CN104744722B - Porous self-cross linking type polymer film and preparation method, the electrolyte obtained by the film and its in the application of lithium ion battery - Google Patents
Porous self-cross linking type polymer film and preparation method, the electrolyte obtained by the film and its in the application of lithium ion battery Download PDFInfo
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Abstract
The invention discloses a kind of porous self-cross linking type polymer film, by pure-acrylic emulsion and the mixing of modified poly (ethylene glycol) solution, it is crosslinked and carries out pore-creating and obtain；The hydroxyl at polyethylene glycol both ends obtains the modified poly (ethylene glycol) by methoxy substitution；The pore-creating is to contact self-cross linking type polymer film with polyethylene glycol good solvent.The porosity of the porous self-cross linking type gelatin polymer film is 40 70%.On this basis, it gives the preparation method of the film and makees the lithium ion battery of electrolyte using the film.Prepare porous self-cross linking type gel polymer electrolyte film be suitable for lithium ion battery electrolyte use, impedance is low, ionic conductivity is high, high power charging-discharging when be not easy to polarize.
Description
Technical field
The present invention relates to the preparation method of a kind of porous self-cross linking type polymer film and the film, further relate to be obtained by the film
The application of the electrolyte arrived and the electrolyte in lithium ion battery, belongs to technical field of lithium ion.
Background technology
The energy density of conventional lithium ion battery is low, electrolyte is easy to reveal, therefore easily causes safety problem.It is emerging in recent years
The gel polymer electrolyte risen, lithium ion transmission speed is fast, and its matrix can adsorb a large amount of liquid electrolytes, be not easy
Liquid leakage occurs, therefore gradual alternative electrolyte is used in lithium ion battery.
Currently, the gel polymer electrolyte of lithium ion battery mainly has Kynoar and vinylidene-hexafluoro third
Alkene copolymer, charge/discharge rates are fast, good mechanical property.But Kynoar and vinylidene-hexafluoropropylene copolymer with
The compatibility of electrolyte is poor, and the ability for adsorbing liquid electrolyte is weak, be easy to cause battery liquid leakage, and above-mentioned two gellike
Polyeletrolyte and interelectrode interface resistance are big, can not stablize with electrode compatible.
In order to overcome Kynoar and the above-mentioned of vinylidene-hexafluoropropylene copolymer gel polymer electrolyte to lack
Point is had and is modified to above-mentioned two substance using polymethyl methacrylate.Such as Chinese patent literature CN101062987A
A kind of porous type polymer electrolyte film is disclosed, is the Kynoar of 33-54%, 3-15% containing mass percent
The 1M lithium hexafluoro phosphate carbonate electrolytes of acrylonitrile-methacylate poly glycol monomethyl ether ester copolymer, 43-52%.It prepares
Step is synthesis of acrylonitrile-Methylacrylic acid polyethylene glycol single armor ether ester copolymer first, is then total to itself and Kynoar
It is mixed to be dissolved in n,N-dimethylacetamide solvent, porous membrane is obtained by immersion precipitation, then adsorb lithium hexafluoro phosphate carbonic acid
Ester electrolyte is made.Gel polymer electrolyte ionic conductivity height, good mechanical property in the technology, receive the energy of electrolyte
Power and simple polyvinylidene fluoride olefinic substance compared with the compatibility of electrode have certain improve；But due to gelatin polymer electricity
It is still to receive electrolyte ability and still not high, the Er Qieshang with the compatibility of electrode using Kynoar as matrix to solve matter
Serious problem of phase separation can be occurred in use for some time by stating the gel polymer electrolyte in technology, lead to making for battery
Use reduced performance.
Due to above-mentioned using Kynoar or vinylidene-hexafluoropropylene copolymer as the gel polymer electrolyte of matrix
Exist and receive electrolyte ability low and the shortcomings that with electrode poor compatibility, thus there is researcher to be considered as completely new substance body
It is the electrolyte ingredient as lithium ion battery.Since the common electrolyte of polyacrylate substance and lithium ion battery has
Similar functional group receives the ability of electrolyte strong, and the functional group of polyacrylate and electrode component compatibility are good,
So that interface impedance is low between polyacrylate and electrode, compatibility is good, so that polyacrylate gelatin polymer is made
It is interesting for the research of lithium ion battery electrolyte.As Chinese patent literature CN1317512A disclose a kind of gel state lithium from
The preparation method of sub- polymer electrolyte and battery, using series of acrylate derivative as monomer, and crosslinking agent is in warm
Initiator causes the lower thermochemical crosslinking method that passes through and forms polyacrylate, and polyacrylate further forms poly- third with electrolyte
Olefin(e) acid gels gel polymer electrolyte, the electrolyte that can be used as lithium ion battery use.
Above-mentioned technology is successfully used using polyacrylate gelatin polymer as lithium ion battery electrolyte, is overcome
This field all the time using Kynoar or vinylidene-hexafluoropropylene copolymer as gel polymer electrolyte matrix when,
It is existing to receive electrolyte ability low and the shortcomings that with electrode poor compatibility；But due to the polyacrylate in above-mentioned technology
Gel polymer electrolyte ontology impedance is higher, and ionic conductivity is low, causes battery in the pole of high power charging-discharging
Change effect is big, and the performance of battery is low.
For how to reduce the ontology impedance of polyacrylate gel polymer electrolyte, to improve with polyacrylic acid
Ester is as this technical problem of the performance of the lithium ion battery of polymer electrolyte matrix, those skilled in the art
It can not find suitable solution always.
