CN109659603A - A kind of ultra-fine solid electrolyte and preparation method thereof - Google Patents
A kind of ultra-fine solid electrolyte and preparation method thereof Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
The invention discloses a kind of ultra-fine solid electrolytes and preparation method thereof.The partial size D10 of the electrolyte is 50~100nm, and D50 is 100~200nm, and D90 is 200~400nm, Dmax≤500nm.It is 1+X:X:2-X:3 that the preparation method of the ultra-fine solid electrolyte, which includes: 1) according to ion ratio Li:Al:M:P, and 0≤X≤1 weighs reaction raw materials, and wet-milling is then carried out in the dispersion containing thickener to partial size less than 1 μm, obtains spraying presoma；2) it is spray-dried, obtains sintered precursor；3) it is sintered, is sanded to partial size Dmax≤500nm, obtains ultra-fine solid electrolyte.The electrolyte processing performance and composite performance are good, and ionic conductivity is high, are suitable for battery applications.The method preparation process is simple, and low raw-material cost is environmental-friendly, and product yield is high, is convenient for industrialized production.
Description
Technical field
The present invention relates to lithium ion battery, lithium metal battery, lithium-sulfur cell, lithium-air battery solid electrolyte field, tools
Body, the present invention relates to a kind of ultra-fine polynary solid electrolyte materials and preparation method thereof.
Background technique
Operating voltage height, service life cycle length, memory-less effect, self discharge is small, environment is friendly because having for lithium ion battery
The advantages that good, it has been widely used in portable electronic product and electric car.Currently, multiple countries including China
Formulated about it is further promoted power battery energy density to 300~400 watt-hours/kilogram medium-term and long-term strategic mesh
Mark.According to reckoning, currently employed high voltage stratiform transition metal oxide and graphite are as composed by positive and negative anodes active material
The gravimetric energy density limit of liquid lithium ion power battery is about 280Wh/kg or so.It introduces silicon-base alloy and substitutes pure graphite work
After negative electrode material, the energy density of lithium-ion-power cell is expected to accomplish 300Wh/kg or more, and the upper limit is about 350Wh/kg.
For further reaching for higher energy density targets, inevitable choice is had become by the lithium metal battery of cathode of lithium metal.This
It is because the capacity of lithium metal is 3860mAh/g, about the 10 of graphite times, due to itself being exactly lithium source, positive electrode selection
Face is wide, can be containing lithium or without the inlaid scheme of lithium, is also possible to sulphur or sulfide even air, it is close to separately constitute energy
Spend higher lithium sulphur and lithium sky battery.But lithium anode still lacks in liquid state batteries there are series of technical so far to be had
The solution of effect, for example lithium metal and the side reaction of liquid electrolyte interface are more, SEI film is unevenly distributed and unstable cause to follow
The ring service life is poor, and the nonuniform deposition of lithium metal and dissolution lead to the uneven formation of Li dendrite and hole, asks to cause safety
Topic.Based on the above reasons, Many researchers place hope on the application problem of solution lithium anode the use of solid electrolyte.
Main thought is the side reaction for avoiding persistently occurring in liquid electrolyte, while utilizing the mechanics and electrology characteristic of solid electrolyte
Inhibit the formation of Li dendrite.
However, the main method for preparing solid electrolyte at present is high temperature solid-state method and sol-gal process, high temperature is solid
Although phase method simple process, it will lead to that presoma mixed effect is bad, and required very high at phase temperature, energy consumption is serious；
Such as non-patent literature (H.Aono.et al, J.Electrochem.Soc.137 (1990) 1023) prepares phosphorus using solid phase method
Sour titanium aluminium lithium solid electrolyte will lead to the phenomenon that product seriously glues sidewall of crucible, and therefore, it is difficult to industrialize.In patent document,
Although a kind of method for preparing solid electrolyte material using collosol and gel can be solid to avoid high temperature disclosed in CN105609881A
The shortcomings that phase method, but collosol and gel needs to be added the additive of organic or inorganic, moreover the process time-consuming that colloidal sol is evaporated is too long,
Lead to the rising of production cost and is unfavorable for industrialized production.CN105406118A, which is disclosed, utilizes spray drying preparation solid-state
Electrolyte, for this method in such a way that only simple presoma is mixed with solvent, the process of operation is not avoided that product is viscous
The phenomenon that wall, influences the yield of product, and finally prepd solid electrolyte partial size will lead to add in this way in a micron order
Work performance and composite performance are very poor, and the resistance between interelectrode interface and particle becomes larger, and are unfavorable for subsequent utilization.Cause
This, the particle size range of optimal solid electrolyte should be in 500nm or less.
Therefore, developing the method that one kind simply and efficiently prepares ultra-fine solid electrolyte material is lithium ion battery, lithium sulphur
The technical problem of battery and lithium-air battery field.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide a kind of ultra-fine solid electrolyte and its preparation sides
Method.Ultra-fine solid electrolyte particle of the invention is extremely tiny, and D10 is 50nm~100nm, and D50 is 100nm~200nm,
D90 is 200nm~400nm, Dmax≤500nm.The preparation method of the ultra-fine solid electrolyte has simple, efficient, energy consumption
It is low, be easy to industrialized feature.
