CN109585910A - A kind of solid union electrolyte and its dielectric film preparation method and application - Google Patents
A kind of solid union electrolyte and its dielectric film preparation method and application Download PDFInfo
- Publication number
- CN109585910A CN109585910A CN201811346058.6A CN201811346058A CN109585910A CN 109585910 A CN109585910 A CN 109585910A CN 201811346058 A CN201811346058 A CN 201811346058A CN 109585910 A CN109585910 A CN 109585910A
- Authority
- CN
- China
- Prior art keywords
- attapulgite
- solid union
- lithium
- dielectric film
- aqueous polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention proposes that a kind of solid union dielectric film and its dielectric film preparation method and application, the solid union electrolyte, raw material include: aqueous polyurethane 85-95%, lithium salts 1-10% and amino graphene coated attapulgite 1-5% by weight percentage.The preparation method of its dielectric film includes: to be mixed and stirred for aqueous polyurethane and amino graphene coated attapulgite, polyurethane composition is obtained, lithium salts is added in Xiang Suoshu polyurethane composition, obtains the polyurethane composition lotion of lithium doping, dry film forming again to get solid union dielectric film.Solid union dielectric film of the present invention uses the material skeleton of aqueous polyurethane and amino graphene coated attapulgite as solid union electrolyte, high ionic conductivity of the electrolyte in large temperature range is not only assigned, but also there is good mechanical performance.
Description
Technical field
The present invention relates to technical field of lithium batteries more particularly to a kind of solid union dielectric film and its dielectric film to prepare
Methods and applications.
Background technique
Lithium ion battery has many advantages, such as energy density high, long service life and memory-less effect, be widely used in mobile phone,
In the electronic equipments such as computer, digital camera, unmanned plane, robot and motion bracelet.In addition, lithium ion battery is in new-energy automobile
Field is also well used as main energy storage device.However the preparation of current lithium ion battery mainly uses liquid
Organic bath, there are volatile, easy firing, the easily security risks such as leakage and explosive, constrain the development of lithium ion battery.
In order to solve the safety problem of lithium ion battery, people prepare all-solid lithium-ion battery using solid polymer electrolyte, keep away
Liquid electrolyte bring safety problem is exempted from.
The solid electrolyte research and development of lithium ion battery probably have 20 years or so, are divided into two types, and one kind is organic polymer
Object electrolyte, another kind are non-organic electrolyte.Non-organic electrolyte has the higher characteristic of conductivity, but synthesizes difficulty
Greatly, processing is complicated, and cost is too high, and external dependency structure has made many researchs, such as Japan Toyota, University to this
Of Tokyo, U.S. Department of Energy subordinate National Laboratory Oak Ridge National Laboratory, representative is special
Sharp US8557445B2.Organic polyelectrolyte it is cheap, process also relatively easy, but almost all polymer is solid
State electrolyte is all based on polyethylene oxide (PEO).Since polyethylene oxide (PEO) can be complexed with salt, pass through molecule
The movement of chain keeps ion mobile, thus conductive.But all solid electrolytes by polyethylene oxide (PEO) conduction are required to
Being heated at least 50 degrees Celsius or more just can have enough conductive capabilities to enable normal battery operation.Thus many scientific research institutions and
Research direction is gone to gel type electrolyte or production high-temperature battery by company.The conductivity of gel type electrolyte is very high, but lacks
Weary mechanical strength, approximate liquid, and processing method is more complicated.
China Patent Publication No. CN103208651A discloses a kind of siloxy group solid electrolyte and its preparation and application,
The component of its electrolyte includes: to lead lithium siloxane polymer 30-70%, bonding agent 25-40%, lithium salts 5- by percentage to the quality
30%.Its disclosed preparation method is: dissolving binder, lithium salts and siloxane polymer by organic solvent, forms liquid
Substance;Cladding process is then used, is coated on matrix;It is dried in vacuo again, depends on and form film on matrix, form it
It is removed from matrix again afterwards.But electrolyte conductivity principle disclosed in CN103208651A is substantially or with PEO ethylene oxide
It is complexed with the anion in lithium salts, forms soft mixture.Using under amorphous state, realized by the movement of strand
Lithium ion conduction.Disadvantage is that: (1) at low temperature, the performance of lithium ion conduction will sharply decline, so as to cause battery
No longer work;(2) main chain for leading lithium siloxane polymer is that Si-O is alternate, and branch essence is still ethylene oxide-[CH2-
CH2-O]n-.Can know from disclosed document, lead the molecular weight of lithium siloxane polymer be actually it is relatively low, point
Son amount needs to produce using cladding process less than 10000, the weakness for having rigidity not high.