Invention content
The technical problem to be solved by the present invention is to polyacrylate gel polymer electrolyte ontology impedance is higher, lead
The performance for sending a telegraph pond is low, and those skilled in the art can not find always suitable method and go to reduce polyacrylate
The impedance of gel polymer electrolyte；And then propose that a kind of impedance is low, ionic conductivity is high, high rate capability is good by high hole
The porous self-cross linking type gel polymer electrolyte that the porous self-cross linking type gelatin polymer film of rate obtains.
On this basis, the invention also provides the lithium-ion electrics for using porous self-cross linking type gel polymer electrolyte
Pond.
In order to solve the above technical problems, the present invention provides a kind of porous self-cross linking type gelatin polymer film,
By pure-acrylic emulsion and the mixing of modified poly (ethylene glycol) solution, it is crosslinked and carries out pore-creating and obtain；
The hydroxyl at polyethylene glycol both ends obtains the modified poly (ethylene glycol) by methoxy substitution.
The pore-creating is that the self-cross linking type polymer film for obtaining crosslinking is contacted with polyethylene glycol good solvent.
The polyethylene glycol good solvent is water, solvent or lithium-ion battery electrolytes in lithium-ion battery electrolytes.
The electrolyte is made of lithium salts and solvent, a concentration of 0.8~1.5mol/L of the lithium salts.
The porosity of the porous self-cross linking type gelatin polymer film is 40-70%.
The glass transition temperature of the pure-acrylic emulsion is -30-70 DEG C.
The glass transition temperature of the pure-acrylic emulsion is -18-60 DEG C.
The weight average molecular weight of the polyethylene glycol is less than 100,000 g/mol.
The weight average molecular weight of the polyethylene glycol is ten thousand g/mol of 100-5.
The solid content of the pure-acrylic emulsion is 40-60wt%, and the solid content of the modified poly (ethylene glycol) solution is 5-80wt%,
The solid weight of the modified poly (ethylene glycol) solution is the 1-50wt% of the pure-acrylic emulsion solid weight.
The solid weight of the modified poly (ethylene glycol) solution is the 5-30wt% of the pure-acrylic emulsion solid weight.
Film thickness is 0.01-110 μm.
Using the porous self-cross linking type gel polymer electrolyte of the porous self-cross linking type gelatin polymer film, by porous
Self-cross linking type gelatin polymer film contact electrolyte obtains.
The conductivity of the porous self-cross linking type gel polymer electrolyte is 7-8.5mS/cm.
The preparation method of the porous self-cross linking type gelatin polymer film, includes the following steps,
(1) it is methoxyl group by the hydroxyl modification at polyethylene glycol both ends, obtains modified poly (ethylene glycol) and wiring solution-forming；
(2) modified poly (ethylene glycol) solution, pure-acrylic emulsion are uniformly mixed, forms mixed liquor；
(3) mixed liquor is coated on electrode surface, forms uncrosslinked film；
(4) the uncrosslinked film is toasted at 20-50 DEG C, forms self-cross linking type polymer film；
(5) after being dried in vacuo the self-cross linking type polymer film, it is good under dry oxygen-free environment to be soaked in polyethylene glycol
In solvent, taking-up.
Step（4）In baking time be 0.01-24h, baking temperature be 30-50 DEG C.
Vacuum drying temperature is 30-50 DEG C, time 10-30h；Soaking time is no less than for 24 hours.
The porous self-cross linking type method for preparing gel polymer electrolyte, by dry porous self-cross linking type gel
Polymer film is soaked in electrolyte in an inert atmosphere, taking-up.
Using the lithium ion battery of the porous self-cross linking type gelatin polymer film, including,
The battery case internal body portion is divided into positive conversion zone and negative reaction by battery groove body and diaphragm, the diaphragm
Region；
Anode is set in the positive conversion zone；
Cathode is set in the negative reaction region；
Electrolyte is filled in the positive conversion zone and negative reaction region；
The porous self-cross linking type gelatin polymer film be set to it is described anode and cathode between, and with it is described anode and it is negative
Pole is in contact；
The anode, cathode, diaphragm and porous self-cross linking type gelatin polymer film immersion are in the electrolyte.
Pure-acrylic emulsion used in the present invention is the lotion for being generally used for making coating in the prior art, is by polypropylene
Acid ester monomer, crosslinking agent, emulsifier and water mixing copolymerization formed with polyacrylate lotion as main component, wherein poly- third
Olefin(e) acid ester monomer is acrylate or derivatives thereof.
The present invention has the advantages that compared with prior art：
（1）Porous self-cross linking type gelatin polymer film of the present invention, it is equal by pure-acrylic emulsion and modified poly (ethylene glycol) solution
Even mixing is crosslinked and obtains porous self-cross linking type gelatin polymer film after contacting immersion with polyethylene glycol good solvent.In order to prevent
Polyethylene glycol participates in self-crosslinking reaction, and the hydroxyl modification at polyethylene glycol both ends is become methoxyl group first, is modified by the application
Polyethylene glycol, by by the mixed liquor heat cross-linking of pure-acrylic emulsion, modified poly (ethylene glycol) solution so that mixture crosslinks,
Three-dimensional crosslinked network structure is formed, modified poly (ethylene glycol) is blended in wherein, is then dissolved and changed using polyethylene glycol good solvent
Property polyethylene glycol, hole will be left on the position that modified poly (ethylene glycol) dissolves, it is poly- to form porous self-cross linking type gel
Compound film, the porous structure so that the gel polymer electrolyte ionic conductivity using the film greatly improves, impedance is dropped significantly
Low, to make, the high rate performance of assembled battery greatly improves, and avoids polyacrylate gel electrostrictive polymer in the prior art
It is higher to solve matter ontology impedance, causes the performance of battery low, and those skilled in the art can not find always suitable side
Method goes the problem of reducing polyacrylate impedance.