In order to achieve the above object, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of ultra-fine solid electrolyte, the partial size D10 of the ultra-fine solid electrolyte is
50nm~100nm, such as 50nm, 60nm, 70nm, 80nm, 90nm or 100nm etc., it is not limited to cited numerical value, it should
Other unlisted numerical value are equally applicable in numberical range；D50 be 100nm~200nm, such as 100nm, 120nm, 140nm,
160nm, 180nm or 200nm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
Sample is applicable in；D90 be 200nm~400nm, such as 200nm, 220nm, 240nm, 260nm, 280nm, 300nm, 320nm, 340nm,
360nm, 380nm or 400nm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
Sample is applicable in；Dmax≤500nm, such as 500nm, 480nm, 460nm, 440nm, 420nm or 400nm etc., it is not limited to institute
The numerical value enumerated, other interior unlisted numerical value of the numberical range are equally applicable.
As currently preferred technical solution, in the ultra-fine solid electrolyte, ion ratio Li:Al:M:P is 1+X:
X:2-X:3,0≤X≤1, such as X are 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9 or 1 etc., but are simultaneously not only limited
It is equally applicable in other unlisted numerical value in cited numerical value, the numberical range；Wherein, in M Ti, Si, Ge, Sn and Zr
Any one or at least two combination, typical but non-limiting combination has: the combination of the combination of Ti and Si, Ge and Sn,
The combination of Sn and Zr, the combination of Ti, Si and Ge, the combination of Ge, Sn and Zr, the combination etc. of Ti, Si, Ge and Sn.
Preferably, the specific surface area of the ultra-fine solid electrolyte is 1m2/ g~20m2/ g, such as 1m2/g、2m2/g、3m2/
g、4m2/g、5m2/g、6m2/g、7m2/g、8m2/g、9m2/g、10m2/g、11m2/g、12m2/g、13m2/g、14m2/g、15m2/g、
16m2/g、17m2/g、18m2/g、19m2/ g or 20m2/ g etc., it is not limited to cited numerical value, in the numberical range other
Unlisted numerical value is equally applicable, preferably 1.5m2/ g~8.0m2/g。
Preferably, lithium ion conductivity of the ultra-fine solid electrolyte under 25 DEG C (room temperature) is 1.0 × 10-2S/m~
1.0×10-6S/m, such as 1.0 × 10-2S/m、1.0×10-3S/m、1.0×10-4S/m、10-5S/m or 10-6S/m etc., but not
It is only limitted to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Ultra-fine solid electrolyte provided by the invention is NASCION type structure, and grain diameter Dmax≤500nm has super
Thin nanostructure, processing and film performance are good, and ionic conductivity is high, can effectively reduce with interelectrode interfacial resistance, it is more suitable
For the application on battery.
Second aspect, the present invention provides a kind of preparation method of ultra-fine solid electrolyte as described in relation to the first aspect, described
Method the following steps are included:
It (1) is 1+X:X:2-X:3 according to ion ratio Li:Al:M:P, 0≤X≤1 weighs reaction raw materials, then containing increasing
Wet-milling is carried out in thick dose of dispersion to partial size less than 1 μm, obtains spraying presoma；
(2) it is spray-dried, obtains sintered precursor；
(3) it is sintered, is sanded to partial size Dmax≤500nm, obtains ultra-fine solid electrolyte；
Wherein, in M Ti, Si, Ge, Sn and Zr any one or at least two combination.
In the present invention, step (1) wet-milling to partial size is less than 1 μm, such as 0.9 μm, 0.8 μm, 0.7 μm, 0.6 μm, 0.5
μm, 0.4 μm, 0.3 μm, 0.2 μm or 0.1 μm etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value it is equally applicable, obtain particle of the partial size less than 1 μm for subsequent spray drying by limiting wet-milling, such partial size
Under, sphericity is more preferable during spray drying, and subsequent required to sinter phase temperature into lower.
The conventional high temperature solid-state method mixing of the spray drying technology comparison that the present invention uses, the technology are in terms of precursor
The wet-mixing of use, reaction raw materials can be sufficiently mixed by comparison solid phase mixing, and reach micron-sized mixing, to realize
The preparation of pure phase electrolyte, and it is at phase temperature comparisons' solid phase method more lower, reach energy-efficient effect；Furthermore it uses
Spray drying technology compares sol-gel, there is faster drying efficiency and the production conducive to industry.
In method of the invention, the partial size D50 of the solid electrolyte after high temperature sintering is at 7 μm or so, partial size ratio
It is larger, be unfavorable for subsequent processing, and conformability of the present invention after high temperature sintering using technique is sanded, obtained nanoscale
Ultra-fine solid electrolyte, Dmax≤500nm.It can be seen that in preparation method provided in the present invention, wet milling techniques, spray
Mist dry technology, high temperature sintering and sand milling are to combine closely, and collective effect is to guarantee to obtain the ultra-fine solid electrolyte.