China Patent Publication No. CN1251347C discloses the patent of invention of Lithium Power Technologies, Inc., the U.S.: a kind of solid polymerization
Object electrolyte, proposition improves polymer-lithium salts system, by the way that a kind of inorganic ions conductor (chalcogenide glass powder) is added
Further increase ionic conductivity.Since the electric conductivity of ion glass entirety itself is very high, but processing difficulties, thus prepare
At powder, by with polymer-lithium salts system combinations, to realize better simply processing and higher conductivity, essentially by
The material of material and a relatively low conductivity that a kind of higher conductivity is added obtains the conductivity of compromise.Due to chalcogenide glass powder
The quality at end accounts for relatively high, and the quality for providing second group of polymer of mechanical strength accounts for smaller, thus its mechanical performance is not
It is high;Solidify after powder is added with salting liquid using molecular weight polymers in embodiment in its technical solution, small molecule polymerization
Solid itself mechanical performance that object is formed is poor.In addition, the higher cost of ion glass, it is high to will lead to processing cost.
Summary of the invention
Technical problems based on background technology, the present invention propose a kind of solid union electrolyte and its dielectric film system
Preparation Method and application, the solid union electrolyte is using aqueous polyurethane and amino graphene coated attapulgite as solid-state
The material skeleton of composite electrolyte not only assigns high ionic conductivity of the electrolyte in large temperature range, but also has
Good mechanical performance.
A kind of solid union electrolyte proposed by the present invention, raw material include: aqueous polyurethane 85- by weight percentage
95%, lithium salts 1-10% and amino graphene coated attapulgite 1-5%.
Preferably, the amino graphene coated attapulgite is by by the concave convex rod of amino graphene solution and purifying
It dries and obtains after soil mixing.Preferably, amino graphene ultrasonic disperse is obtained concentration in deionized water is 0.1-0.5wt%
Amino graphene solution, the amino graphene solution is added dropwise in the attapulgite of purifying, the graphene solution with
The envelope-bulk to weight ratio of the attapulgite is (1-6) mL:10g, then dries at 75-100 DEG C to get the amino graphene packet
Cover attapulgite.
Preferably, the amino graphene is the amination modified graphene that surface has amino group.Preferably, described
Amino graphene is to add ethylenediamine, the weight ratio of ethylenediamine and graphene oxide by the way that graphene oxide to be dissolved in NMP
For 1:8-15, after being stirred to react 3-5h at 70-90 DEG C, reducing agent NaBH is added4, reducing agent NaBH4With the weight of graphene oxide
Amount is stirred to react 3-5h at 90-100 DEG C, filters, washing obtains the amino graphene than being 1-2:1.
Preferably, the method for purifying attapulgite includes: to add water to modulate after obtaining ore pulp solution attapulgite powder, is added
Calgon and sodium hydroxide ultrasonic agitation, immerse sulfuric acid solution, filter, calcine the bumps to get purifying after centrifuge separation
Stick soil.Preferably, the method for purifying attapulgite includes: after attapulgite is pulverized plus water is modulated to obtain concentration to be 20-
The calgon of 1.2-1.8wt% and the hydrogen-oxygen of 0.5-1wt% is added in the ore pulp solution of 30wt% on the basis of attapulgite
Change sodium, 0.5-1h is stirred by ultrasonic at 30-50 DEG C, it is dense according to solid and liquid weight ratio 1:1-3 immersion at 100-110 DEG C after centrifuge separation
0.1-0.5h in the sulfuric acid solution of 4-7mol/L is spent, is filtered, drying, then 1-2h is calcined at 300-400 DEG C to get the recessed of purifying
Convex stick soil.
Preferably, the synthesis material of the aqueous polyurethane includes: aliphatic polycarbonate diol 35-65 by weight
Part, 18-40 parts of diisocyanate, 2-8 parts of hydrophilic chain extender, 1-5 parts of triethylamine, 0.01-0.1 parts of catalyst, water 150-250
Part;Preferably, the aliphatic polycarbonate diol is poly- (carbonic acid 1,4-butanediol ester) glycol, poly- (carbonic acid 1,5- penta 2
Alcohol ester) one of glycol, poly- (carbonic acid 1,6- hexylene glycol ester) glycol or poly- (carbonic acid 1,10- decanediol ester) glycol or a variety of;
The diisocyanate is isophorone diisocyanate, hexamethylene diisocyanate, toluene di-isocyanate(TDI), 4,4'- bis-
One of methylenebis phenyl isocyanate or 4,4'- dicyclohexyl methyl hydride diisocyanate are a variety of;The hydrophilic chain extension
Agent is dihydromethyl propionic acid or dimethylolpropionic acid;The catalyst is stannous octoate, di-n-butyltin dilaurate, organic zinc
Or one of organo-bismuth or a variety of.Preferably, the aliphatic polycarbonate diol can refer to publication file
Method in CN102120818A is prepared.