（2）The solid content of porous self-cross linking type gelatin polymer film of the present invention, the pure-acrylic emulsion is 40-60wt%,
The solid content of the modified poly (ethylene glycol) solution is 5-80wt%, and the solid weight of the modified poly (ethylene glycol) solution is described pure
The 1-50wt% of acrylic emulsion solid weight.The mixed liquor that above-mentioned solid content, the pure-acrylic emulsion of ratio, polyglycol solution are formed is handed over
Finally formed porous self-cross linking type gelatin polymer film after connection, with electrolyte, electrode compatibility more preferably, further reduce
The generation of battery leakage problem further reduced the impedance between electrolyte and interface.
（3）Porous self-cross linking type gelatin polymer film of the present invention, film thickness are 0.01-110 μm, are soaked by electrolyte
Porous self-cross linking type gel polymer electrolyte obtained can form the film of any thickness as needed after stain, applied widely
Lithium ion battery that is general, can be used for making existing any capacity.
（4）The preparation method of porous self-cross linking type gelatin polymer film of the present invention, by the hydroxyl at polyethylene glycol both ends
It is modified as methyl, obtains modified poly (ethylene glycol) and wiring solution-forming；Modified poly (ethylene glycol) solution, pure-acrylic emulsion are uniformly mixed, shape
At mixed liquor；Mixed liquor is coated on electrode surface and forms uncrosslinked film, uncrosslinked film is toasted to crosslinking at 20-50 DEG C, it
It is soaked under confined conditions in polyethylene glycol good solvent in ambiance afterwards and porous self-cross linking type gelatin polymer film is made.It should
Method is simple, easy to operate, and energy consumption is very low, greatly reduces production cost, while obtained porous self-cross linking type gel polymerisation
The ontology impedance of object electrolyte is low, conductivity is high.
（5）In lithium ion battery of the present invention using porous self-cross linking type gel polymer electrolyte, porous selfing
Connection type gel polymer electrolyte can be arranged between a positive electrode and a negative electrode, and be in contact with anode and cathode, be preferably provided at
On any surface of one or several components in the positive electrode, the negative electrode and the separator or on all surface.
Description of the drawings
In order to make present disclosure be more easily understood, present invention combination the drawings and specific embodiments are to the present invention's
Content is further detailed；
Fig. 1 is the stereoscan photograph of porous self-cross linking type gelatin polymer film described in the embodiment of the present invention 2；
Specific implementation mode
Embodiment 1
(1) it is methoxyl group by the polyethylene glycol both ends hydroxyl modification of 80,000 g/mol of weight average molecular weight, it is poly- obtains bi-methoxy
Ethylene glycol；Its method of modifying is as follows：
The metallic sodium of 0.002mol is first added into the polyethylene glycol of 0.001mol, reaction generates polyethylene glycol sodium and releases
The polyethylene glycol sodium of obtained 0.001mol is carried out Williamson with the methyl iodide of 0.002mol and synthesized, obtained double by hydrogen
Methoxy poly (ethylene glycol).
（2）The Varonic DM 55 for being 11wt% by pure-acrylic emulsion A, 18g solid content that 100g solid contents are 40wt%
Solution uniformly mixes, and forms mixed liquor；
The pure-acrylic emulsion A is mixed by the P1005 of the P1040 and 50g of 50g, and P1040 and P1005 are Shanghai love
The pure-acrylic emulsion product that high Chemical Co., Ltd. sells, through being furnished with cryogenic system（FT100）METTLER DSC823e test,
The glass transition temperature of P1040 and P1005 is respectively 54 DEG C and -12 DEG C, calculates the vitrifying temperature of pure-acrylic emulsion A according to the following equation
Degree is 17 DEG C.
Wherein, W1For the mass fraction of P1040 in pure-acrylic emulsion A, W2For the mass fraction of P1005 in pure-acrylic emulsion A, Tg1
For the glass transition temperature of P1040（Kelvin degree）, Tg2For the glass transition temperature of P1005（Kelvin degree）, Tg is pure third breast
The glass transition temperature of liquid A（Kelvin degree）.
(3) mixed liquor is coated on 100 μm of thickness on lithium ion battery positive plate, negative plate and PTFE plates
Form uncrosslinked film；
(4) the uncrosslinked film comprising positive plate and negative plate is cut into the disk of a diameter of 13mm, by PTFE plates not
Cross linking membrane strips down the disk for being cut into a diameter of 17mm, and is put in again on PTFE plates, then by positive plate, negative plate and
Uncrosslinked film on PTFE plates（Cut out disk）It is toasted at 20 DEG C for 24 hours, forms self-cross linking type polymer film；
(5) by above-mentioned self-cross linking type polymer film（Film on PTFE plates need to be taken off）After being immersed in water for 24 hours, at 30 DEG C
After lower dry 30h, respectively obtain positive plate, negative plate and porous self-cross linking type gelatin polymer film Ca1, the Cb1 of self-supporting and
Cc1；
(6) by the porous self-cross linking type gelatin polymer film in 1x10-3Pa, at 30 DEG C after vacuum drying 30h, it is rapid to turn
It moves on in the glove box full of argon gas, and Cc1 is soaked in electrolyte for 24 hours, the electrolyte liquid is 1 by volume ratio：1：1
After EC/EMC/DMC mixing, the LiPF of 2.5wt%VC and 1mol/L is added6Composition, it is to obtain porous self-cross linking type gel to gather to take out
Polymer electrolyte Mc1；
The lithium piece negative electrode for being kept apart the positive electrode and a diameter of 16mm that are covered with Ca1 in battery case body using diaphragm, is added
Enter electrolyte sealing into 2016 type Li/LiCoO2Polymer Li-ion battery 1.