As currently preferred technical solution, in step (1), the thickener includes but is not limited to polyethylene, poly- second
Enol, polyethylene glycol, polyvinylpyrrolidone, polyurethane, sodium carboxymethylcellulose, polyethylene oxide, gathers acid polyethylene methyl esters
In oxireme or polybutadiene any one or at least two combination, typical but non-limiting combination has: polyethylene
With the combination of polyvinyl alcohol, the combination of acid polyethylene methyl esters and polyethylene glycol, the combination of polyvinylpyrrolidone and polyurethane gathers
The combination of ethylene, polyvinyl alcohol and acid polyethylene methyl esters, the combination of polyethylene glycol, polyvinylpyrrolidone and polyurethane, carboxylic first
Base sodium cellulosate, polyethylene oxide, Pluronic F-127 and combination of polybutadiene etc..
Preferably, in step (1), by the reaction raw materials and the gross mass of the dispersion containing thickener be 100% in terms of,
The mass fraction of the thickener is 0.05%~10%, such as 0.05%, 0.5%, 1%, 2%, 5%, 7%, 9% or 10%
Deng it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, in step (1), in the dispersion containing thickener, dispersing agent is deionized water, ethyl alcohol, second two
In alcohol, isopropanol or acetone any one or at least two combination, typical but non-limiting combination has: deionized water and
The combination of the combination of the combination of ethyl alcohol, ethylene glycol and isopropanol, isopropanol and acetone, the combination of ionized water, ethyl alcohol and ethylene glycol,
Ethylene glycol, isopropanol and combination of acetone etc..
In the present invention, the use of appropriate amount thickener, so that the dry sintered precursor sphericity obtained of subsequent spray is high,
The phenomenon that sintering is not in viscous sidewall of crucible improves the yield of product.
As currently preferred technical solution, in step (1), the derived compound of the Li is lithium hydroxide, carbonic acid
In lithium, lithia or lithium phosphate any one or at least two combination, typical but non-limiting combination has: lithium hydroxide
With the combination of lithium carbonate, the combination of lithium carbonate and lithia, the combination of lithia and lithium phosphate, lithium hydroxide, lithium carbonate and oxygen
Change the combination of lithium, lithium carbonate, lithia and combination of lithium phosphate etc..
Preferably, in step (1), the derived compound of the Al is aluminum oxide, aluminum phosphate, aluminium hydroxide, isopropyl
In aluminium alcoholates or aluminum nitrate any one or at least two combination, typical but non-limiting combination has: aluminum oxide and
The combination of the combination of the combination of aluminum phosphate, aluminum phosphate and aluminium hydroxide, aluminium isopropoxide and aluminum nitrate, aluminum oxide, aluminum phosphate
With the combination of aluminium hydroxide, aluminium hydroxide, aluminium isopropoxide and the combination of aluminum nitrate etc..
Preferably, the derived compound of M described in step (1) is titanium dioxide, butyl titanate, germanium dioxide, dioxy
In SiClx, stannic oxide or zirconium dioxide any one or at least two combination, typical but non-limiting combination has: two
The combination of the combination of the combination of titanium oxide and butyl titanate, germanium dioxide and silica, stannic oxide and zirconium dioxide, two
The combination of titanium oxide, butyl titanate and germanium dioxide, silica, stannic oxide and combination of zirconium dioxide etc..
Preferably, the derived compound of P described in step (1) is phosphoric acid, phosphorus pentoxide, ammonium phosphate, ammonium dihydrogen phosphate
In diammonium hydrogen phosphate any one or at least two combination, typical but non-limiting combination has: phosphoric acid and five oxidations
The combination of the combination of the combination of two phosphorus, phosphorus pentoxide and ammonium phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate, phosphoric acid, five oxidations
The combination of two phosphorus and ammonium phosphate, ammonium phosphate, ammonium dihydrogen phosphate and combination of diammonium hydrogen phosphate etc..
As the present invention preferably technical solution, in step (1), slurry solid content in the wet-grinding technology and relative device 15%~
50%, such as 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% etc., it is not limited to cited numerical value,
Other unlisted numerical value are equally applicable in the numberical range.
Preferably, in step (1), mixing speed in the wet-grinding technology and relative device is 20Hz~60Hz, such as 20Hz, 25Hz,
30Hz, 35Hz, 40Hz, 45Hz, 50Hz, 55Hz or 60Hz etc., it is not limited to cited numerical value, in the numberical range its
His unlisted numerical value is equally applicable, preferably 40Hz~60Hz；
Preferably, in step (1), mixing time in the wet-grinding technology and relative device is 6h~15h, for example, 6h, 7h, 8h, 9h,
10h, 11h, 12h, 13h, 14 or 15h etc., it is not limited to cited numerical value, other interior unlisted numbers of the numberical range
It is worth equally applicable.