Preferably, the method for synthesizing the aqueous polyurethane includes: by aliphatic polycarbonate diol, diisocyanate
Prepolymerization reaction is carried out, adding hydrophilic chain extender, organic solvent and catalyst, the reaction was continued, is added after cooling in triethylamine and anti-
It answers, adds water high-speed stirred, remove organic solvent to get the aqueous polyurethane;Preferably, diisocyanate, aliphatic
Polycarbonate glycol is that 1.5-2.0 carries out prepolymerization reaction according to NCO/OH ratio.Preferably, the aqueous polyurethane is synthesized
Method includes: that aliphatic polycarbonate diol, diisocyanate are reacted 3-5h at 70-90 DEG C, adds hydrophilic chain extension
Agent, NMP and catalyst, the reaction was continued at 70-90 DEG C 2-3h are added triethylamine neutralization reaction after being cooled to 30-40 DEG C, then plus
Enter water high-speed stirred under 3000-5000r/min rate, removes NMP to get the aqueous polyurethane.
Preferably, the lithium salts is lithium perchlorate, bis trifluoromethyl sulfimide lithium, double fluorine sulfimide lithiums, hexafluoro phosphorus
One of sour lithium, dioxalic acid lithium borate or LiBF4 are a variety of.
The invention also provides a kind of methods that aforementioned solid composite electrolyte prepares dielectric film, comprising: will be aqueous poly-
Urethane and amino graphene coated attapulgite are mixed and stirred for, and obtain polyurethane composition, in Xiang Suoshu polyurethane composition
Lithium salts is added, obtains the polyurethane composition lotion of lithium doping, then dries film forming to get solid union dielectric film.
Preferably, drying film forming procedure includes: 60-100 DEG C of dry 20-30h under vacuum conditions.
Present invention further propose that a kind of application of solid union dielectric film of above method preparation in lithium battery.
Compared with prior art, the present invention has the advantage that
(1) in solid union electrolyte provided by the invention, aqueous polyurethane is used as solid electrolyte material, operating process
It reduces and uses solvent, to the less pollution of environment, while solving the problems, such as environmental protection and inflammable problem;
It (2) include amino graphene coated attapulgite, passing through will be recessed in solid union electrolyte provided by the invention
Convex stick soil is compound with graphene, increases the specific surface area and porosity of attapulgite, can adsorb and be desorbed various atoms and
Molecule provides ideal environment for ionic conduction so that the solid union electrolyte comprising the substance reach preferably from
Electron conductivity.Aqueous polyurethane is a kind of copolymer with more blocks, has excellent comprehensive performance, due to polar difference
Different, the soft and hard segments of aqueous polyurethane are inclined to each self-contained phase, and selecting polycarbonate at this time is soft segment, are guaranteeing the same of ionic conductivity
When impart the good mechanical performance of electrolyte.
(2) in solid union electrolyte provided by the invention, in order to enable aqueous polyurethane and amino graphene coated are recessed
Convex stick soil can be effectively compound, by the reaction process of control aqueous polyurethane, obtains the aqueous polyurethane of NCO sealing end, can
It is reacted with the amino graphene coated with attapulgite's surface, so that the two is effectively compound, passes through the compound institute of the two
The solid electrolyte film of acquisition sufficiently combines amino graphene coated attapulgite and the excellent physics and chemistry of aqueous polyurethane
Matter, copolymer solid electrolyte as made from it have the advantages that high mechanical degrees, high conductivity.
Specific embodiment
Embodiment 1
A kind of solid union electrolyte includes: aqueous polyurethane 85%, lithium perchlorate 10% and amino by weight percentage
Graphene coated attapulgite 5%.It include: by above-mentioned weight percent when the solid union electrolyte is prepared into dielectric film
Above-mentioned property of water-bearing polyurethane and amino graphene coated attapulgite are mixed and stirred for, polyurethane composition, Xiang Suoshu are obtained
Lithium perchlorate is added in polyurethane composition, the polyurethane composition lotion of lithium doping is obtained, then under vacuum conditions, at 60 DEG C
Dry 30h is to get solid union dielectric film.
Wherein, the aqueous polyurethane synthesizes obtain with the following method: by weight by poly- (carbonic acid 1,4-butanediol
Ester) 35 parts of glycol, 40 parts of isophorone diisocyanate react 5h at 70 DEG C, add 2 parts of dihydromethyl propionic acid, NMP and
0.1 part of stannous octoate, the reaction was continued at 70 DEG C 3h, 5 parts of neutralization reactions of triethylamine are added after 30 DEG C of cooling, add water 150
Part high-speed stirred under 3000r/min rate removes NMP to get the aqueous polyurethane;
The amino graphene coated attapulgite is by mixing amino graphene solution with the attapulgite of purifying
Drying obtains afterwards, specifically, graphene oxide is dissolved in NMP, adds ethylenediamine, the weight of ethylenediamine and graphene oxide
Than after being stirred to react 3h at 90 DEG C, reducing agent NaBH is added for 1:84, reducing agent NaBH4Weight ratio with graphene oxide is
2:1 is stirred to react 5h at 90 DEG C, filters, and washing obtains amino graphene;After attapulgite is pulverized plus water is modulated
The ore pulp solution that concentration is 20wt% is obtained, the calgon and 0.5wt% of 1.8wt% are added on the basis of attapulgite
0.5h is stirred by ultrasonic at 50 DEG C in sodium hydroxide, immerses concentration 7mol/ according to solid and liquid weight ratio 1:1 at 110 DEG C after centrifuge separation
0.1h in the sulfuric acid solution of L is filtered, drying, then calcines 1h at 400 DEG C, the attapulgite purified;By amino graphene
Ultrasonic disperse obtains the amino graphene solution that concentration is 0.5wt% in deionized water, and the amino graphene solution is dripped
It being added in the attapulgite of purifying, the envelope-bulk to weight ratio of the graphene solution and the attapulgite is 1mL:10g, then
Drying is at 100 DEG C to get the amino graphene coated attapulgite.