Embodiment 2
(1) it is methoxyl group by the polyethylene glycol both ends hydroxyl modification of 50,000 g/mol of weight average molecular weight, it is poly- obtains bi-methoxy
Ethylene glycol, specific method are shown in embodiment 1；
(2) Varonic DM 55 for pure-acrylic emulsion B, 50g solid content 18wt% that 100g solid contents are 60wt% is molten
Liquid uniformly mixes, and forms mixed liquor；
The pure-acrylic emulsion B is mixed by the P1005 of the P1040 and 20g of 80g, the glass of mixed pure-acrylic emulsion B
It is 38 DEG C to change temperature, and product producer and temperature computation method are the same as embodiment 1.
(3) mixed liquor is coated on 100 μm of thickness on lithium ion battery positive plate, negative plate and PTFE plates
Form uncrosslinked film；
(4) the uncrosslinked film comprising positive plate and negative plate is cut into the disk of a diameter of 13mm, by PTFE plates not
Cross linking membrane strips down the disk for being cut into a diameter of 17mm, and is put in again on PTFE plates, then by positive plate, negative plate and
Uncrosslinked film on PTFE plates（Cut out disk）0.01h is toasted at 50 DEG C, forms self-cross linking type polymer film；
(5) by above-mentioned self-cross linking type polymer film（Film on PTFE plates need to be taken off）In ambiance air-proof condition
Under be soaked in DMC for 24 hours, at 30 DEG C be dried in vacuo 30h after, respectively obtain positive plate, negative plate and the porous selfing of self-supporting
Connection type gelatin polymer film Ca2, Cb2 and Cc2；
(6) by the porous self-cross linking type gelatin polymer film in 1x10-3Pa, at 30 DEG C after vacuum drying 30h, it is rapid to turn
It moves on in the glove box full of argon gas, and Cc2 is soaked in electrolyte for 24 hours, the electrolyte liquid is 1 by volume ratio：1：1
After EC/EMC/DMC mixing, the LiPF of 2.5wt%VC and 1mol/L is added6Composition, it is to obtain porous self-cross linking type gel to gather to take out
Polymer electrolyte Mc2, Mc2 structure is shown in Fig. 1.
The lithium piece negative electrode for being kept apart the positive electrode and a diameter of 16mm that are covered with Ca2 in battery case body using diaphragm, is added
Enter electrolyte sealing into 2016 type Li/LiCoO2Polymer Li-ion battery 2.
Embodiment 3
(1) it is methoxyl group by the polyethylene glycol both ends hydroxyl modification of weight average molecular weight 100g/mol, it is poly- obtains bi-methoxy
Ethylene glycol；Method of modifying detailed in Example 1.
(2) Varonic DM 55 for pure-acrylic emulsion C, 22g solid content 69wt% that 100g solid contents are 50wt% is molten
Liquid uniformly mixes, and forms mixed liquor；
The pure-acrylic emulsion C is P1040, and glass transition temperature is 54 DEG C, and product producer is the same as embodiment 1.
(3) mixed liquor is coated on 100 μm of thickness on lithium ion battery positive plate, negative plate and PTFE plates
Form uncrosslinked film；
(4) the uncrosslinked film comprising positive plate and negative plate is cut into the disk of a diameter of 13mm, by PTFE plates not
Cross linking membrane strips down the disk for being cut into a diameter of 17mm, and is put in again on PTFE plates, then by positive plate, negative plate and
Uncrosslinked film on PTFE plates（Cut out disk）10h is toasted at 30 DEG C, forms self-cross linking type polymer film；
(5) by above-mentioned self-cross linking type polymer film（Film on PTFE plates need to be taken off）It is soaked under ambiance air-proof condition
It steeps in 36h in EMC, after being dried in vacuo 30h at 30 DEG C, respectively obtains positive plate, negative plate and the porous self-cross linking type of self-supporting
Gelatin polymer film Ca3, Cb3 and Cc3；
(6) by the porous self-cross linking type gelatin polymer film in 1x10-3Pa, at 30 DEG C after vacuum drying 30h, it is rapid to turn
It moves on in the glove box full of argon gas, and Cc3 is soaked in electrolyte for 24 hours, the electrolyte liquid is 1 by volume ratio：1：1
After EC/EMC/DMC mixing, the LiPF of 2.5wt%VC and 1mol/L is added6Composition, it is to obtain porous self-cross linking type gel to gather to take out
Polymer electrolyte Mc3；
The lithium piece negative electrode for being kept apart the positive electrode and a diameter of 16mm that are covered with Ca3 in battery case body using diaphragm, is added
Enter electrolyte sealing into 2016 type Li/LiCoO2Polymer Li-ion battery 3.
Embodiment 4
(1) it is methoxyl group by the polyethylene glycol both ends hydroxyl modification of weight average molecular weight 4000g/mol, it is poly- obtains bi-methoxy
Ethylene glycol；Its method detailed in Example 1.
(2) Varonic DM 55 for being 53wt% by pure-acrylic emulsion A, 4.7g solid content that 100g solid contents are 50wt%
Solution uniformly mixes, and forms mixed liquor；
The pure-acrylic emulsion A is mixed by the P1005 of the P1040 and 50g of 50g.The glass of mixed pure-acrylic emulsion A
It is 17 DEG C to change temperature, and product producer and temperature computation method are the same as embodiment 1.