Preferably, in step (1), the wet-grinding technology and relative device is carried out using wet milk.
Preferably, in step (1), in the wet-grinding technology and relative device, wet-milling system is the dispersion containing zirconium ball.
Preferably, in step (1), in wet-milling system, the diameter of zirconium ball is 1mm.
As currently preferred technical solution, in step (2), the spray dryer that is used in the drying process with atomizing
For any one in open type spray dryer or inert gas shielding enclosed spray dryer.
Preferably, in step (2), according to open type spray dryer in the drying process with atomizing, then inlet temperature is
180 DEG C~280 DEG C, such as 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 240 DEG C, 250 DEG C, 260 DEG C, 270 DEG C
Or 280 DEG C etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable；Outlet
Temperature is 80 DEG C~120 DEG C, such as 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C or 120 DEG C etc., but
It is not limited in cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, in step (2), according to inert gas shielding enclosed spray dryer in the drying process with atomizing,
Then inlet temperature is 120 DEG C~160 DEG C, such as 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C
Or 160 DEG C etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable；Outlet
Temperature is 60 DEG C~80 DEG C, such as 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 80 DEG C etc., it is not limited to cited numerical value, it should
Other unlisted numerical value are equally applicable in numberical range.
Preferably, in step (2), the atomizer used in the drying process with atomizing flows for centrifugal, two fluids or four
In body atomizer any one or at least two combination, typical but non-limiting combination has: centrifugal and two fluid mists
The combination of change device, the combination of two fluids and four fluid atomizers, centrifugal and four fluid atomizers combinations are centrifugal, second-rate
The combination of body and four fluid atomizers.
As currently preferred technical solution, in step (2), the median particle diameter for being spray-dried obtained powder is
4 μm~10 μm, such as 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm etc., it is not limited to cited numerical value, the numerical value
Other unlisted numerical value are equally applicable in range.
As currently preferred technical solution, in step (3), the temperature of the sintering is 600 DEG C~950 DEG C, such as
600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C or 950 DEG C etc., it is not limited to cited numerical value,
Other unlisted numerical value are equally applicable in the numberical range, and preferably 700 DEG C~900 DEG C.
Preferably, in step (3), time of the sintering is 4h~12h, for example, 4h, 5h, 6h, 7h, 8h, 9h, 10h,
11h or 12h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, in step (3), the heating rate of the sintering is warming up to as 1 DEG C/min~20 DEG C/min, such as 1 DEG C/
min、2℃/min、4℃/min、6℃/min、8℃/min、10℃/min、12℃/min、14℃/min、16℃/min、18℃/
Min or 20 DEG C/min etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally suitable
With.
Preferably, in step (3), the sintering carries out under air atmosphere and/or oxygen atmosphere.It is of the present invention " empty
It can be air atmosphere that gas atmosphere and/or oxygen atmosphere ", which refers to, or oxygen atmosphere can also be the mixed of air and oxygen
Close atmosphere.
As currently preferred technical solution, in step (3), the sand milling technique carries out in sand mill, the sand
The revolving speed of grinding machine is preferably 2000rpm~3000rpm, such as 2000rpm, 2200rpm, 2400rpm, 2600rpm, 2800rpm
Or 3000rpm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, in step (3), in the technique of the sand milling, time of sand milling is 4h~10h, for example, 4h, 5h, 6h,
7h, 8h, 9h or 10h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally suitable
With.
Preferably, in step (3), in the technique of the sand milling, sand milling system is the dispersion containing zirconium ball.
Preferably, in step (3), in the sand milling system, the diameter of zirconium ball is appointing in 0.1mm, 0.2mm or 0.3mm
It anticipates one kind.
Preferably, in step (3), in the sand milling system, dispersing agent is in deionized water, ethyl alcohol, acetone or isopropanol
Any one or at least two combination, typical but non-limiting combination has: the combination of deionized water and ethyl alcohol, ethyl alcohol and
The combination of the combination of acetone, acetone and isopropanol, the combination of ionized water, ethyl alcohol and acetone, ionized water, ethyl alcohol, acetone and isopropyl
The combination etc. of alcohol.
Compared with the prior art, the invention has the following beneficial effects:
(1) ultra-fine solid electrolyte D10 provided by the invention is 50~100nm, and D50 is 100~200nm, D90 200
~400nm, Dmax≤500nm, specific surface area is up to 20m2/ g, lithium ion conductivity is up to 1.83 × 10-2S/m, and have super
Thin nanostructure, processing and film performance are good, and ionic conductivity is high, can effectively reduce with interelectrode interfacial resistance,
Especially suitable for fields such as lithium ion battery, lithium-sulfur cell and lithium-air batteries.
