling after 2h, Gained finished product is garnet-type solid electrolyte film of the present invention.
Sufficiently to study influence of the sintering temperature to garnet-type solid electrolyte film, distinguish according to the method for embodiment 4 Garnet-type solid electrolyte film has been obtained in 1200 DEG C, 1150 DEG C and 1100 DEG C sintering, and has carried out X-ray diffraction reality to it It tests and is tested with cross-section morphology, it is as a result as shown in Figure 3-4 respectively.
From the figure 3, it may be seen that during tape casting added organic additive on the object of solid electrolyte mutually without influence, 1100 DEG C, Li obtained by 1150 DEG C and 1200 DEG C of sintering6.4Ga0.2La3Zr2O12Solid electrolyte film, object are mutually pure cubic phase.By scheming 4 it is found that the garnet-type solid electrolyte film thickness prepared by this casting molding processes uniformly and compact structure.

Claims (10)

1. a kind of preparation method of micron order carbuncle type inorganic solid electrolyte film, which comprises the following steps:
(a) ball milling will be carried out after carbuncle type inorganic solid electrolyte and solvent, dispersant, obtains first time ball milling slurry Material；
(b) second of ball milling is carried out after mixing first time ball milling slurry with plasticiser, binder, obtains second of ball milling slurry Material；
(c) micron order stone is obtained then through drying, hot pressing, dumping, sintering processes using second of ball milling slurry casting film-forming Garnet type inorganic solid electrolyte film.
2. preparation method as described in claim 1, it is characterised in that: the carbuncle type inorganic solid electrolyte is using preceding needing It carries out being ground up, sieved processing, the powder that average grain diameter is no more than 50 μm is made.
3. preparation method as described in claim 1, it is characterised in that: the carbuncle type inorganic solid electrolyte is solid by tradition Xiang Fa, sol-gal process, coprecipitation, microwave sintering method, plasma activated sintering method, field help any one side in sintering process Method is prepared, and ingredient specifically includes Li7La3Zr2O12、Li5La3Nb2O12Or its Al, Ta, Ga doped compound etc..
4. preparation method as described in claim 1, it is characterised in that: the solvent is selected from ethyl alcohol, butanone, methyl ethyl ketone, trichlorine Ethylene, toluene, in dimethylbenzene any one or in which it is several, the dispersing agent is selected from castor oil, phosphate ester, ethyoxyl chemical combination Object, fish oil, any one in KD-1 dispersing agent；The plasticiser is selected from polyethylene glycol, phthalic acid lipid compound, second Any one in glycol；The binder is any in polyvinyl butyral, polyacrylic acid formicester, ethyl cellulose It is a kind of.
5. preparation method as described in claim 1, it is characterised in that: carbuncle type inorganic solid electrolyte when first time ball milling It is 100:0.5-5:50-200 with the mass ratio of dispersing agent, solvent, plasticiser, binder and the pomegranate that when second of ball milling is added The mass ratio of stone-type inorganic solid electrolyte is 3-10:3-10:100.
6. preparation method as described in claim 1, it is characterised in that: twice in mechanical milling process, ball milling ball and carbuncle type without The mass ratio of machine solid electrolyte is 2-5:1, drum's speed of rotation 100-600r/min, Ball-milling Time 6-48h.
7. preparation method as described in claim 1, it is characterised in that: be cast into after second of ball milling removing bubbles from slurry through casting machine Gained wet film is then placed in 15-80 DEG C of environment dry 6-48h by film, and the temperature of hot-pressing processing is 40-100 DEG C, hot pressing time For 0.5-10h.
8. preparation method as described in claim 1, it is characterised in that: with the heating rate of 0.5-10 DEG C/min by film when dumping Base rises to 500-1000 DEG C from room temperature, then heat preservation 1-5h cools to room temperature with the furnace.
9. preparation method as described in claim 1, which is characterized in that sintering detailed process are as follows: under protective atmosphere, with 3-20 DEG C/film base rises to 1000-1200 DEG C from room temperature by the heating rate of min, 1-8h is kept the temperature, then cools to room temperature with the furnace.
10. such as the described in any item preparation methods of claim 1-9, it is characterised in that: the micron order carbuncle type is inorganic solid Body dielectric film is conductive at 300 DEG C or less, with a thickness of (20-200) μm, at room temperature ionic conductivity be (1-16) × 10-4S/cm。
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Application publication date: 20190222