(3) mixed liquor is coated on 100 μm of thickness on lithium ion battery positive plate, negative plate and PTFE plates
Form uncrosslinked film；
(4) the uncrosslinked film comprising positive plate and negative plate is cut into the disk of a diameter of 13mm, by PTFE plates not
Cross linking membrane strips down the disk for being cut into a diameter of 17mm, and is put in again on PTFE plates, then by positive plate, negative plate and
Uncrosslinked film on PTFE plates（Cut out disk）0.05h is toasted at 50 DEG C, forms self-cross linking type polymer film；
(5) by above-mentioned self-cross linking type polymer film（Film on PTFE plates need to be taken off）It is soaked under ambiance air-proof condition
It steeps in deionized water for 24 hours, after being dried in vacuo 30h at 30 DEG C, respectively obtains positive plate, negative plate and the porous selfing of self-supporting
Connection type gelatin polymer film Ca4, Cb4 and Cc4；
(6) by the porous self-cross linking type gelatin polymer film in 1x10-3Pa, at 30 DEG C after vacuum drying 30h, it is rapid to turn
It moves on in the glove box full of argon gas, and Cc4 is soaked in electrolyte for 24 hours, the electrolyte liquid is 1 by volume ratio：1：1
After EC/EMC/DMC mixing, the LiPF of 2.5wt%VC and 1mol/L is added6Composition, it is to obtain porous self-cross linking type gel to gather to take out
Polymer electrolyte Mc4；
The lithium piece negative electrode for being kept apart the positive electrode and a diameter of 16mm that are covered with Ca4 in battery case body using diaphragm, is added
Enter electrolyte sealing into 2016 type Li/LiCoO2Polymer Li-ion battery 4.
Embodiment 5
(1) it is methoxyl group by the polyethylene glycol both ends hydroxyl modification of weight average molecular weight 200g/mol, it is poly- obtains bi-methoxy
Ethylene glycol；Its method is：The metallic sodium of 1mol is first added into the polyethylene glycol of 0.5mol, reaction generates polyethylene glycol sodium and puts
Go out hydrogen.By the methyl iodide of the polyethylene glycol sodium of obtained 0.5mol and 1mol by Williamson synthetic methods, double first are obtained
Oxygroup polyethylene glycol.
(2) the poly- second of bi-methoxy two for being 60wt% by pure-acrylic emulsion B, 12.5g solid content that 100g solid contents are 50wt%
Alcoholic solution uniformly mixes, and forms mixed liquor；
The pure-acrylic emulsion B is mixed by the P1005 of the P1040 and 20g of 80g, the glass of mixed pure-acrylic emulsion B
It is 38 DEG C to change temperature, and product producer and temperature computation method are the same as embodiment 1.
(3) mixed liquor is coated on 100 μm of thickness on lithium ion battery positive plate, negative plate and PTFE plates
Form uncrosslinked film；
(4) the uncrosslinked film comprising positive plate and negative plate is cut into the disk of a diameter of 13mm, by PTFE plates not
Cross linking membrane strips down the disk for being cut into a diameter of 17mm, and is put in again on PTFE plates, then by positive plate, negative plate and
Uncrosslinked film on PTFE plates（Cut out disk）8h is toasted at 40 DEG C, forms self-cross linking type polymer film；
(5) by above-mentioned self-cross linking type polymer film（Film on PTFE plates need to be taken off）It is soaked under ambiance air-proof condition
It steeps in water for 24 hours, after being dried in vacuo 30h at 30 DEG C, it is solidifying to respectively obtain positive plate, negative plate and the porous self-cross linking type of self-supporting
Xanthan polymer film Ca5, Cb5 and Cc5；
(6) by the porous self-cross linking type gelatin polymer film in 1x10-3Pa, at 30 DEG C after vacuum drying 30h, it is rapid to turn
It moves on in the glove box full of argon gas, and Cc5 is soaked in electrolyte for 24 hours, the electrolyte liquid is 1 by volume ratio：1：1
After EC/EMC/DMC mixing, the LiPF of 2.5wt%VC and 1mol/L is added6Composition, it is to obtain porous self-cross linking type gel to gather to take out
Polymer electrolyte Mc5；
The lithium piece negative electrode for being kept apart the positive electrode and a diameter of 16mm that are covered with Ca5 in battery case body using diaphragm, is added
Enter electrolyte sealing into 2016 type Li/LiCoO2Polymer Li-ion battery 5.
Embodiment 6
(1) it is methoxyl group by the polyethylene glycol both ends hydroxyl modification of weight average molecular weight 3000g/mol, it is poly- obtains bi-methoxy
Ethylene glycol；Its method is：The metallic sodium of 1mol is first added into the polyethylene glycol of 0.5mol, reaction generates polyethylene glycol sodium and puts
Go out hydrogen.By the halogenated hydrocarbons methyl iodide of the polyethylene glycol sodium of obtained 0.5mol and 1mol by Williamson synthetic methods, obtain
To Varonic DM 55.
(2) the poly- second of bi-methoxy two for being 42wt% by pure-acrylic emulsion C, 35.7g solid content that 100g solid contents are 50wt%
Alcohol solution uniformly mixes, and forms mixed liquor；
The pure-acrylic emulsion C is P1040, and glass transition temperature is 54 DEG C., product producer is the same as embodiment 1.
