CN107681196A - Without synthetic polymer flexible solid dielectric film and its preparation method and its application - Google Patents
Without synthetic polymer flexible solid dielectric film and its preparation method and its application Download PDFInfo
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Abstract
One kind is without synthetic polymer flexible solid dielectric film and its preparation method and its application, the nano-cellulose for including the powder of solid electrolyte and handling to obtain by TEMPO oxycelluloses and mechanical impact as raw material using renewable fiber, elasticity and gap structure are provided by nano-cellulose, improve the interior spatial structure of flexible solid dielectric film, it is higher relatively low with elasticity to avoid the fragility of ceramiic solid electrolyte, therefore improves the security performance of lithium-ion-power cell.
Description
Technical field
It is especially a kind of poly- without synthesis the present invention relates to a kind of flexible solid dielectric film and its preparation method and its application
Compound flexible solid dielectric film and its preparation method and its application.
Background technology
Lithium battery has the characteristics that energy density is high, has extended cycle life, high magnification, can be widely applied to electric automobile with
And in electric tool, with the development of society and science and technology, current lithium battery production technology is horizontal and battery material is all difficult
To meet the requirement of electric automobile continuation of the journey over long distances, we expect that capacity is higher, the bigger safer battery of energy density, currently
Lithium battery system be using lithium metal as electrode material, although with very high capacity, its easily with it is organic in battery
Qualitative response is electrolysed, gas is produced and causes battery tympanites, or even battery case rupture, or in multiple charge and discharge cycles process
In, produce Li dendrite and puncture membrane for polymer and cause short circuit, battery will be generated heat, tympanites is even burnt, and have very big peace
Full hidden danger.If substituting current organic solvent-organic electrolysis plastidome using solid ceramic electrolyte, these safety are hidden
Trouble can avoid completely, because solid electrolyte has higher chemically stable window, and have chemistry between lithium metal
Inertia, therefore as the solid electrolyte of zirconium, titanium, thallium-base can be completely applied to Li-S batteries, Li-AIR batteries, have
Solvent electrolyte incomparable heat endurance and chemical stability.Li-AIR batteries are 10 times of current lithium battery capacity,
And the reaction mechanism of Li-AIR batteries is the diffusion of lithium ion in electrolyte in charge and discharge process, and with positive pole porous carbon with
Oxygen reaction, it is one of most environmentally friendly, capacity highest battery, therefore, the solid state battery of high-energy-density is whole lithium battery
The general orientation of industry development, and the fragility of ceramiic solid electrolyte is higher and elasticity is relatively low.
Based on existing technical problem, technical characteristic and technique effect, application technical scheme of the invention is made.
The content of the invention
The object of the present invention be it is a kind of without synthetic polymer flexible solid dielectric film,
The object of the present invention is a kind of preparation method of no synthetic polymer flexible solid dielectric film,
The object of the present invention is a kind of application of no synthetic polymer flexible solid dielectric film.
In order to overcome above-mentioned technical disadvantages, it is an object of the invention to provide one kind without synthetic polymer flexible solid electrolyte
Film and its preparation method and its application, therefore improve the security performance of lithium-ion-power cell.
To reach above-mentioned purpose, the present invention adopts the technical scheme that：One kind is without synthetic polymer flexible solid electrolyte
Film, include the powder of solid electrolyte and pass through by raw material of renewable fiber at TEMPO oxycelluloses and mechanical impact
Manage obtained nano-cellulose.
Due to devising the powder and nano-cellulose of solid electrolyte, provide elasticity by nano-cellulose and space is tied
Structure, the interior spatial structure of flexible solid dielectric film is improved, the fragility for avoiding ceramiic solid electrolyte is higher and elastic
It is relatively low, therefore improve the security performance of lithium-ion-power cell.
The present invention devises, and the powder of solid electrolyte is arranged to using the salt containing lithium or oxide be that raw material passes through co-precipitation
Method, sol-gel process or solid phase method handle obtained nanometer grade powder.
The present invention devises, and also includes binding agent and binding agent is arranged to CMC i.e. carboxymethyl cellulose, PVP and gathered
Vinylpyrrolidone, PVA are in polyvinyl alcohol, PAA i.e. polyacrylic acid, PEO i.e. polyethylene glycol oxide, PVDF i.e. Kynoar
It is a kind of.
The present invention devises, a kind of preparation method of no synthetic polymer flexible solid dielectric film, and its step is：With
Salt or oxide containing lithium are that raw material passes through coprecipitation, and sol-gel process or solid phase method handle obtained solid electrolyte
Powder and the nano-cellulose for handling to obtain by TEMPO oxycelluloses and mechanical impact as raw material using renewable fiber mix
Close, slurry is made, slurry is applied on support film, flexible solid dielectric film is obtained after film forming.
The present invention devises, and its step is：
First, the preparation of the powder of solid electrolyte
By sol-gel process or solid-phase synthesis, lithium salts is weighed by metering ratio, zirconates, lanthanum salt is dissolved in the mixing of deionized water
Liquid, chelating agent is added, chelating agent is citric acid or glycine, the one or more in EDTA, dries moisture in an oven, obtains
Colloidal sol, the further calcination at 400-600 DEG C, light component is removed, obtains xerogel further in 900-1400 DEG C of high temperature furnace
Middle sintering 10-24 hours, nanoscale solids electrolyte ceramicses powder is obtained after the crushing that cools,
Or hydroxide and zirconium oxide with lithium, lanthana, by being sanded, obtain nano-oxide, the oxygen as reactant
Compound powder further sinters 10-24 hours in 900-1400 DEG C of high temperature furnace, and obtaining nanoscale after the crushing that cools consolidates
Body electrolyte ceramicses powder,
2nd, the preparation of nano-cellulose
To the wood-fibred of high polymerization degree, bamboo fibre, cotton fibriia, stalk fibre, with TEMPO oxycelluloses, by glucose list
The hydroxyl of first C6 positions is oxidized to carboxyl, and the cellulose that the degree of polymerization reduces passes through homogeneous high-pressure unit, fine in a limited space
Dimension element is reached 1500-2000Bar by normal pressure by moment pressure and extruded, and superpower mechanical impacting with high pressure, cellulose bundle is torn
Split, turn into nano-cellulose, mechanical high pressure impingement circular treatment 5 times, 60% cellulose diameter≤10 nanometer,
3rd, the preparation of flexible solid dielectric film
After nano-cellulose is mixed with the powder of solid electrolyte, absolute ethyl alcohol, or acetone, or 1-METHYLPYRROLIDONE are added
As solvent, nano-cellulose adds the binding agent for being contained in 0wt%-1wt% admittedly, it is 5wt%- always to contain admittedly admittedly containing being 5wt%-50wt%
45wt% slurry, with the method for scraper for coating or transfer coated by slurry even spread to PP, PE or PET for supporter
On film, after drying and processing, upper and lower two layers independent winding obtains coiled flexible solid dielectric film and repeats what is utilized
Support film.