Embodiment 2
A kind of solid union electrolyte includes: aqueous polyurethane 95%, bis trifluoromethyl sulfimide by weight percentage
Lithium 1% and amino graphene coated attapulgite 4%.It include: by upper when the solid union electrolyte is prepared into dielectric film
It states weight percent to be mixed and stirred for above-mentioned property of water-bearing polyurethane and amino graphene coated attapulgite, it is multiple to obtain polyurethane
Object is closed, lithium salts is added in Xiang Suoshu polyurethane composition, obtains the polyurethane composition lotion of lithium doping, then in vacuum condition
Under, dry 20h is at 100 DEG C to get solid union dielectric film.
Wherein, the aqueous polyurethane synthesizes obtain with the following method: by weight by poly- (carbonic acid 1,5-PD
Ester) 65 parts of glycol, 40 parts of hexamethylene diisocyanate react 3h at 90 DEG C, add 8 parts of dimethylolpropionic acid, NMP and
0.01 part of di-n-butyltin dilaurate, the reaction was continued at 90 DEG C 2h, 1 part of neutralization reaction of triethylamine is added after 40 DEG C of cooling,
250 parts of high-speed stirreds under 5000r/min rate of water are added, remove NMP to get the aqueous polyurethane;
The amino graphene coated attapulgite is by mixing amino graphene solution with the attapulgite of purifying
Drying obtains afterwards, specifically, graphene oxide is dissolved in NMP, adds ethylenediamine, the weight of ethylenediamine and graphene oxide
Than after being stirred to react 5h at 70 DEG C, reducing agent NaBH is added for 1:154, reducing agent NaBH4With the weight ratio of graphene oxide
For 1:1, it is stirred to react 3h at 100 DEG C, filters, washing obtains amino graphene;Add water tune after attapulgite is pulverized
The ore pulp solution that concentration is 30wt% is made, the calgon and 1wt% of 1.2wt% are added on the basis of attapulgite
1h is stirred by ultrasonic at 30 DEG C in sodium hydroxide, immerses concentration 4mol/L according to solid and liquid weight ratio 1:3 at 100 DEG C after centrifuge separation
Sulfuric acid solution in 0.5h, filter, drying then calcines 2h at 300 DEG C, the attapulgite purified;By amino graphene
Ultrasonic disperse obtains the amino graphene solution that concentration is 0.1wt% in deionized water, and the amino graphene solution is dripped
It is added in the attapulgite of purifying, the envelope-bulk to weight ratio of the graphene solution and the attapulgite is 6mL:10g, then 75
Drying is at DEG C to get the amino graphene coated attapulgite.
Embodiment 3
A kind of solid union electrolyte includes: aqueous polyurethane 90%, double fluorine sulfimide lithiums 8% by weight percentage
With amino graphene coated attapulgite 2%.It include: by above-mentioned weight when the solid union electrolyte is prepared into dielectric film
Above-mentioned property of water-bearing polyurethane and amino graphene coated attapulgite are mixed and stirred for by percentage, obtain polyurethane composition,
Double fluorine sulfimide lithiums are added into the polyurethane composition, obtain the polyurethane composition lotion of lithium doping, then in vacuum
Under the conditions of, dry 25h is at 80 DEG C to get solid union dielectric film.
Wherein, the aqueous polyurethane synthesizes obtain with the following method: by weight by poly- (carbonic acid 1,6- hexylene glycol
Ester) 50 parts of glycol, 30 parts of toluene di-isocyanate(TDI) react 4h at 80 DEG C, add 5 parts of dihydromethyl propionic acid, NMP and organic
0.05 part of zinc, the reaction was continued at 80 DEG C 2.5h, 3 parts of neutralization reactions of triethylamine are added after being cooled to 35 DEG C, add 200 parts of water
The high-speed stirred under 4000r/min rate removes NMP to get the aqueous polyurethane;
The amino graphene coated attapulgite is by mixing amino graphene solution with the attapulgite of purifying
Drying obtains afterwards, specifically, graphene oxide is dissolved in NMP, adds ethylenediamine, the weight of ethylenediamine and graphene oxide
Than after being stirred to react 4h at 80 DEG C, reducing agent NaBH is added for 1:104, reducing agent NaBH4With the weight ratio of graphene oxide
For 1.5:1, it is stirred to react 4h at 95 DEG C, filters, washing obtains amino graphene;Attapulgite is pulverized Hou Jiashui
Modulation obtain concentration be 25wt% ore pulp solution, on the basis of attapulgite be added 1.5wt% calgon and
0.8h is stirred by ultrasonic at 40 DEG C in the sodium hydroxide of 0.7wt%, immerses at 105 DEG C according to solid and liquid weight ratio 1:2 after centrifuge separation
0.3h in the sulfuric acid solution of concentration 5mol/L is filtered, drying, then calcines 1.5h at 350 DEG C, the attapulgite purified;
Amino graphene ultrasonic disperse is obtained into the amino graphene solution that concentration is 0.2wt% in deionized water, by the amino
Graphene solution is added dropwise in the attapulgite of purifying, and the envelope-bulk to weight ratio of the graphene solution and the attapulgite is
3mL:10g, then dry at 90 DEG C to get the amino graphene coated attapulgite.