(3) mixed liquor is coated on 100 μm of thickness on lithium ion battery positive plate, negative plate and PTFE plates
Form uncrosslinked film；
(4) the uncrosslinked film comprising positive plate and negative plate is cut into the disk of a diameter of 13mm, by PTFE plates not
Cross linking membrane strips down the disk for being cut into a diameter of 17mm, and is put in again on PTFE plates, then by positive plate, negative plate and
Uncrosslinked film on PTFE plates（Cut out disk）10h is toasted at 50 DEG C, forms self-cross linking type polymer film；
(5) by above-mentioned self-cross linking type polymer film（Film on PTFE plates need to be taken off）After being immersed in water for 24 hours, at 30 DEG C
After lower vacuum drying 30h, positive plate, negative plate and porous self-cross linking type gelatin polymer film Ca6, the Cb6 of self-supporting are respectively obtained
And Cc6；
(6) by the porous self-cross linking type gelatin polymer film in 1x10-3Pa, at 30 DEG C after vacuum drying 30h, it is rapid to turn
It moves on in the glove box full of argon gas, and Cc6 is soaked in electrolyte for 24 hours, the electrolyte liquid is 1 by volume ratio：1：1
After EC/EMC/DMC mixing, the LiPF of 2.5wt%VC and 1mol/L is added6Composition, it is to obtain porous self-cross linking type gel to gather to take out
Polymer electrolyte Mc6；
The lithium piece negative electrode for being kept apart the positive electrode and a diameter of 16mm that are covered with Ca6 in battery case body using diaphragm, is added
Enter electrolyte sealing into 2016 type Li/LiCoO2Polymer Li-ion battery 6.
Comparative example 1
In the glove box full of argon gas, according to the methyl methacrylate of 9wt%, the phthalic acid diethyl of 2.5wt%
The LiPF of omega-diol diacrylate, the dibenzoyl peroxide of 0.5wt% and a concentration of 1M of 88wt%6The ratio of electrolyte mixes
Mixed liquor is coated in positive electrode, negative electrode by the mixed liquor for forming transparence, good fluidity in glove box using coating method
On PTFE plates, thermal polymerization is carried out after being sealed in glove box at 85-90 DEG C, time 15-20min is made and loads respectively
Self-cross linking type polymer dielectric Aa1, Ab1 and Ac1 on positive plate, negative plate and PTFE plates.And will include positive plate
It is cut into the disk of a diameter of 13mm with Aa1, Ab1 of negative plate, and the Ac1 stripped down from PTFE plates is cut into diameter
The disk of 17mm, whole process all carry out under an inert atmosphere.（This step has been added in electrolyte, so what is obtained is solidifying
Xanthan polymer electrolyte）
Keep apart the positive electrode for being covered with Aa1 in battery case body using diaphragm（Disk）With bearing for the lithium piece of a diameter of 16mm
Electrolyte sealing is added into 2016 type Li/LiCoO in electrode2Polymer Li-ion battery P.
Comparative example 2
(1) the pure-acrylic emulsion C that 100g solid contents are 50wt% is coated on lithium ion battery anode with 100 μm of thickness
Uncrosslinked film is formed on piece, negative plate and aluminium foil；The pure-acrylic emulsion C is P1040, and glass transition temperature is 54 DEG C, product factory
Family is the same as embodiment 1.
(2) the uncrosslinked film comprising positive electrode and negative electrode is cut into the disk of diameter 13mm, and comprising
The uncrosslinked film of aluminium foil is cut into the disk of a diameter of 17mm, and then film stripping uncrosslinked on aluminium foil is got off,
It is placed on PTFE plates, the uncrosslinked film on positive electrode, negative electrode and PTFE plates will be included（Cut out disk）It is toasted at 50 DEG C
10h is to get to self-cross linking type polymer film Aa2, Ab2 and the Ac2 being supported on respectively on positive plate, negative plate and PTFE plates；
3) by all self-cross linking type polymer films in 1x10-3Pa, it at 40 DEG C after vacuum drying 20h, is quickly transferred to be full of
In the glove box of argon gas, and Ac2 is removed from PTFE plates and is soaked in electrolyte for 24 hours, the electrolyte liquid is by volume ratio
1：1：After 1 EC/EMC/DMC mixing, the LiPF of 2.5wt%VC and 1mol/L is added6Composition, it is to obtain self-cross linking type to coagulate to take out
Xanthan polymer electrolyte Bc2；
The lithium piece negative electrode for being kept apart the positive electrode and a diameter of 16mm that are covered with Aa2 in battery case body using diaphragm, is added
Enter electrolyte sealing into 2016 type Li/LiCoO2Polymer Li-ion battery Q.
Positive electrode in above-described embodiment and comparative example is the positive electrode and conductive agent, bonding that will be used for lithium ion battery
Agent, which is tuned into slurry and is coated in metal foil, to be made.Positive electrode used removes the above-mentioned cobalt-lithium oxide used（LiCoO2）Outside, it also wraps
Any other positive electrode that can be used for lithium ion battery is included, such as nickel oxide lithium（LiNiO2）, manganese oxide lithium（LiMn2O4）, phosphoric acid
Ferrous lithium（LiFePO4）With ternary composite cathode material and its transformed lines show etc..Negative electrode in above-described embodiment and comparative example
It is lithium piece, in addition to this above-mentioned negative electrode can also be by that will be used for the negative material and conductive agent, binder tune of lithium ion battery
It is coated in metal foil and is made at slurry, negative material used includes the negative material that arbitrarily can be used for lithium ion battery, such as stone
Ink, soft carbon, hard carbon etc..The metal foil includes that can arbitrarily play the metal foil of electric action, such as copper foil, aluminium foil.
Diaphragm in above-described embodiment and comparative example is the diaphragm for being arbitrarily applicable to lithium ion battery, such as PP diaphragms, PE
Diaphragm and PE/PP/PE three-layer membranes etc..
The electrolyte can be made of lithium salts and solvent, wherein a concentration of 0.8-1.5mol/L of lithium salts；The lithium salts can
Select lithium hexafluoro phosphate（LiPF6）, lithium perchlorate（LiClO4）And LiBF4（LiBF4）Deng；Ethylene carbonate can be selected in solvent
Ester（EC）, propene carbonate（PC）, dimethyl carbonate（DMC）, methyl ethyl carbonate（EMC）And diethyl carbonate（DEC）, carbonic acid it is sub-
Vinyl acetate（VC）In one or more mixing.