(2) preparation method provided by the invention in the system containing thickener by carrying out this high-energy ball milling skill of wet-milling
Art, spray drying technology, high temperature sintering combine with sand milling, and the ultra-fine solid state electrolysis with a variety of advantageous properties has been made
Matter.The method preparation process is simple, low raw-material cost, and product yield is high, environmental-friendly, is convenient for industrialized production.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram piece of ultra-fine solid electrolyte prepared by the embodiment of the present invention 1；
Fig. 2 is the X-ray diffractogram of ultra-fine solid electrolyte prepared by the embodiment of the present invention 1；
Fig. 3 is the room temperature AC impedance figure of ultra-fine solid electrolyte prepared by the embodiment of the present invention 1；
Fig. 4 is the AC impedance figure under the different temperatures of ultra-fine solid electrolyte prepared by the embodiment of the present invention 1；
Fig. 5 is the photo for the ultra-fine solid electrolyte that comparative example 1 of the present invention obtains；
Fig. 6 is the electrochemical impedance spectrogram for the solid electrolyte that comparative example 2 of the present invention obtains.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.But following reality
Applying example is only simple example of the invention, does not represent or limit the scope of the present invention, the scope of the present invention
It is subject to claims.
Embodiment 1
Present embodiments provide it is a kind of prepare ultra-fine solid electrolyte, method particularly includes:
It (1) is that 1.4:0.4:1.6:3 weighs a certain amount of lithium carbonate, aluminium oxide, two according to ion ratio Li:Al:Ti:P
Then these reactant feeds are added the wet milk containing 1mm zirconium ball, then added pure by titanium oxide and ammonium dihydrogen phosphate
Water, adjustment solid content to 40%, first low whipping speed are to stir 2h under 15Hz, then add the thickener of mass fraction 5%
(polyvinylpyrrolidone), then low whipping speed are to stir 2h under 15Hz, under the speed that then low whipping speed is 60Hz again,
After stirring 6h, less than 1 μm spraying precursor pulp of partial size is obtained；
(2) spraying precursor pulp is spray-dried using twin-fluid spray dryer, 260 DEG C of inlet temperature, out
At 85 DEG C, having obtained microscopic appearance is spherical sintered precursor for mouth temperature control；
(3) sintering precursor is placed in box atmosphere furnace, is passed through oxygen, the flow of oxygen is 50ml/min, and with 3
DEG C/min heating rate is warming up to 850 DEG C, 5h is kept the temperature, cooled to room temperature has just obtained the solid electrolyte of bulky grain；Most
The solid electrolyte of bulky grain is subjected to sanded treatment afterwards, wherein the revolving speed being sanded is 2400rpm, be utilized respectively 0.3mm and
2h is respectively sanded in the zirconium ball of 0.1mm, so that it may obtain the final products that partial size Dmax is 150nm, i.e., ultra-fine solid electrolyte, life
Entitled LATP-900-RT.
Fig. 1 is the scanning electron microscope diagram piece of ultra-fine solid electrolyte prepared by the embodiment of the present invention 1, can from Fig. 1
To find out the electrolyte granular partial size being synthesized within 100nm, illustrate after being sanded, the particle of solid electrolyte is to receive
Rice structure, such structure are conducive to subsequent processing.
Fig. 2 is the X-ray diffractogram of ultra-fine solid electrolyte prepared by the embodiment of the present invention 1, as can be seen from Figure 2 material
With the characteristic peak of apparent NASICON structure in material, other miscellaneous peaks are not found, illustrate that the solid electrolyte being synthesized is pure
Spend very high, and peak intensity becomes weak and wide, also the indirect proof crystal grain very little of solid electrolyte.
Fig. 3 is the room temperature AC impedance figure of ultra-fine solid electrolyte prepared by the embodiment of the present invention 1, utilizes the exchange of Fig. 3
The lithium ion conductivity that impedance spectrum is calculated is 1.83 × 10-4It is very high to illustrate that the electrolyte being synthesized has by S/cm
Ionic conductivity.
Fig. 4 is to synthesize the AC impedance figure of electrolyte at different temperatures, is illustrated as the temperature rises, lithium ion conductance
It is gradually increasing.
Embodiment 2
Present embodiments provide it is a kind of prepare ultra-fine solid electrolyte, method particularly includes:
(1) according to ion ratio Li:Al:Ti:P be 1.3:0.3:1.7:3 weigh a certain amount of lithium hydroxide, aluminum nitrate,
Then these reactant feeds are added the wet milk containing 1mm zirconium ball, then added pure by titanium dioxide and ammonium dihydrogen phosphate
Water, adjustment solid content to 50% stir 1.5h, then add the increasing of mass fraction 8% first in the case where revolving speed is the speed of 18Hz
It thick dose (carboxymethyl cellulose), keeps revolving speed is constant to continue to stir 3h, then improves revolving speed and just obtained after stirring 8h to 50Hz
Less than 1 μm spraying precursor pulp of partial size；
(2) spraying precursor pulp is spray-dried using centrifugal spray dryer, 280 DEG C of inlet temperature, out
Mouth temperature control is spherical sintered precursor through the spraying microscopic appearance that just obtained at 110 DEG C；
(3) sintered precursor is placed in box atmosphere furnace, is passed through oxygen, be warming up to 750 with 3 DEG C/min heating rate
DEG C, 10h is kept the temperature, cooled to room temperature has just obtained the solid electrolyte of bulky grain；Finally by the solid electrolyte of bulky grain
Sanded treatment is carried out, wherein the revolving speed being sanded is 2200rpm, so that it may obtain the final products of partial size Dmax≤400nm, i.e., it is super
Thin solid electrolyte.