Embodiment 4
A kind of solid union electrolyte includes: aqueous polyurethane 87%, lithium hexafluoro phosphate 9% and ammonia by weight percentage
Base graphene coated attapulgite 4%.It include: by above-mentioned weight percent when the solid union electrolyte is prepared into dielectric film
Than above-mentioned property of water-bearing polyurethane and amino graphene coated attapulgite to be mixed and stirred for, polyurethane composition is obtained, to institute
It states and lithium hexafluoro phosphate is added in polyurethane composition, obtain the polyurethane composition lotion of lithium doping, then under vacuum conditions, 90
Dry 28h is at DEG C to get solid union dielectric film.
Wherein, the aqueous polyurethane synthesizes obtain with the following method: by weight by poly- (carbonic acid 1,10- decanediol
Ester) 35 parts of glycol, 18 parts of 4,4'- methyl diphenylene diisocyanate react 4h at 90 DEG C, add dimethylolpropionic acid 4
Part, NMP and 0.06 part of organic zinc, 4 parts of neutralization reactions of triethylamine are added in the reaction was continued at 75 DEG C 2.5h after 40 DEG C of cooling, then
180 parts of high-speed stirreds under 5000r/min rate of water are added, remove NMP to get the aqueous polyurethane;
The amino graphene coated attapulgite is by mixing amino graphene solution with the attapulgite of purifying
Drying obtains afterwards, specifically, graphene oxide is dissolved in NMP, adds ethylenediamine, the weight of ethylenediamine and graphene oxide
Than after being stirred to react 4.5h at 75 DEG C, reducing agent NaBH is added for 1:124, reducing agent NaBH4With the weight of graphene oxide
Than being stirred to react 4.5h at 98 DEG C for 1.8:1, filter, washing obtains amino graphene;After attapulgite is pulverized
Add water to modulate to obtain the ore pulp solution that concentration is 28wt%, be added on the basis of attapulgite 1.6wt% calgon and
0.7h is stirred by ultrasonic at 45 DEG C in the sodium hydroxide of 0.8wt%, soaks at 100 DEG C according to solid and liquid weight ratio 1:2.5 after centrifuge separation
Enter 0.2h in the sulfuric acid solution of concentration 6mol/L, filters, drying, then 1.8h is calcined at 360 DEG C, the concave convex rod purified
Soil;Amino graphene ultrasonic disperse is obtained into the amino graphene solution that concentration is 0.3wt% in deionized water, by the ammonia
Base graphene solution is added dropwise in the attapulgite of purifying, and the envelope-bulk to weight ratio of the graphene solution and the attapulgite is
4mL:10g, then dry at 80 DEG C to get the amino graphene coated attapulgite.