It, can also other than using the positive plate for being covered with self-cross linking type polymer film, lithium piece negative electrode in above-described embodiment
It is used as follows：The negative plate and lithium of overlay film are separated with the general diaphragm of lithium ion battery such as in the glove box full of argon gas
Electrolyte is added in piece, seals into polymer Li-ion battery；With the general diaphragm of lithium ion battery in the glove box full of argon gas
The negative plate of overlay film positive plate and overlay film is separated, electrolyte sealing is added into polymer Li-ion battery.
In addition, the pure-acrylic emulsion in above-described embodiment and comparative example is other than two kinds of P1040 and P1005, in the prior art
Any pure-acrylic emulsion be suitable for the present invention.
Method of modifying in above-described embodiment is not unique, any in the prior art to replace the hydroxyl at polyethylene glycol both ends
It is suitable for the present invention for the method for methoxyl group.
Test case
（1）Measure the porosity of Cc1-Cc7 and Ac2：The radius r and thickness d for measuring disc-shaped film, weigh up mass M0After soak
The 2h in n-butanol is steeped, then takes out and blots the liquid of film surface with filter paper and weigh mass M at this time, according to following formula
Porosity is calculated, the results are shown in Table 1；
（2）Measure the imbibition rate of Cc1-Cc7 and Ac2：It is put into the glove box full of argon gas after disc-shaped film is dried,
It weighs up to be immersed in electrolyte after quality W to then take out for 24 hours and blots the liquid of film surface with filter paper and weigh quality at this time
Wi, imbibition rate is calculated according to the following equation, the results are shown in Table 1；
（3）Measure the conductivity of Mc1-Mc6, Ac1 and Bc2：The disc-shaped film after enough electrolyte will be absorbed and be placed on two
Stainless steel（SS）Between electrode, it is sealed in 2016 type button cells (Shenzhen East China Zheng Tai mechanical ＆ electronic equipment corporation, Ltds）Afterwards, it adopts
Ac impedance measurement is carried out with the CHI604b types electrochemical workstation of Shanghai Chen Hua, measures the ontology impedance R of film, according to the following formula
The conductivity of film is calculated, the results are shown in Table 1：
σ=L/A·R
Wherein, L indicates that film thickness, A are the real contact area of stainless steel electrode and film；
Table 1
As shown in Table 1, porosity, the imbibition rate for the porous self-cross linking type gelatin polymer film that prepared by the method for the invention
Be far above comparative example with the conductivity of porous self-cross linking type gel polymer electrolyte, thus its to the acceptance of electrolyte and from
Electron conductivity is above comparative example.Meanwhile the ontology impedance of porous self-cross linking type gel polymer electrolyte of the present invention is low
Self-cross linking type gel polymer electrolyte in comparative example.
（4）The charge-discharge property of lithium ion battery 1-6, P and Q measure：Using BK6016 type performance of lithium ion batteries
Test cabinet（Guangzhou Lanqi Electronic Industrial Co., Ltd.）It is tested, with 0.075mA/cm2Electric current first by constant-current charging of battery
To 4.2V, then constant-voltage charge at 4.2v, cut-off current 0.038mA/cm2, charging capacity is recorded, then with 0.075mA/
cm2By battery constant-current discharge to 3.0V, record discharge capacity.According to specific capacity=discharge capacity/LiCoO2Electrode quality, for the first time
Discharge capacity/initial charge capacity × 100% of efficiency for charge-discharge=for the first time, obtains specific capacity and first charge-discharge efficiency, as a result sees
Table 2；
Table 2
| Lithium ion battery | Specific capacity（mAh/g） | First charge-discharge efficiency（%） |
| 1 | 144 | 98.14 |
| 2 | 143 | 97.96 |
| 3 | 146 | 97.93 |
| 4 | 141 | 98.33 |
| 5 | 142 | 97.99 |
| 6 | 145 | 99.27 |
| P | 140 | 95.59 |
| Q | 144 | 96.17 |
As shown in Table 2, the charge and discharge for the first time for the porous self-cross linking type gel polymer electrolyte that prepared by the method for the invention
Electrical property is higher than comparative example.
（5）The multiplying power of lithium ion battery 1-6, P and Q charge and multiplying power discharging property test, using BK6016 type lithium ions
Battery performance test cabinet（Guangzhou Lanqi Electronic Industrial Co., Ltd.）Lithium ion battery after completion first charge-discharge is carried out
Multiplying power charges and multiplying power discharging test, using discharge capacity for the first time as battery rated capacity：
I. first by battery 0.1C constant-current constant-voltage chargings to 4.2V, after shelving 5min, battery is discharged to 3.0V with 0.1C,
It shelves 5min, then uses 0.2C/0.5C/1C/3C constant-current charges to 4.2V respectively, then constant-voltage charge at 4.2v, cut-off current
For 0.02C, charging capacity under each multiplying power is recorded, the results are shown in Table 3；
Ii. by battery 0.1C constant-current charges to 4.2V, then constant-voltage charge, cut-off current 0.02C are put at 4.2v
5min is set, is discharged to 3.0V with 0.2C/0.5C/1C/3C respectively, each multiplying power discharge capacity is recorded, the results are shown in Table 4；
Table 3
Table 4
By table 3-4 it is found that the lithium ion of porous self-cross linking type gel polymer electrolyte prepared by the method for the invention
The charging of each multiplying power of battery and each multiplying power discharging property have compared with comparative example largely to be improved, this is because in the present invention it is porous from
The impedance of cross-linking type gel polymer electrolyte reduces, and conductivity is high, can reduce the polarization phenomena in charge and discharge process, favorably
In the migration of lithium ion.