The present invention devises, and the thickness of flexible solid dielectric film is arranged to 8-40 microns.
The present invention devises, and salt or oxide containing lithium are arranged to LiNO3, LiOH, Li（CH3COO）, Li2One kind in O
Or two kinds, lanthanum salt or and its oxide such as La (NO3)3,La(OH)3,La(CH3COO)3, La(CH3COCHCOCH3)3•XH2O,
La2O3One or both of, zirconates and its oxide or hydroxide such as Zr (NO3)4, Zr (OH)4, Zr（CH3COO）4,
Zr (CH3COCHCOCH3)4,ZrO2One or both of, titanium-containing compound such as Ti (OCH2CH2CH2CH3)4,TiCl4,TiO2
In one kind or Ta salt and its oxide.
The present invention devises, and nano-cellulose mass ratio in solid electrolyte film is 5 wt%-40wt%.
The present invention devises, cellulose preparation method, and its step is：
Cellulosic material crosses 60-80 mesh sieves after crushing, renewable fiber is in wood-fibred, cotton fiber, flaxen fiber, stalk cellulose
One kind, in deionized water be swelled after renewable fiber, regulation dry pulp mass fraction be 1wt%-10wt%, addition dry pulp matter
1wt%-5wt% TEMPO, dry pulp quality 8wt%-35wt% NaBr is measured, while stirring, 12wt% NaClO, drop is added dropwise
Dosage is the 3-12ml/g of dry pulp quality, between adjusting PH=10-11 with dilute NaOH, mixing speed 300-1000rpm, and reaction
2-6 hours, after reaction terminates, slurries filtration or centrifuge washing 3 times, PH are neutrality, obtain TEMPO oxidation processes disposed slurries,
TEMPO oxidation processes disposed slurries, deionized water is added, with 280-320rpm mixing speeds in agitator tank, is uniformly mixing to obtain
Solid content is 0.1wt%-3wt% cellulose paste, with high pressure homogenizer circular treatment 3-20 times, obtains nano-cellulose.
The present invention devises, and renewable fiber is arranged to one kind in wood-fibred, cotton fiber, flaxen fiber, stalk cellulose.
The present invention devises, and binding agent is arranged to CMC i.e. carboxymethyl cellulose, PVP i.e. polyvinylpyrrolidone, PVA i.e.
Polyvinyl alcohol, PAA are one kind in polyacrylic acid, PEO i.e. polyethylene glycol oxide, PVDF i.e. Kynoar, in flexible solid electricity
Mass ratio is arranged to as 0 wt%-1wt% in solution plasma membrane.
The present invention devises, and handles to obtain by TEMPO oxycelluloses and mechanical impact using renewable fiber as raw material
Application of the nano-cellulose in the solid electrolyte of Li-AIR batteries.
The present invention devises, and one kind is without synthetic polymer flexible solid dielectric film as solid electrolyte in Li-AIR
Application in battery.
The technical effects of the invention are that：Nano-cellulose is that natural plant fibre passes through Mechanical Method, chemical dissociation method etc.
The material with high length-diameter ratio, high-specific surface area, high intensity and high Young's modulus that means obtain, and thermal coefficient of expansion is than general
Ceramics are lower.And nano-cellulose can exist in water system with the form stable of colloid.By nano-cellulose and solid electrolytic
Matter is combined together, and not only solves the fragility of ceramiic solid electrolyte, it is most important that so that ceramic electrolyte film has bullet
Property, can effectively solve the problem that interface impedance problem, and this is also that solid electrolyte application needs most one of problem overcome, the solid
The diameter of porosity and fiber on dielectric film is linear, and the big porosity of nanofiber diameter is with regard to big, nanofiber
Plain diameter aperture gap rate is with regard to small.Can be by adjusting fibre diameter size come adjustment apertures rate size.The cellulose solids electrolyte
The percent thermal shrinkage of film is very low, Gu the nanometer that the nano-cellulose containing 50wt% is compound with the solid lithium lanthanum zirconium oxygen ceramic powder containing 50wt%
Cellulose membrane, with PP films at 160 degree, after toasting 50 minutes, the percent thermal shrinkage of PP lithium battery diaphragms is 40%, and nano-cellulose
Composite film heat shrinks almost nil.After nano cellulose composite film and PP lithium battery diaphragms were in 180 degree 50 minutes, PP films shrink
Rate is 70%, is almost melted, and nano cellulose composite film passes through contrast, fiber of the invention almost without Volume Changes as schemed
Plain solid electrolyte film heat endurance is significantly better than PP barrier films, which significantly improves lithium battery when heated diaphragm retracts cause it is short
The danger on road.And bonding agent uses few in film forming procedure, it might even be possible to which, without bonding agent, ion on-state rate is high, forthright again
Can be more preferable, moreover it is possible to save cost.
In the technical program, CMC be carboxymethyl cellulose, PVP i.e. polyvinylpyrrolidone, PVA i.e. polyvinyl alcohol,
PAA is polyacrylic acid, PEO i.e. polyethylene glycol oxide, PVDF i.e. Kynoar.
In the technical program, handled using renewable fiber as raw material by TEMPO oxycelluloses and mechanical impact
The nano-cellulose arrived is important technical characteristic, without synthetic polymer flexible solid dielectric film and its preparation method and its should
In technical field, there is novelty, creativeness and practicality, the term in the technical program is all that can use this technology
Patent document in field is explained and understood.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is nano-cellulose-solid electricity of the cellulose solids electrolyte complex film of the different enlargement ratios of the present invention
Solve the SEM figures of plasma membrane；
Fig. 2 is the nano-cellulose electrolyte compound film for solid and PP films before cellulose composite membrane and PP the films heat treatment of the present invention
Thermal contraction comparison diagram；
Fig. 3 is that the nano-cellulose solid electrolyte of the cellulose composite membrane and PP films of the present invention by 180 degree heat treatment is compound
The thermal contraction comparison diagram of film and PP films.