Embodiment 5
A kind of solid union electrolyte includes: aqueous polyurethane 92%, 7% and of dioxalic acid lithium borate by weight percentage
Amino graphene coated attapulgite 1%.It include: by above-mentioned weight hundred when the solid union electrolyte is prepared into dielectric film
Point than above-mentioned property of water-bearing polyurethane and amino graphene coated attapulgite to be mixed and stirred for, polyurethane composition is obtained, to
Dioxalic acid lithium borate is added in the polyurethane composition, obtains the polyurethane composition lotion of lithium doping, then in vacuum condition
Under, dry 28h is at 80 DEG C to get solid union dielectric film;
Wherein, the aqueous polyurethane synthesizes obtain with the following method: by weight by poly- (carbonic acid 1,6- hexylene glycol
Ester) 40 parts of glycol, 20 parts of 4,4'- dicyclohexyl methyl hydride diisocyanate react 3.5h at 75 DEG C, add dihydroxymethyl fourth
5 parts of acid, NMP and 0.08 part of stannous octoate, the reaction was continued at 85 DEG C 2.8h, 5 parts of triethylamine neutralizations of addition after being cooled to 30 DEG C
Reaction adds 220 parts of high-speed stirreds under 4000r/min rate of water, removes NMP to get the aqueous polyurethane;
The amino graphene coated attapulgite is by mixing amino graphene solution with the attapulgite of purifying
Drying obtains afterwards, specifically, graphene oxide is dissolved in NMP, adds ethylenediamine, the weight of ethylenediamine and graphene oxide
Than after being stirred to react 3.5h at 80 DEG C, reducing agent NaBH is added for 1:114, reducing agent NaBH4With the weight of graphene oxide
Than being stirred to react 4.5h at 98 DEG C for 1.6:1, filter, washing obtains amino graphene;After attapulgite is pulverized
Add water to modulate to obtain the ore pulp solution that concentration is 29wt%, be added on the basis of attapulgite 1.3wt% calgon and
0.5h is stirred by ultrasonic at 50 DEG C in the sodium hydroxide of 0.9wt%, immerses at 105 DEG C according to solid and liquid weight ratio 1:1 after centrifuge separation
0.5h in the sulfuric acid solution of concentration 7mol/L is filtered, drying, then calcines 1.2h at 380 DEG C, the attapulgite purified;
Amino graphene ultrasonic disperse is obtained into the amino graphene solution that concentration is 0.2wt% in deionized water, by the amino
Graphene solution is added dropwise in the attapulgite of purifying, and the envelope-bulk to weight ratio of the graphene solution and the attapulgite is
3mL:10g, then dry at 95 DEG C to get the amino graphene coated attapulgite.
Conductivity test is carried out at different temperatures to the dielectric film that the above embodiments 1-5 is obtained.Test method is
AC impedence method, the AC impedance at a temperature of measuring 25-100 DEG C by electrochemical workstation, frequency range from 100KHz to
0.01Hz, disturbance voltage 10mV;Recycle formula σ=L/ (R × S) that Conductivity Results data are calculated as shown in table 1.Its
Middle σ is ionic conductivity, and L is the thickness of dielectric film, and R is the resistance value of dielectric film, and S is dielectric film and stainless steel electrode
Contact area.The dielectric film that embodiment 1-5 is obtained it can be seen from 1 data of table has all reached at 100 DEG C or less can be practical
The conductivity level of change provides good application prospect for the preparation of lithium ion battery.
The ionic conductivity of the dielectric film of 1 embodiment 1-5 of table preparation at different temperatures
Further, tensile strength test is carried out to the dielectric film that the above embodiments 1-5 is obtained, as a result such as 2 institute of table
Show:
The tensile strength properties of the dielectric film of 2 embodiment 1-5 of table preparation
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art within the technical scope of the present invention, according to the technique and scheme of the present invention and its invents
It is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of solid union electrolyte, which is characterized in that its raw material include: by weight percentage aqueous polyurethane 85-95%,
Lithium salts 1-10% and amino graphene coated attapulgite 1-5%.
2. solid union electrolyte according to claim 1, which is characterized in that the amino graphene coated attapulgite is
It is obtained by being dried after mixing amino graphene solution with the attapulgite of purifying.
3. solid union electrolyte according to claim 1 or claim 2, which is characterized in that the amino graphene has for surface
The amination modified graphene of amino group.
4. the solid union electrolyte according to Claims 2 or 3, which is characterized in that the method for purifying attapulgite include: by
Attapulgite powder adds water to modulate after obtaining ore pulp solution, calgon and sodium hydroxide ultrasonic agitation is added, after centrifuge separation
Sulfuric acid solution is immersed, is filtered, the attapulgite to get purifying is calcined.
5. any one of -4 solid union electrolyte according to claim 1, which is characterized in that the synthesis of the aqueous polyurethane
Raw material includes: 35-65 parts of aliphatic polycarbonate diol, 18-40 parts of diisocyanate, hydrophilic chain extender 2- by weight
8 parts, 1-5 parts of triethylamine, 0.01-0.1 parts of catalyst, 150-250 parts of water;Preferably, the aliphatic polycarbonate diol
For poly- (carbonic acid 1,4-butanediol ester) glycol, poly- (carbonic acid 1,5-PD ester) glycol, poly- (carbonic acid 1,6- hexylene glycol ester) glycol
Or one of poly- (carbonic acid 1,10- decanediol ester) glycol or a variety of;The diisocyanate be isophorone diisocyanate,
Hexamethylene diisocyanate, toluene di-isocyanate(TDI), 4,4'- methyl diphenylene diisocyanate or 4,4'- dicyclohexyl first
One of alkane diisocyanate is a variety of;The hydrophilic chain extender is dihydromethyl propionic acid or dimethylolpropionic acid;It is described
Catalyst is one of stannous octoate, di-n-butyltin dilaurate, organic zinc or organo-bismuth or a variety of.
6. solid union electrolyte according to claim 5, which is characterized in that synthesize the method packet of the aqueous polyurethane
Include: by aliphatic polycarbonate diol, diisocyanate carry out prepolymerization reaction, add hydrophilic chain extender, organic solvent and
The reaction was continued for catalyst, and triethylamine neutralization reaction is added after cooling, adds water high-speed stirred, removes the organic solvent, i.e.,
Obtain the aqueous polyurethane;Preferably, diisocyanate, aliphatic polycarbonate diol are 1.5- according to NCO/OH ratio
2.0 carry out prepolymerization reaction.