Embodiment 3
Present embodiments provide it is a kind of prepare ultra-fine solid electrolyte, method particularly includes:
(1) according to ion ratio Li:Al:Ge:P be 1.3:0.3:1.7:3 weigh a certain amount of lithium hydroxide, aluminum nitrate,
Then these reactant feeds are added the wet milk containing 1mm zirconium ball, then added pure by germanium dioxide and ammonium dihydrogen phosphate
Then water, adjustment solid content to 40%, first low whipping speed add mass fraction to stir at low speed 2h under the speed of 15Hz
10% thickener (polyethylene glycol), is stirred for 3h, then improves revolving speed again to 45Hz, after 10h, has just obtained partial size less than 1 μ
M is sprayed precursor pulp；
(2) spraying precursor pulp is spray-dried using four fluid spray dryers, 260 DEG C of inlet temperature, out
Mouth temperature control is spherical sintered precursor through the spraying microscopic appearance that just obtained at 110 DEG C；
(3) sintered precursor is placed in box atmosphere furnace, is passed through oxygen, be warming up to 950 with 3 DEG C/min heating rate
DEG C, 5h is kept the temperature, cooled to room temperature has just obtained the solid electrolyte of bulky grain；Finally by the solid electrolyte of bulky grain
Sanded treatment is carried out, wherein revolving speed is 2400rpm, so that it may obtain the final products of partial size Dmax≤400nm, i.e., ultra-fine consolidates
State electrolyte.
Embodiment 4
Present embodiments provide it is a kind of prepare ultra-fine solid electrolyte, method particularly includes:
It (1) is that 2:1:1:3 weighs a certain amount of lithia, aluminum nitrate, zirconium dioxide according to ion ratio Li:Al:Zr:P
And diammonium hydrogen phosphate, the wet milk containing 1mm zirconium ball then is added in these reactant feeds, then adds pure water, is adjusted
For solid content to 15%, first 20Hz stirs at low speed 2h, then adds the thickener (acid polyethylene methyl esters) of mass fraction 10%, then
30Hz stirs at low speed 2h, after then opening 60Hz high-speed stirred 2h again, has just obtained less than 1 μm spraying precursor pulp of partial size；
(2) spraying precursor pulp is spray-dried using twin-fluid spray dryer, 180 DEG C of inlet temperature, out
Mouth temperature control is spherical sintered precursor through the spraying microscopic appearance that just obtained at 80 DEG C；
(3) sintering precursor is placed in box atmosphere furnace, is passed through oxygen, the flow of oxygen is 50ml/min, and with 1
DEG C/min heating rate is warming up to 900 DEG C, 4h is kept the temperature, cooled to room temperature has just obtained the solid electrolyte of bulky grain；Most
The solid electrolyte of bulky grain is sanded afterwards, is sanded in sand mill first with the zirconium ball of 0.3mm with the revolving speed of 2000rpm
2h recycles the zirconium ball of 0.1mm that 8h is sanded with the revolving speed of 3000rpm, so that it may obtain the final production of partial size Dmax≤300nm
Product, i.e., ultra-fine solid electrolyte.
Embodiment 5
Present embodiments provide it is a kind of prepare ultra-fine solid electrolyte, method particularly includes:
It (1) is that 1:2:3 weighs a certain amount of lithium phosphate, stannic oxide and phosphorus pentoxide according to ion ratio Li:Sn:P,
Then the wet milk containing 1mm zirconium ball is added in these reactant feeds, then adds pure water, adjustment solid content to 50%,
First 30Hz stirs at low speed 2h, then adds the thickener (polyurethane) of mass fraction 0.05%, then 30Hz stirs at low speed 3h, so
After opening 50Hz high-speed stirred 7h again afterwards, less than 1 μm spraying precursor pulp of partial size has just been obtained；
(2) spraying precursor pulp is spray-dried using twin-fluid spray dryer, 260 DEG C of inlet temperature, out
Mouth temperature control is spherical sintered precursor through the spraying microscopic appearance that just obtained at 120 DEG C；
(3) sintering precursor is placed in box atmosphere furnace, is passed through oxygen, the flow of oxygen is 50ml/min, and with 20
DEG C/min heating rate is warming up to 700 DEG C, 12h is kept the temperature, cooled to room temperature has just obtained the solid electrolyte of bulky grain；
Finally the solid electrolyte of bulky grain is sanded, first with the zirconium ball of 0.3mm with the revolving speed sand of 2000rpm in sand mill
3h is ground, recycles the zirconium ball of 0.1mm that 4h is sanded with the revolving speed of 2500rpm, so that it may obtain the final production of partial size Dmax≤250nm
Product, i.e., ultra-fine solid electrolyte.