Although the present invention has carried out detailed elaboration by above-mentioned specific embodiment to it, this profession is common
Technical staff should be understood that made on this basis without departing from any form of claims and the change of details
Change, belongs to invention which is intended to be protected.
Claims (15)
1. a kind of porous self-cross linking type gelatin polymer film, which is characterized in that
It by pure-acrylic emulsion and the mixing of modified poly (ethylene glycol) solution, is crosslinked and carries out pore-creating and obtain, the pore-creating is that will be crosslinked to obtain
Self-cross linking type polymer film contacted with polyethylene glycol good solvent, the weight average molecular weight of the polyethylene glycol is less than 100,000 g/mol；
The hydroxyl at polyethylene glycol both ends obtains the modified poly (ethylene glycol) by methoxy substitution, and the solid content of the pure-acrylic emulsion is
The solid content of 40-60wt%, the modified poly (ethylene glycol) solution are 5-80wt%, the solid weight of the modified poly (ethylene glycol) solution
Amount is the 1-50wt% of the pure-acrylic emulsion solid weight；
The porosity of the porous self-cross linking type gelatin polymer film is 40-70%.
2. porous self-cross linking type gelatin polymer film according to claim 1, which is characterized in that the polyethylene glycol is good molten
Agent is water, solvent or lithium-ion battery electrolytes in lithium-ion battery electrolytes.
3. porous self-cross linking type gelatin polymer film according to claim 2, which is characterized in that the electrolyte is by lithium salts
It is formed with solvent, a concentration of 0.8~1.5mol/L of the lithium salts.
4. according to any porous self-cross linking type gelatin polymer films of claim 1-3, which is characterized in that pure third breast
The glass transition temperature of liquid is -30-70 DEG C.
5. porous self-cross linking type gelatin polymer film according to claim 4, which is characterized in that the glass of the pure-acrylic emulsion
Glass temperature is -18-60 DEG C.
6. porous self-cross linking type gelatin polymer film according to claim 5, which is characterized in that the weight of the polyethylene glycol
Average molecular weight is ten thousand g/mol of 100-5.
7. porous self-cross linking type gelatin polymer film according to claim 6, which is characterized in that the modified poly (ethylene glycol)
The solid weight of solution is the 5-30wt% of the pure-acrylic emulsion solid weight.
8. the porous self-cross linking type gelatin polymer film described according to claim 6 or 7, which is characterized in that film thickness 0.01-
110μm。
9. using the porous self-cross linking type gelatin polymer of any porous self-cross linking type gelatin polymer films of claim 1-8
Electrolyte, which is characterized in that obtained by porous self-cross linking type gelatin polymer film contact electrolyte.
10. porous self-cross linking type gel polymer electrolyte according to claim 9, which is characterized in that it is described it is porous from
The conductivity of cross-linking type gel polymer electrolyte is 7-8.5mS/cm.
11. the preparation method of any porous self-cross linking type gelatin polymer films of claim 1-8, includes the following steps,
(1) it is methoxyl group by the hydroxyl modification at polyethylene glycol both ends, obtains modified poly (ethylene glycol) and wiring solution-forming；
(2) modified poly (ethylene glycol) solution, pure-acrylic emulsion are uniformly mixed, forms mixed liquor；
(3) mixed liquor is coated on electrode surface, forms uncrosslinked film；
(4) the uncrosslinked film is toasted at 20-50 DEG C, forms self-cross linking type polymer film；
(5) after being dried in vacuo the self-cross linking type polymer film, polyethylene glycol good solvent is soaked under dry oxygen-free environment
It is interior, taking-up.
12. preparation method according to claim 11, which is characterized in that the baking time in step (4) is 0.01-24h,
Baking temperature is 30-50 DEG C.
13. preparation method according to claim 11 or 12, which is characterized in that vacuum drying temperature be 30-50 DEG C, when
Between be 10-30h；Soaking time is no less than for 24 hours.
It, will be dry porous 14. the porous self-cross linking type method for preparing gel polymer electrolyte described in claim 9 or 10
Self-cross linking type gelatin polymer film is soaked in electrolyte in an inert atmosphere, taking-up.
15. using the lithium ion battery of any porous self-cross linking type gelatin polymer films of claim 1-8, including,
The battery case internal body portion is divided into positive conversion zone and negative reaction area by battery groove body and diaphragm, the diaphragm
Domain；
Anode is set in the positive conversion zone；
Cathode is set in the negative reaction region；
Electrolyte is filled in the positive conversion zone and negative reaction region；
The porous self-cross linking type gelatin polymer film be set to it is described anode and cathode between, and with it is described anode and cathode phase
Contact；
The anode, cathode, diaphragm and porous self-cross linking type gelatin polymer film immersion are in the electrolyte.
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| CN102324561A (en) * | 2011-09-20 | 2012-01-18 | 西南石油大学 | P(MAh-AA)-PEG4000-based gel polymer electrolyte and preparation method thereof |
| CN102956910A (en) * | 2012-12-07 | 2013-03-06 | 中国海洋大学 | Hydrogel-based medium-high temperature PEM (Proton Exchange Membrane), preparation method thereof and application of hydrogel-based medium-high temperature PEM |
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| CN102324561A (en) * | 2011-09-20 | 2012-01-18 | 西南石油大学 | P(MAh-AA)-PEG4000-based gel polymer electrolyte and preparation method thereof |
| CN102956910A (en) * | 2012-12-07 | 2013-03-06 | 中国海洋大学 | Hydrogel-based medium-high temperature PEM (Proton Exchange Membrane), preparation method thereof and application of hydrogel-based medium-high temperature PEM |
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