Embodiment
According to guidelines for examination, such as " having ", "comprising" and " comprising " term used in the present invention should be understood
Not allot the presence or addition of one or more of the other element or its combination.
In the description of the invention, it is necessary to explanation, term " " center ", " on ", " under ", "left", "right", " vertical ",
The orientation or position relationship of the instruction such as " level ", " interior ", " outer " be based on orientation shown in the drawings or position relationship, merely to
Be easy to the description present invention and simplify description, rather than instruction or imply signified device or element must have specific orientation,
With specific azimuth configuration and operation, therefore it is not considered as limiting the invention.In addition, term " first ", " second ",
" the 3rd " is only used for describing purpose, and it is not intended that instruction or hint relative importance.
In the description of the invention, it is necessary to illustrate, unless otherwise clearly defined and limited, term " installation ", " phase
Even ", " connection " should be interpreted broadly, for example, it may be being fixedly connected or being detachably connected, or be integrally connected；Can
To be mechanical connection or electrical connection；Can be joined directly together, can also be indirectly connected by intermediary, Ke Yishi
The connection of two element internals.For the ordinary skill in the art, with concrete condition above-mentioned term can be understood at this
Concrete meaning in invention.
As long as in addition, technical characteristic involved in invention described below different embodiments non-structure each other
It is be combined with each other into conflict can.
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
One kind one embodiment, is arranged to include solid electrolyte without synthetic polymer flexible solid dielectric film
Powder and the nano-cellulose that handles to obtain by TEMPO oxycelluloses and mechanical impact as raw material using renewable fiber.
In the present embodiment, it is that raw material passes through co-precipitation that the powder of solid electrolyte, which is arranged to using the salt containing lithium or oxide,
Method, sol-gel process or solid phase method handle obtained nanometer grade powder.
Second embodiment, the powder of solid electrolyte are arranged to handle by coprecipitation using the salt containing lithium as raw material
The nanometer grade powder arrived.
3rd embodiment, the powder of solid electrolyte are arranged to using the salt containing lithium be that raw material passes through at sol-gel process
Manage obtained nanometer grade powder.
4th embodiment, the powder of solid electrolyte are arranged to handle to obtain by solid phase method using the salt containing lithium as raw material
Nanometer grade powder.
5th embodiment, the powder of solid electrolyte are arranged to using the oxide containing lithium be that raw material passes through at coprecipitation
Manage obtained nanometer grade powder.
6th embodiment, the powder of solid electrolyte are arranged to pass through sol-gel by raw material of the oxide containing lithium
Method handles obtained nanometer grade powder.
7th embodiment, the powder of solid electrolyte are arranged to handle by solid phase method using the oxide containing lithium as raw material
Obtained nanometer grade powder.
A kind of preparation method of no synthetic polymer flexible solid dielectric film, with reference to embodiment, enters to the present invention
One step describes, and following examples are intended to illustrate invention rather than limitation of the invention further.One embodiment, it is walked
Suddenly it is：
First, the preparation of the powder of solid electrolyte
By sol-gel process or solid-phase synthesis, lithium salts is weighed by metering ratio, zirconates, lanthanum salt is dissolved in the mixing of deionized water
Liquid, chelating agent is added, chelating agent is citric acid or glycine, the one or more in EDTA, dries moisture in an oven, obtains
Colloidal sol, the further calcination at 400-600 DEG C, light component is removed, obtains xerogel further in 900-1400 DEG C of high temperature furnace
Middle sintering 10-24 hours, nanoscale solids electrolyte ceramicses powder is obtained after the crushing that cools,
Or hydroxide and zirconium oxide with lithium, lanthana, by being sanded, obtain nano-oxide, the oxygen as reactant
Compound powder further sinters 10-24 hours in 900-1400 DEG C of high temperature furnace, and obtaining nanoscale after the crushing that cools consolidates
Body electrolyte ceramicses powder.
2nd, the preparation of nano-cellulose
To the wood-fibred of high polymerization degree, bamboo fibre, cotton fibriia, stalk fibre, with TEMPO oxycelluloses, by glucose list
The hydroxyl of first C6 positions is oxidized to carboxyl, and the cellulose that the degree of polymerization reduces passes through homogeneous high-pressure unit, fine in a limited space
Dimension element is reached 1500-2000Bar by normal pressure by moment pressure and extruded, and superpower mechanical impacting with high pressure, cellulose bundle is torn
Split, turn into nano-cellulose, mechanical high pressure impingement circular treatment 5 times, 60% cellulose diameter≤10 nanometer,
3rd, the preparation of flexible solid dielectric film
After nano-cellulose is mixed with the powder of solid electrolyte, absolute ethyl alcohol, or acetone, or 1-METHYLPYRROLIDONE are added
As solvent, nano-cellulose adds the binding agent for being contained in 0wt%-1wt% admittedly, it is 5wt%- always to contain admittedly admittedly containing being 5wt%-50wt%
45wt% slurry, with the method for scraper for coating or transfer coated by slurry even spread to PP, PE or PET for supporter
On film, after drying and processing, upper and lower two layers independent winding obtains coiled flexible solid dielectric film and repeats what is utilized
Support film.
In the present embodiment, the thickness of flexible solid dielectric film is arranged to 8-40 microns.
In the present embodiment, the support film of reusable edible is arranged to PP, PE or PET film.
In the present embodiment, the salt containing lithium or oxide are arranged to LiNO3, LiOH, Li（CH3COO）, Li2One kind in O
Or two kinds, lanthanum salt or and its oxide such as La (NO3)3,La(OH)3,La(CH3COO)3, La(CH3COCHCOCH3)3•XH2O,
La2O3One or both of, zirconates and its oxide or hydroxide such as Zr (NO3)4, Zr (OH)4, Zr（CH3COO）4,
Zr (CH3COCHCOCH3)4,ZrO2One or both of, titanium-containing compound such as Ti (OCH2CH2CH2CH3)4,TiCl4,TiO2
In one kind or Ta salt and its oxide.
In the present embodiment, nano-cellulose mass ratio in solid electrolyte film is 5 wt%-40wt%.
In the present embodiment, cellulose preparation method, its step are：
Cellulosic material crosses 60-80 mesh sieves after crushing, renewable fiber is wood-fibred, cotton fiber, flaxen fiber, stalk cellulose
In one kind.Renewable fiber after being swelled in deionized water, regulation dry pulp mass fraction is 1wt%-10wt%, adds dry pulp
Quality 1wt%-5wt% TEMPO, dry pulp quality 8wt%-35wt% NaBr, while stirring, 12wt% NaClO is added dropwise,
Dripping quantity is the 3-12ml/g of dry pulp quality, between adjusting PH=10-11 with dilute NaOH, mixing speed 300-1000rpm, instead
To answer 2-6 hours, after reaction terminates, slurries filtration or centrifuge washing 3 times, PH are neutrality, obtain TEMPO oxidation processes disposed slurries,
TEMPO oxidation processes disposed slurries, deionized water is added, with 300rpm mixing speeds in agitator tank, is uniformly mixing to obtain solid
Content is 0.1wt%-3wt% cellulose paste, with high pressure homogenizer circular treatment 3-20 times, obtains nano-cellulose.
In the present embodiment, renewable fiber is arranged to one kind in wood-fibred, cotton fiber, flaxen fiber, stalk cellulose.
In the present embodiment, binding agent is arranged to CMC（Carboxymethyl cellulose）、PVP（Polyvinylpyrrolidone）、PVA（It is poly-
Vinyl alcohol）、PAA（Polyacrylic acid）、PEO（Polyethylene glycol oxide）、PVDF（Kynoar）In one kind, mass ratio is 0 wt%-
1wt%。
Second embodiment, its step are：
First, the preparation of the powder of solid electrolyte
By sol-gel process or solid-phase synthesis, lithium salts is weighed by metering ratio, zirconates, lanthanum salt is dissolved in the mixing of deionized water
Liquid, chelating agent is added, chelating agent is citric acid or glycine, the one or more in EDTA, dries moisture in an oven, obtains
Colloidal sol, the further calcination at 400 DEG C, light component is removed, obtaining xerogel, further sintering 10 is small in 900 DEG C of high temperature furnace
When, nanoscale solids electrolyte ceramicses powder is obtained after the crushing that cools,
2nd, the preparation of nano-cellulose
To the wood-fibred of high polymerization degree, bamboo fibre, cotton fibriia, stalk fibre, with TEMPO oxycelluloses, by glucose list
The hydroxyl of first C6 positions is oxidized to carboxyl, and the cellulose that the degree of polymerization reduces passes through homogeneous high-pressure unit, fine in a limited space
Dimension element is reached 1500Bar by normal pressure by moment pressure and extruded, and superpower mechanical impacting with high pressure, cellulose bundle is torn, into
For nano-cellulose, mechanical high pressure impingement circular treatment 5 times, 60% cellulose diameter≤9 nanometer,
3rd, the preparation of flexible solid dielectric film
After nano-cellulose is mixed with the powder of solid electrolyte, absolute ethyl alcohol, or acetone, or 1-METHYLPYRROLIDONE are added
As solvent, nano-cellulose is solid containing be 5wt%, adds the binding agent for being contained in 0wt% admittedly, total solid containing the slurry for being 5wt%, with scraping
The method of cutter painting cloth or transfer coated by slurry even spread to PP, PE or PET film for supporter, by drying and processing
Afterwards, upper and lower two layers independent winding obtains coiled flexible solid dielectric film and the repeatable support film utilized.
In the present embodiment, the thickness of flexible solid dielectric film is arranged to 8 microns.
In the present embodiment, the support film of reusable edible is arranged to PP.
In the present embodiment, the salt containing lithium or oxide are arranged to LiNO3, LiOH, Li（CH3COO）, Li2One kind in O
Or two kinds.
In the present embodiment, nano-cellulose mass ratio in solid electrolyte film is 5 wt%.
In the present embodiment, cellulose preparation method, its step are：
Cellulosic material crosses 60 mesh sieves after crushing, and renewable fiber is wood-fibred, the renewable fibre after being swelled in deionized water
Dimension, regulation dry pulp mass fraction is 1wt%, adds dry pulp quality 1wt% TEMPO, dry pulp quality 8wt% NaBr, in stirring
Meanwhile 12wt% NaClO is added dropwise, and dripping quantity is the 3ml/g of dry pulp quality, between adjusting PH=10 with dilute NaOH, mixing speed
For 300rpm, react 2 hours, after reaction terminates, slurries filtration or centrifuge washing 3 times, PH is neutrality, is obtained at TEMPO oxidations
Disposed slurry is managed, TEMPO oxidation processes disposed slurries, adds deionized water, it is equal with 280rpm mixing speeds, stirring in agitator tank
It is even to obtain the cellulose paste that solid content is 0.1wt%wt%, with high pressure homogenizer circular treatment 3 times, obtain nano-cellulose.
In the present embodiment, renewable fiber is arranged to wood-fibred.
In the present embodiment, binding agent is arranged to CMC（Carboxymethyl cellulose）, mass ratio is 0 wt%.
3rd embodiment, its step are：
First, the preparation of the powder of solid electrolyte
By sol-gel process or solid-phase synthesis, lithium salts is weighed by metering ratio, zirconates, lanthanum salt is dissolved in the mixing of deionized water
Liquid, chelating agent is added, chelating agent is citric acid or glycine, the one or more in EDTA, dries moisture in an oven, obtains
Colloidal sol, the further calcination at 600 DEG C, light component is removed, xerogel is obtained and further sinters 24 in 1400 DEG C of high temperature furnace
Hour, nanoscale solids electrolyte ceramicses powder is obtained after the crushing that cools,
2nd, the preparation of nano-cellulose
To the wood-fibred of high polymerization degree, bamboo fibre, cotton fibriia, stalk fibre, with TEMPO oxycelluloses, by glucose list
The hydroxyl of first C6 positions is oxidized to carboxyl, and the cellulose that the degree of polymerization reduces passes through homogeneous high-pressure unit, fine in a limited space
Dimension element is reached 2000Bar by normal pressure by moment pressure and extruded, and superpower mechanical impacting with high pressure, cellulose bundle is torn, into
For nano-cellulose, mechanical high pressure impingement circular treatment 5 times, 60% cellulose diameter≤10 nanometer,
3rd, the preparation of flexible solid dielectric film
After nano-cellulose is mixed with the powder of solid electrolyte, absolute ethyl alcohol, or acetone, or 1-METHYLPYRROLIDONE are added
As solvent, nano-cellulose is solid containing being 50wt%, adds the binding agent for being contained in 1wt% admittedly, total solid slurry containing for 45wt%, uses
The method of scraper for coating or transfer coated by slurry even spread to PP, PE or PET film for supporter, at drying
After reason, upper and lower two layers independent winding obtains coiled flexible solid dielectric film and the repeatable support film utilized.
In the present embodiment, the thickness of flexible solid dielectric film is arranged to 40 microns.
In the present embodiment, the support film of reusable edible is arranged to PE.
In the present embodiment, the salt containing lithium or oxide are arranged to lanthanum salt or and its oxide such as La (NO3)3,La(OH)3,
La(CH3COO)3, La(CH3COCHCOCH3)3•XH2O,La2O3In one kind.
In the present embodiment, nano-cellulose mass ratio in solid electrolyte film is 40wt%.
In the present embodiment, cellulose preparation method, its step are：
Cellulosic material crosses 80 mesh sieves after crushing, renewable fiber is in wood-fibred, cotton fiber, flaxen fiber, stalk cellulose
It is a kind of.Renewable fiber after being swelled in deionized water, regulation dry pulp mass fraction is 10wt%, adds dry pulp quality 5wt%
TEMPO, dry pulp quality 35wt% NaBr, while stirring, 12wt% NaClO is added dropwise, dripping quantity is dry pulp quality
12ml/g, with dilute NaOH adjust PH=11, mixing speed 1000rpm, react 6 hours, reaction terminate after, slurries filtration or from
The heart washs 3 times, and PH is neutrality, obtains TEMPO oxidation processes disposed slurries, TEMPO oxidation processes disposed slurries, adds deionization
Water, with 300rpm mixing speeds in agitator tank, the cellulose paste that solid content is 3wt% is uniformly mixing to obtain, use is high-pressure homogeneous
Machine circular treatment 20 times, obtains nano-cellulose.
In the present embodiment, renewable fiber is arranged to cotton fiber.
In the present embodiment, binding agent is arranged to PVP（Polyvinylpyrrolidone）, mass ratio 1wt%.
4th embodiment, its step are：
First, the preparation of the powder of solid electrolyte
By sol-gel process or solid-phase synthesis, lithium salts is weighed by metering ratio, zirconates, lanthanum salt is dissolved in the mixing of deionized water
Liquid, chelating agent is added, chelating agent is citric acid or glycine, the one or more in EDTA, dries moisture in an oven, obtains
Colloidal sol, the further calcination at 500 DEG C, light component is removed, xerogel is obtained and further sinters 16 in 1200 DEG C of high temperature furnace
Hour, nanoscale solids electrolyte ceramicses powder is obtained after the crushing that cools,
2nd, the preparation of nano-cellulose
To the wood-fibred of high polymerization degree, bamboo fibre, cotton fibriia, stalk fibre, with TEMPO oxycelluloses, by glucose list
The hydroxyl of first C6 positions is oxidized to carboxyl, and the cellulose that the degree of polymerization reduces passes through homogeneous high-pressure unit, fine in a limited space
Dimension element is reached 2000Bar by normal pressure by moment pressure and extruded, and superpower mechanical impacting with high pressure, cellulose bundle is torn, into
For nano-cellulose, mechanical high pressure impingement circular treatment 5 times, 60% cellulose diameter≤9.5 nanometer,
3rd, the preparation of flexible solid dielectric film
After nano-cellulose is mixed with the powder of solid electrolyte, absolute ethyl alcohol, or acetone, or 1-METHYLPYRROLIDONE are added
As solvent, nano-cellulose is solid containing being 50wt%, adds the binding agent for being contained in 1wt% admittedly, total solid slurry containing for -45wt%, uses
The method of scraper for coating or transfer coated is by slurry even spread to the PET film for supporter, after drying and processing, on
Lower two layers of independent winding obtains coiled flexible solid dielectric film and the repeatable support film utilized.
In the present embodiment, the thickness of flexible solid dielectric film is arranged to 24 microns.
In the present embodiment, the support film of reusable edible is arranged to PET film.
In the present embodiment, the salt containing lithium or oxide are arranged to zirconates and its oxide or hydroxide such as Zr (NO3)4,
Zr (OH)4, Zr（CH3COO）4, Zr (CH3COCHCOCH3)4,ZrO2One or both of.
In the present embodiment, nano-cellulose mass ratio in solid electrolyte film is 17wt%.
In the present embodiment, cellulose preparation method, its step are：
Cellulosic material crosses 70 mesh sieves after crushing, renewable fiber is in wood-fibred, cotton fiber, flaxen fiber, stalk cellulose
It is a kind of.Renewable fiber after being swelled in deionized water, regulation dry pulp mass fraction is 5wt%, adds dry pulp quality 3wt%
TEMPO, dry pulp quality 24wt% NaBr, while stirring, 12wt% NaClO is added dropwise, dripping quantity is dry pulp quality
8ml/g, between adjusting PH=10-11 with dilute NaOH, mixing speed 600rpm, react 4 hours, after reaction terminates, slurries filtration
Or centrifuge washing 3 times, PH are neutrality, obtain TEMPO oxidation processes disposed slurries, TEMPO oxidation processes disposed slurries, add go from
Sub- water, with 300rpm mixing speeds in agitator tank, the cellulose paste that solid content is 1.5wt% is uniformly mixing to obtain, uses high pressure
Homogenizer circular treatment 13 times, obtains nano-cellulose.
In the present embodiment, renewable fiber is arranged to flaxen fiber.
In the present embodiment, binding agent is arranged to PAA（Polyacrylic acid）, mass ratio is 0.5 wt%.
5th embodiment, its step are：
The preparation of the powder of solid electrolyte
With the hydroxide and zirconium oxide of lithium, lanthana, by being sanded, obtains nano-oxide, the oxidation as reactant
Thing powder further sinters 10-24 hours in 900-1400 DEG C of high temperature furnace, and nanoscale solids are obtained after the crushing that cools
Electrolyte ceramicses powder.
In the present embodiment, the salt containing lithium or oxide are arranged to LiNO3, LiOH, Li（CH3COO）, Li2One kind in O
Or two kinds, lanthanum salt or and its oxide such as La (NO3)3,La(OH)3,La(CH3COO)3, La(CH3COCHCOCH3)3•XH2O,
La2O3One or both of, zirconates and its oxide or hydroxide such as Zr (NO3)4, Zr (OH)4, Zr（CH3COO）4,
Zr (CH3COCHCOCH3)4,ZrO2One or both of, titanium-containing compound such as Ti (OCH2CH2CH2CH3)4,TiCl4,TiO2
In one kind or Ta salt and its oxide.
In the present embodiment, renewable fiber is arranged to one kind in wood-fibred, cotton fiber, flaxen fiber, stalk cellulose.
In the present embodiment, binding agent is arranged to CMC（Carboxymethyl cellulose）、PVP（Polyvinylpyrrolidone）、PVA（It is poly-
Vinyl alcohol）、PAA（Polyacrylic acid）、PEO（Polyethylene glycol oxide）、PVDF（Kynoar）In one kind, mass ratio is 0 wt%-
1wt%。
6th embodiment, its step are：
The preparation of the powder of solid electrolyte
With the hydroxide and zirconium oxide of lithium, lanthana, by being sanded, obtains nano-oxide, the oxidation as reactant
Thing powder is further sintered 10 hours in 900 DEG C of high temperature furnace, and nanoscale solids electrolyte pottery is obtained after the crushing that cools
Porcelain powder.
In the present embodiment, the salt containing lithium or oxide are arranged to zirconates and its oxide or hydroxide such as Zr (NO3)4,
Zr (OH)4, Zr（CH3COO）4, Zr (CH3COCHCOCH3)4,ZrO2One or both of.
In the present embodiment, renewable fiber is arranged to stalk cellulose.
In the present embodiment, binding agent is arranged to PAA（Polyacrylic acid）.
7th embodiment, its step are：
The preparation of the powder of solid electrolyte
With the hydroxide and zirconium oxide of lithium, lanthana, by being sanded, obtains nano-oxide, the oxidation as reactant
Thing powder is further sintered 24 hours in 1400 DEG C of high temperature furnace, and nanoscale solids electrolyte pottery is obtained after the crushing that cools
Porcelain powder.
In the present embodiment, the salt containing lithium or oxide are arranged to titanium-containing compound such as Ti (OCH2CH2CH2CH3)4,
TiCl4,TiO2。
In the present embodiment, renewable fiber is arranged to flaxen fiber.
In the present embodiment, binding agent is arranged to PEO（Polyethylene glycol oxide）,
8th embodiment, its step are：
The preparation of the powder of solid electrolyte
With the hydroxide and zirconium oxide of lithium, lanthana, by being sanded, obtains nano-oxide, the oxidation as reactant
Thing powder is further sintered 16 hours in 1100 DEG C of high temperature furnace, and nanoscale solids electrolyte pottery is obtained after the crushing that cools
Porcelain powder.
In the present embodiment, the salt containing lithium or oxide are arranged to Ta salt and its oxide.
In the present embodiment, renewable fiber is arranged to stalk cellulose.
In the present embodiment, binding agent is arranged to PVDF（Kynoar）.
Embodiment two to five is based on embodiment one, and embodiment six to eight is based on embodiment five.
The percent thermal shrinkage of the solid electrolyte film obtained by the present embodiment one, electrical conductivity are tested, battery punctures effect,
Common PE battery diaphragm is control, and with iron phosphate lithium positive pole pole piece, graphite cathode pole piece is assembled into battery, injection electrolysis
Liquid, test battery performance.
By the solid electrolyte film and iron phosphate lithium positive pole pole piece, graphite cathode pole piece is assembled into battery, injection control electricity
The electrolyte of the amount of pond 1/2, test battery performance.Test the battery and control group cycle performance of battery.
Solid electrolyte film battery performance test result.
9th embodiment, its step are：
By La (NO3)3•6H2O、(C16H36O4)Ti、LiNO3It is dissolved in by metering ratio in ethanol, uniform solution, wherein lithium mistake is made
Amount 30%.Then, appropriate citric acid is added, is stirred continuously at 70 DEG C, after ethanol volatilization completely, forms fluffy do
Gel.Gel is incubated 4 hours under 550 DEG C of air atmospheres, carbon and light component is removed, that is, has obtained nanometer grade powder.Powder
Body continues to be heated to 900 DEG C and sintered 12 hours, and tabletting is crushed after cooling, then is incubated 8 hours at 1000 DEG C, obtains nano level
Li0.5La0.5TiO3Solid electrolyte,
Using the birchwood fiber sheet after bleaching as raw material, 80 mesh sieves are crossed after crushing, it is solid containing being to adjust the wet pulp with deionized water
1wt%, it is separately added into dry wood-fibred quality 1.8wt% TEMPO and 10wt% NaBr.Then under 500rpm stirring conditions,
10mL/g NaClO solution and 0.4moL/L NaOH solution is added dropwise simultaneously, it is 10.5 or so to control pH value, and stirring is anti-at room temperature
Answer 2 hours.Reaction terminates, and slurry is washed with deionized to neutrality, and homogenizer is handled 3 times after readjusting suitable solid content,
Obtain nano-cellulose,
By solid electrolyte powder Li0.5La0.5TiO3Mixed according to a certain percentage with nano-cellulose, it is 0.2Wt% that addition contains admittedly
PVDF be binding agent, DMF is that solvent is deployed into slurry, is applied on porous PET basement membranes, dries, basement membrane and solid electrolyte
Film is independently wound.
The percent thermal shrinkage of solid electrolyte film, electrical conductivity are tested, battery punctures effect.
By the solid electrolyte film and iron phosphate lithium positive pole pole piece, graphite cathode pole piece is assembled into battery, injects control group
The amount electrolyte of battery 1/4, test battery performance.
Tenth embodiment, its step are：
By La (NO3)3•6H2O、Zr（C16H36O4）、LiNO3Ethanol, wherein lithium excess 20wt% are dissolved in, then adds appropriate lemon
Acid, dry under the conditions of 80 DEG C, you can obtain fluffy xerogel.Gel is incubated 2 hours under 500 DEG C of air atmospheres, removes carbon
And light component, obtain nanometer grade powder.Powder continues to be heated to 900 DEG C and sintered 12 hours, crushes tabletting after cooling, then
1000 DEG C are incubated 6 hours, obtain nano level Li7La3Zr2O12Solid electrolyte,
Using the bamboo fibre after bleaching as raw material, 80 mesh sieves are crossed after crushing, the solid content starched with deionized water regulation bamboo fibre is
2wt%, it is separately added into dry fibers 1.6wt% TEMPO and 15wt% NaBr.Then under the conditions of 500rpm, it is added dropwise simultaneously
12mL/g NaClO solution and 0.4moL/L NaOH solution, it is 10.5 or so to control pH value, at room temperature stirring reaction 2 hours.
Reaction terminates, and slurry is washed with deionized to neutrality, is handled 5 times, is received with homogenizer after readjusting suitable solid content
Rice cellulose,
By solid electrolyte powder Li7La3Zr2O12Mixed with nano-cellulose in suitable ratio, the PEO using 0.5wt% is viscous
Tie agent, acetone be solvent be deployed into slurry, be applied on PP basement membranes, drying, independently winding obtain solid electrolyte film and
Former PP basement membranes,
The percent thermal shrinkage of solid electrolyte film, electrical conductivity are tested, battery punctures effect.
By the solid electrolyte film and iron phosphate lithium positive pole pole piece, graphite cathode pole piece is assembled into battery, injects control group
The amount electrolyte of battery 1/4, test battery performance.
Tenth one embodiment, its step are：
By La2O3、LiOH、ZrO2、Ta2O5Ethanol is scattered in, ball milling 10 hours, is received in zirconium pearl-polyurethane ball-milling pot
Meter level powder wet-milling.After drying, powder is heated to 900 DEG C and sintered 12 hours, tabletting is crushed after cooling, then in 1140 DEG C of insulations
16 hours, obtain nano level Li6.5La3Zr1.5Ta0.5O12Solid electrolyte,
Using the stalk fibre after bleaching as raw material, 60 mesh sieves are crossed after crushing, it is 0.5wt% to adjust solid content with deionized water, respectively
Add stalk fibre 2wt% TEMPO and 12wt% NaBr.Then under the conditions of 500rpm, while 12mL/g NaClO is added dropwise
The NaOH solution of solution and 0.4moL/L, it is 11 or so to control pH value, at room temperature stirring reaction 2 hours.After reaction terminates, spend
Ion water washing is handled 10 times with homogenizer after readjusting suitable solid content, obtains nano-cellulose to neutrality,
By solid electrolyte powder Li6.5La3Zr1.5Ta0.5O12Mix, be added without any in suitable ratio with nano-cellulose
Bonding agent, ethanol are that solvent is deployed into slurry, are applied on PE basement membranes, drying, winding obtains solid electrolyte film and PE respectively
Basement membrane,
The percent thermal shrinkage of solid electrolyte film, electrical conductivity are tested, battery punctures effect.
By the solid electrolyte film and iron phosphate lithium positive pole pole piece, graphite cathode pole piece is assembled into battery, injects control group
The electrolyte of 1/6 amount, test battery performance.
One kind is without application of the synthetic polymer flexible solid dielectric film as solid electrolyte in Li-AIR batteries.
Wherein：The Nanowire for handling to obtain by TEMPO oxycelluloses and mechanical impact as raw material using renewable fiber
Application of the dimension element in the solid electrolyte of Li-AIR batteries.
The present invention has lower feature：
1st, due to devising the powder and nano-cellulose of solid electrolyte, pass through that nano-cellulose provides elasticity and space is tied
Structure, the interior spatial structure of flexible solid dielectric film is improved, the fragility for avoiding ceramiic solid electrolyte is higher and elastic
It is relatively low, therefore improve the security performance of lithium-ion-power cell.
2nd, due to devising outer layer 2, second of packaging is implemented to internal layer 1, more extends the release time of chemical fertilizer.
3rd, due to devising the powder of solid electrolyte, overcome that the hot melting temperature of general polymer barrier film is low, and temperature is too high
The shortcomings that easily shrinking, prevents the battery short circuit caused by Li dendrite punctures barrier film, so as to effectively raise battery security
Energy.
4th, due to devising binding agent, when with minimal amount of bonding agent can film forming because cellulose have in itself it is a large amount of
Hydroxyl, hydrogen bond can be formed, without bonding agent also can film forming characteristic, therefore can further improve solid electrolyte ion pass
Conductance, moreover it is possible to reduce production cost.
5th, porous synthetic polymer PP, PE or PET film are played a supporting role in wet pulp, reusable edible, reduce production
Cost
6th, the restriction of number range has been carried out to planform due to devising, it is in technical scheme to make number range
Technical characteristic, be not to be calculated by formula or the number range is shown by the technical characteristic that draws of limited number of time experiment, experiment
Technical characteristic achieve good technique effect.
7th, due to devising the technical characteristic of the present invention, in the effect of the independent and mutual set of technical characteristic,
Shown by experiment, property indices of the invention are at least 1.7 times for existing property indices, have by assessing
There is good market value.
Also others by TEMPO oxycelluloses and mechanical impact using renewable fiber as raw material with handling to obtain
Nano-cellulose it is same or like as technical characteristic be all one of embodiments of the invention, and embodiment described above
Each technical characteristic can be combined arbitrarily, no longer right to meet Patent Law, patent regulation and the requirement of guidelines for examination
The embodiment of all possible combination of each technical characteristic in above-described embodiment is all described.
Above-described embodiment is no synthetic polymer flexible solid dielectric film and its preparation method provided by the present invention
And its application a kind of way of realization, according to scheme provided by the present invention other deformation, increase or reduce it is therein into
Part or step, or the present invention is used for close technical fields other and of the invention, belong to protection scope of the present invention.
Claims (10)
1. it is a kind of without synthetic polymer flexible solid dielectric film, it is characterized in that：Include the powder of solid electrolyte and with can
Regenerated fiber is the nano-cellulose that raw material handles to obtain by TEMPO oxycelluloses and mechanical impact.
2. no synthetic polymer flexible solid dielectric film according to claim 1, it is characterized in that：The powder of solid electrolyte
End is arranged to receive by what coprecipitation, sol-gel process or solid phase method handled to obtain as raw material using the salt containing lithium or oxide
Nanoscale powder,
Or also include binding agent and binding agent is arranged to CMC i.e. carboxymethyl cellulose, PVP i.e. polyvinylpyrrolidone, PVA
I.e. polyvinyl alcohol, PAA are one kind in polyacrylic acid, PEO i.e. polyethylene glycol oxide, PVDF i.e. Kynoar.
3. a kind of preparation method of no synthetic polymer flexible solid dielectric film, its step are：With the salt containing lithium or oxidation
Thing is that raw material passes through coprecipitation, the powder for the solid electrolyte that sol-gel process or solid phase method handle to obtain and with renewable
Fiber is the nano-cellulose mixing that raw material handles to obtain by TEMPO oxycelluloses and mechanical impact, and slurry is made,
Slurry is applied on support film, and flexible solid dielectric film is obtained after film forming.
4. the preparation method of no synthetic polymer flexible solid dielectric film according to claim 3, it is characterized in that：It is walked
Suddenly it is：
First, the preparation of the powder of solid electrolyte
By sol-gel process or solid-phase synthesis, lithium salts is weighed by metering ratio, zirconates, lanthanum salt is dissolved in the mixing of deionized water
Liquid, chelating agent is added, chelating agent is citric acid or glycine, the one or more in EDTA, dries moisture in an oven, obtains
Colloidal sol, the further calcination at 400-600 DEG C, light component is removed, obtains xerogel further in 900-1400 DEG C of high temperature furnace
Middle sintering 10-24 hours, nanoscale solids electrolyte ceramicses powder is obtained after the crushing that cools,
Or hydroxide and zirconium oxide with lithium, lanthana, by being sanded, obtain nano-oxide, the oxygen as reactant
Compound powder further sinters 10-24 hours in 900-1400 DEG C of high temperature furnace, and obtaining nanoscale after the crushing that cools consolidates
Body electrolyte ceramicses powder,
2nd, the preparation of nano-cellulose
To the wood-fibred of high polymerization degree, bamboo fibre, cotton fibriia, stalk fibre, with TEMPO oxycelluloses, by glucose list
The hydroxyl of first C6 positions is oxidized to carboxyl, and the cellulose that the degree of polymerization reduces passes through homogeneous high-pressure unit, fine in a limited space
Dimension element is reached 1500-2000Bar by normal pressure by moment pressure and extruded, and superpower mechanical impacting with high pressure, cellulose bundle is torn
Split, turn into nano-cellulose, mechanical high pressure impingement circular treatment 5 times, 60% cellulose diameter≤10 nanometer,
3rd, the preparation of flexible solid dielectric film
After nano-cellulose is mixed with the powder of solid electrolyte, absolute ethyl alcohol, or acetone, or 1-METHYLPYRROLIDONE are added
As solvent, nano-cellulose adds the binding agent for being contained in 0wt%-1wt% admittedly, it is 5wt%- always to contain admittedly admittedly containing being 5wt%-50wt%
45wt% slurry, with the method for scraper for coating or transfer coated by slurry even spread to PP, PE or PET for supporter
On film, after drying and processing, upper and lower two layers independent winding obtains coiled flexible solid dielectric film and repeats what is utilized
Support film.
5. the preparation method of no synthetic polymer flexible solid dielectric film according to claim 3, it is characterized in that：It is flexible
The thickness of solid electrolyte film is arranged to 8-40 microns.
6. the preparation method of no synthetic polymer flexible solid dielectric film according to claim 3, it is characterized in that：Containing lithium
Salt or oxide be arranged to LiNO3, LiOH, Li（CH3COO）, Li2One or both of O, lanthanum salt or and its oxide such as
La(NO3)3,La(OH)3,La(CH3COO)3, La(CH3COCHCOCH3)3•XH2O,La2O3One or both of, zirconates and its
Oxide or hydroxide such as Zr (NO3)4, Zr (OH)4, Zr（CH3COO）4, Zr (CH3COCHCOCH3)4,ZrO2In one
Kind or two kinds, titanium-containing compound such as Ti (OCH2CH2CH2CH3)4,TiCl4,TiO2In one kind or Ta salt and its oxide.
7. the preparation method of no synthetic polymer flexible solid dielectric film according to claim 3, it is characterized in that：Nanometer
Cellulose mass ratio in solid electrolyte film is 5 wt%-40wt%,
Or cellulose preparation method, its step are：
Cellulosic material crosses 60-80 mesh sieves after crushing, renewable fiber is in wood-fibred, cotton fiber, flaxen fiber, stalk cellulose
One kind, in deionized water be swelled after renewable fiber, regulation dry pulp mass fraction be 1wt%-10wt%, addition dry pulp matter
1wt%-5wt% TEMPO, dry pulp quality 8wt%-35wt% NaBr is measured, while stirring, 12wt% NaClO, drop is added dropwise
Dosage is the 3-12ml/g of dry pulp quality, between adjusting PH=10-11 with dilute NaOH, mixing speed 300-1000rpm, and reaction
2-6 hours, after reaction terminates, slurries filtration or centrifuge washing 3 times, PH are neutrality, obtain TEMPO oxidation processes disposed slurries,
TEMPO oxidation processes disposed slurries, deionized water is added, with 280-320rpm mixing speeds in agitator tank, is uniformly mixing to obtain
Solid content is 0.1wt%-3wt% cellulose paste, with high pressure homogenizer circular treatment 3-20 times, obtains nano-cellulose,
Or renewable fiber is arranged to one kind in wood-fibred, cotton fiber, flaxen fiber, stalk cellulose.
8. the preparation method of no synthetic polymer flexible solid dielectric film according to claim 3, it is characterized in that：Bond
Agent is arranged to CMC i.e. carboxymethyl cellulose, PVP i.e. polyvinylpyrrolidone, PVA i.e. polyvinyl alcohol, PAA i.e. polyacrylic acid, PEO
I.e. polyethylene glycol oxide, PVDF are one kind in Kynoar, and mass ratio is arranged to as 0 in flexible solid dielectric film
wt%-1wt%。
9. a kind of application of no synthetic polymer flexible solid dielectric film, aoxidized using renewable fiber as raw material by TEMPO
Application of the nano-cellulose that cellulose and mechanical impact handle to obtain in the solid electrolyte of Li-AIR batteries.
10. one kind is without application of the synthetic polymer flexible solid dielectric film as solid electrolyte in Li-AIR batteries.
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| CN113097561A (en) * | 2021-04-09 | 2021-07-09 | 浙江大学山东工业技术研究院 | Ultrathin ceramic matrix composite solid electrolyte membrane and preparation method and application thereof |
| CN115020919A (en) * | 2022-07-22 | 2022-09-06 | 上海恩捷新材料科技有限公司 | Coating slurry, diaphragm, preparation method of diaphragm and battery |
| CN115020919B (en) * | 2022-07-22 | 2023-08-01 | 上海恩捷新材料科技有限公司 | Coating slurry, separator, preparation method of separator and battery |
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