7. any one of -6 solid union electrolyte according to claim 1, which is characterized in that the lithium salts be lithium perchlorate,
One in bis trifluoromethyl sulfimide lithium, double fluorine sulfimide lithiums, lithium hexafluoro phosphate, dioxalic acid lithium borate or LiBF4
Kind is a variety of.
8. a kind of method that any one of -7 solid union electrolyte prepare dielectric film according to claim 1, feature exist
In, comprising: aqueous polyurethane and amino graphene coated attapulgite are mixed and stirred for, polyurethane composition is obtained, to institute
It states and lithium salts is added in polyurethane composition, obtain the polyurethane composition of lithium doping, then dry film forming to get solid union electrolysis
Plasma membrane.
9. the preparation method of dielectric film according to claim 8, which is characterized in that the process for drying film forming includes: true
Under empty condition, dry 20-30h at 60-100 DEG C.
10. a kind of application of solid union dielectric film of the preparation of method according to claim 8 or claim 9 in lithium battery.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811346058.6A CN109585910B (en) | 2018-11-13 | 2018-11-13 | Solid composite electrolyte and preparation method and application of electrolyte membrane thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811346058.6A CN109585910B (en) | 2018-11-13 | 2018-11-13 | Solid composite electrolyte and preparation method and application of electrolyte membrane thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109585910A true CN109585910A (en) | 2019-04-05 |
CN109585910B CN109585910B (en) | 2021-06-18 |
Family
ID=65922194
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811346058.6A Active CN109585910B (en) | 2018-11-13 | 2018-11-13 | Solid composite electrolyte and preparation method and application of electrolyte membrane thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109585910B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112421106A (en) * | 2020-11-23 | 2021-02-26 | 浙江锋锂新能源科技有限公司 | Composite film capable of prolonging cycle life of lithium battery and preparation method thereof |
CN117987067A (en) * | 2024-03-29 | 2024-05-07 | 四川汇利实业有限公司 | Preparation method of polyurethane adhesive for medicine packaging composite film and composition of polyurethane adhesive |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103232584A (en) * | 2013-04-23 | 2013-08-07 | 东莞长联新材料科技股份有限公司 | High-performance environment-friendly type water-borne polyurethane and preparation method thereof |
CN103357380A (en) * | 2013-07-18 | 2013-10-23 | 江苏澳特邦非金属矿业有限公司 | Preparation method of absorptive decolorant special for rapeseed oil refining |
CN104852085A (en) * | 2015-05-06 | 2015-08-19 | 深圳高远通新材料科技有限公司 | Graphene polymer electrolyte and preparation method thereof |
CN105684207A (en) * | 2013-11-05 | 2016-06-15 | 索尼公司 | Battery, separator, electrode, paint, battery pack, electronic apparatus, electric vehicle, electricity storage device, and power system |
CN106549186A (en) * | 2016-12-02 | 2017-03-29 | 中国科学院广州能源研究所 | The preparation method of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte |
CN106711502A (en) * | 2016-12-29 | 2017-05-24 | 中国科学院过程工程研究所 | Inorganic composite nanoparticle, as well as preparation method thereof, and application of inorganic composite nanoparticle to all-solid-state lithium ion battery |
CN107417872A (en) * | 2017-07-24 | 2017-12-01 | 合肥思敬齐化工材料有限责任公司 | A kind of preparation method of high crosslinking ultraviolet light solidfication water polyurethane |
CN107799699A (en) * | 2017-09-21 | 2018-03-13 | 中国科学院兰州化学物理研究所 | A kind of clay mineral composite lithium battery membrane and preparation method thereof |
CN108075118A (en) * | 2017-12-01 | 2018-05-25 | 江苏海四达电源股份有限公司 | A kind of sulfur-based positive electrode material and preparation method thereof, lithium battery anode and lithium battery |
CN108400380A (en) * | 2018-04-24 | 2018-08-14 | 珠海光宇电池有限公司 | A kind of preparation method and lithium ion battery of composite polymer electrolyte membrane |
-
2018
- 2018-11-13 CN CN201811346058.6A patent/CN109585910B/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103232584A (en) * | 2013-04-23 | 2013-08-07 | 东莞长联新材料科技股份有限公司 | High-performance environment-friendly type water-borne polyurethane and preparation method thereof |
CN103357380A (en) * | 2013-07-18 | 2013-10-23 | 江苏澳特邦非金属矿业有限公司 | Preparation method of absorptive decolorant special for rapeseed oil refining |
CN105684207A (en) * | 2013-11-05 | 2016-06-15 | 索尼公司 | Battery, separator, electrode, paint, battery pack, electronic apparatus, electric vehicle, electricity storage device, and power system |
US20160254511A1 (en) * | 2013-11-05 | 2016-09-01 | Sony Corporation | Battery, separator, electrode, coating material, battery pack, electronic apparatus, electrically driven vehicle, electrical storage device, and electric power system |