Embodiment 6
Present embodiments provide it is a kind of prepare ultra-fine solid electrolyte, referring to embodiment 3, difference is specific method:
In step (1), the thickener (polyethylene oxide) of mass fraction 3% is added；
In step (2), spraying precursor pulp is done by spraying using four fluid spray dryer of inert gas shielding
Dry, 120 DEG C of inlet temperature, outlet temperature is controlled at 70 DEG C；
In step (3), it is warming up to 600 DEG C and is sintered.
Finally obtain the final products of partial size Dmax≤300nm, i.e., ultra-fine solid electrolyte.
Embodiment 7
Present embodiments provide it is a kind of prepare ultra-fine solid electrolyte, referring to embodiment 3, difference is specific method:
In step (1), the thickener (sodium carboxymethylcellulose) of mass fraction 1% is added；
In step (2), spraying precursor pulp is done by spraying using four fluid spray dryer of inert gas shielding
Dry, 140 DEG C of inlet temperature, outlet temperature is controlled at 60 DEG C；
Finally obtain the final products of partial size Dmax≤280nm, i.e., ultra-fine solid electrolyte.
Embodiment 8
Present embodiments provide it is a kind of prepare ultra-fine solid electrolyte, referring to embodiment 3, difference is specific method:
In step (1), the thickener (polybutadiene) of mass fraction 7% is added；
In step (2), spraying precursor pulp is done by spraying using four fluid spray dryer of inert gas shielding
Dry, 160 DEG C of inlet temperature, outlet temperature is controlled at 80 DEG C；
Finally obtain the final products of partial size Dmax≤280nm, i.e., ultra-fine solid electrolyte.
Comparative example 1
The specific method reference implementation example 1 of this comparative example, difference is: thickener is not used in step (1).
Fig. 5 is the photo of the ultra-fine solid electrolyte product obtained after sintering, it can be seen that product goes out without using thickener
The phenomenon that having showed viscous crucible causes product to be difficult to collect, the efficiency and production capacity of strong influence production.
Comparative example 2
The specific method reference implementation example 1 of this comparative example, difference is: without using sand milling technique in step (3).
Fig. 6 is the electrochemical impedance spectroscopy for the solid electrolyte product for not carrying out sanded treatment that this comparative example obtains
(Electrochemical Impedance Spectroscopy, EIS) figure, it is ultra-fine after the sand milling that comparative example 1 obtains
Solid electrolyte product (Fig. 3), it can be seen that the ionic conductance for the solid electrolyte product not being sanded is after being significantly larger than sanded
Ultra-fine solid electrolyte product.
The method of the invention it can be seen from above embodiments 1-8 and comparative example 1-2, by by wet milling techniques, spraying dry
Dry technology, high temperature sintering combine with sand milling, and the cooperation with thickener, have been prepared of the present invention ultra-fine solid
State electrolyte, the solid electrolyte Dmax≤500nm, large specific surface area, lithium ion conductivity is high, processing performance and plyability
Can be good, it is highly suitable for using on battery.And comparative example all can not using addition thickener or without using sand milling technology
Obtain the ultra-fine solid electrolyte of the present invention with a variety of excellent performances.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of ultra-fine solid electrolyte, which is characterized in that the partial size D10 of the ultra-fine solid electrolyte is 50nm~100nm,
D50 is 100nm~200nm, and D90 is 200nm~400nm, Dmax≤500nm.
2. ultra-fine solid electrolyte according to claim 1, which is characterized in that in the ultra-fine solid electrolyte, ion
Ratio Li:Al:M:P be 1+X:X:2-X:3,0≤X≤1, wherein in M Ti, Si, Ge, Sn and Zr any one or at least
Two kinds of combination；
Preferably, the specific surface area of the ultra-fine solid electrolyte is 1m2/ g~20m2/ g, preferably 1.5m2/ g~8.0m2/g；
Preferably, lithium ion conductivity of the ultra-fine solid electrolyte at 25 DEG C is 1.0 × 10-2S/m~1.0 × 10-6S/
m。
3. the preparation method of ultra-fine solid electrolyte as claimed in claim 1 or 2, which is characterized in that the method includes with
Lower step:
It (1) is 1+X:X:2-X:3 according to ion ratio Li:Al:M:P, 0≤X≤1 weighs reaction raw materials, is then containing thickener
Dispersion in carry out wet-milling to partial size less than 1 μm, obtain spraying presoma；
(2) it is spray-dried, obtains sintered precursor；
(3) it is sintered, is sanded to partial size Dmax≤500nm, obtains ultra-fine solid electrolyte；
Wherein, in M Ti, Si, Ge, Sn and Zr any one or at least two combination.
4. according to the method described in claim 3, it is characterized in that, the thickener includes polyethylene, poly- second in step (1)
Enol, polyethylene glycol, polyvinylpyrrolidone, polyurethane, sodium carboxymethylcellulose, polyethylene oxide, gathers acid polyethylene methyl esters
In oxireme or polybutadiene any one or at least two combination；
Preferably, in step (1), by the reaction raw materials and the gross mass of the dispersion containing thickener be 100% in terms of, it is described
The mass fraction of thickener is 0.05%~10%；
Preferably, in step (1), in the dispersion containing thickener, dispersing agent is deionized water, ethyl alcohol, ethylene glycol, different
In propyl alcohol or acetone any one or at least two combination.
5. the method according to claim 3 or 4, which is characterized in that in step (1), the derived compound of the Li is hydrogen
In lithia, lithium carbonate, lithia or lithium phosphate any one or at least two combination；
Preferably, in step (1), the derived compound of the Al is aluminum oxide, aluminum phosphate, aluminium hydroxide, aluminium isopropoxide
In aluminum nitrate any one or at least two combination；
Preferably, the derived compound of M described in step (1) be titanium dioxide, butyl titanate, germanium dioxide, silica,
In stannic oxide or zirconium dioxide any one or at least two combination；
Preferably, the derived compound of P described in step (1) is phosphoric acid, phosphorus pentoxide, ammonium phosphate, ammonium dihydrogen phosphate or phosphorus
In sour hydrogen diammonium any one or at least two combination.
6. according to method described in claim 3-5, which is characterized in that in step (1), the slurry in the wet-grinding technology and relative device contains admittedly
Amount is 15%~50%；
Preferably, in step (1), the mixing speed in the wet-grinding technology and relative device is 20Hz~60Hz；
Preferably, in step (1), the mixing time in the wet-grinding technology and relative device is 6h~15h；
Preferably, in step (1), the wet-grinding technology and relative device is carried out using wet milk；
Preferably, in step (1), in the wet-grinding technology and relative device, wet-milling system is the dispersion containing zirconium ball；
Preferably, in step (1), in the wet-milling system, the diameter of zirconium ball is 1mm.
7. according to the described in any item methods of claim 3-6, which is characterized in that in step (2), used in drying process with atomizing
Spray dryer be any one in open type spray dryer or inert gas shielding enclosed spray dryer；
Preferably, in step (2), according to open type spray dryer in the drying process with atomizing, then inlet temperature is 180 DEG C
~280 DEG C, outlet temperature is 80 DEG C~120 DEG C；
Preferably, in step (2), according to inert gas shielding enclosed spray dryer in the drying process with atomizing, then into
Mouth temperature is 120 DEG C~160 DEG C, and outlet temperature is 60 DEG C~80 DEG C；
Preferably, in step (2), the atomizer used in the drying process with atomizing is centrifugal, two fluids or four fluid mist
Change device in any one or at least two combination.
8. according to the described in any item methods of claim 3-7, which is characterized in that in step (2), what the spray drying obtained
The median particle diameter of powder is 4 μm~10 μm.
9. according to the described in any item methods of claim 3-8, which is characterized in that in step (3), the temperature of the sintering is
600 DEG C~950 DEG C, preferably 700 DEG C~900 DEG C；
Preferably, in step (3), the time of the sintering is 4h~12h；
Preferably, in step (3), the heating rate for being warming up to the sintering temperature is 1 DEG C/min~20 DEG C/min；
Preferably, in step (3), the sintering carries out under air atmosphere and/or oxygen atmosphere.
10. according to the described in any item methods of claim 3-9, which is characterized in that in step (3), the sand milling technique is in sand
It is carried out in grinding machine, the revolving speed of the sand mill is preferably 2000rpm~3000rpm；
Preferably, in step (3), in the technique of the sand milling, the time of sand milling is 4h~10h；
Preferably, in step (3), in the technique of the sand milling, sand milling system is the dispersion containing zirconium ball；
Preferably, in step (3), in the sand milling system, the diameter of zirconium ball is any one in 0.1mm, 0.2mm or 0.3mm
Kind；
Preferably, in step (3), in the sand milling system, dispersing agent is appointing in deionized water, ethyl alcohol, acetone or isopropanol
It anticipates a kind of or at least two combinations.
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| CN111786015A (en) * | 2020-08-05 | 2020-10-16 | 长沙理工大学 | Novel composite anode and manufacturing method of all-solid-state lithium battery |
| CN111786014A (en) * | 2020-08-05 | 2020-10-16 | 长沙理工大学 | Garnet type solid electrolyte powder with superfine particle size and preparation method thereof |
| CN112768755A (en) * | 2021-01-04 | 2021-05-07 | 长沙矿冶研究院有限责任公司 | Preparation method of NASION type solid electrolyte aluminum-containing phosphate |
| CN113224378A (en) * | 2021-04-27 | 2021-08-06 | 长江大学 | Lithium battery, solid electrolyte, and preparation method and application thereof |
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