CN104852085A (en) * | 2015-05-06 | 2015-08-19 | 深圳高远通新材料科技有限公司 | Graphene polymer electrolyte and preparation method thereof |
CN106549186A (en) * | 2016-12-02 | 2017-03-29 | 中国科学院广州能源研究所 | The preparation method of attapulgite hydridization polymethyl methacrylate lithium battery gel electrolyte |
CN106711502A (en) * | 2016-12-29 | 2017-05-24 | 中国科学院过程工程研究所 | Inorganic composite nanoparticle, as well as preparation method thereof, and application of inorganic composite nanoparticle to all-solid-state lithium ion battery |
CN107417872A (en) * | 2017-07-24 | 2017-12-01 | 合肥思敬齐化工材料有限责任公司 | A kind of preparation method of high crosslinking ultraviolet light solidfication water polyurethane |
CN107799699A (en) * | 2017-09-21 | 2018-03-13 | 中国科学院兰州化学物理研究所 | A kind of clay mineral composite lithium battery membrane and preparation method thereof |
CN108075118A (en) * | 2017-12-01 | 2018-05-25 | 江苏海四达电源股份有限公司 | A kind of sulfur-based positive electrode material and preparation method thereof, lithium battery anode and lithium battery |
CN108400380A (en) * | 2018-04-24 | 2018-08-14 | 珠海光宇电池有限公司 | A kind of preparation method and lithium ion battery of composite polymer electrolyte membrane |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112421106A (en) * | 2020-11-23 | 2021-02-26 | 浙江锋锂新能源科技有限公司 | Composite film capable of prolonging cycle life of lithium battery and preparation method thereof |
CN117987067A (en) * | 2024-03-29 | 2024-05-07 | 四川汇利实业有限公司 | Preparation method of polyurethane adhesive for medicine packaging composite film and composition of polyurethane adhesive |
Also Published As
Publication number | Publication date |
---|---|
CN109585910B (en) | 2021-06-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Cao et al. | Strategies of regulating Zn 2+ solvation structures for dendrite-free and side reaction-suppressed zinc-ion batteries | |
CN109638349A (en) | A kind of organic-inorganic nanocomposite solid electrolyte diaphragm and its preparation method and application | |
CN107039680A (en) | Solid electrolyte and the lithium battery for including the solid electrolyte | |
CN108878959A (en) | A kind of preparation and its application of organo-mineral complexing solid electrolyte | |
JP2009016090A (en) | High ion-conductive solid electrolyte, its manufacturing method, and electrochemical system utilizing this solid electrolyte | |
CN113330608A (en) | Electrode with electrode additive for high performance batteries and use thereof | |
CN106785029B (en) | Pluronic block copolymer-based hydrogel electrolyte and application thereof | |
Bhattacharyya | Ion transport in liquid salt solutions with oxide dispersions:“Soggy Sand” electrolytes | |
Wang et al. | Vinyl-functionalized imidazolium ionic liquids as new electrolyte additives for high-voltage Li-ion batteries | |
CN109585910A (en) | A kind of solid union electrolyte and its dielectric film preparation method and application | |
CN107317049A (en) | A kind of single ion conductive polymer electrolyte and its production and use | |
CN111180790B (en) | Polymer electrolyte, preparation method thereof and solid-state lithium-air battery | |
CN109728342A (en) | A kind of selfreparing composite solid electrolyte, quasi-solid electrolyte and lithium battery | |
CN112670543A (en) | Composite solid electrolyte membrane based on hollow MOF (metal organic framework) and preparation method and application thereof | |
Song et al. | An examination and prospect of stabilizing Li metal anode in lithium–sulfur batteries: A review of latest progress | |
Getie et al. | Development of electrolytes for rechargeable zinc-air batteries: Current progress, challenges, and future outlooks | |
KR101681297B1 (en) | All solid lithium secondary batteries and method for manufacturing the same | |
Zhang et al. | Design of co-continuous structure of cellulose/PAA-based alkaline solid polyelectrolyte for flexible zinc-air battery | |
Chen et al. | Abundant Hydrogen Bonds Formed in a Urea‐Based Gel Polymer Electrolyte Improve Interfacial Stability in Lithium Metal Batteries | |
CN105870442A (en) | Electrochemical energy storage device | |
CN109585916A (en) | A kind of flame-retardant polymer solid electrolyte material and its dielectric film and application | |
KR102539971B1 (en) | Solid Electrolyte Composition, Preparation Method thereof, and Battery Comprising the Same | |
CN101924245A (en) | Preparation method of polyphosphazene urethane single ion solid electrolyte | |
CN114843594A (en) | Sodium ion composite solid electrolyte, preparation method thereof and battery | |
Kufian et al. | Prospects and challenges in the selection of polymer electrolytes in advanced lithium–air batteries |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |