CN104752760B - A kind of porous self-cross linking type gel polymer electrolyte, the electrolyte preparation method and its application in lithium ion battery - Google Patents
A kind of porous self-cross linking type gel polymer electrolyte, the electrolyte preparation method and its application in lithium ion battery Download PDFInfo
- Publication number
- CN104752760B CN104752760B CN201310754009.7A CN201310754009A CN104752760B CN 104752760 B CN104752760 B CN 104752760B CN 201310754009 A CN201310754009 A CN 201310754009A CN 104752760 B CN104752760 B CN 104752760B
- Authority
- CN
- China
- Prior art keywords
- linking type
- cross linking
- porous self
- electrolyte
- type polymer
- 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.)
- Active
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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
-
- 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
- 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
-
- 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
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of porous self-cross linking type gel polymer electrolyte, the aqueous solution mixing formed by the pure-acrylic emulsion that glass transition temperature is 30 70 DEG C and the polyethylene glycol oxide that weight average molecular weight is 50,000 800 ten thousand g/mol, electrostatic spinning are simultaneously cross-linked to form；The pure-acrylic emulsion is made up of polyacrylate material, crosslinking agent, emulsifying agent and water；The porosity of the porous self-cross linking type polymer film is 60 90%.On this basis, the electrolyte preparation method and the lithium ion battery using the electrolyte are given.The porous self-cross linking type gel polymer electrolyte electrolyte that is adapted as lithium ion battery prepared is used, its impedance is low, ionic conductivity is high, high power charging-discharging when be difficult polarization.
Description
Technical field
The present invention relates to a kind of porous self-cross linking type gel polymer electrolyte, the preparation side of the electrolyte is given
Method, and application of the electrolyte in lithium ion battery, belong to technical field of lithium ion.
Background technology
The energy density of conventional lithium ion battery is low, electrolyte is easy to leakage, therefore easily triggers security incident.It is emerging in recent years
The gel polymer electrolyte risen, its ion transport speed is fast, and its matrix can adsorb a large amount of liquid electrolytes, be difficult hair
Raw liquid leakage, therefore gradually alternative electrolyte is being used in lithium ion battery.
At present, the gel polymer electrolyte of lithium ion battery mainly has Kynoar and vinylidene-hexafluoro third
Alkene copolymer, its good mechanical property.But, Kynoar and vinylidene-hexafluoropropylene copolymer and electrolyte it is affine
Property it is poor, the ability of adsorptive liquid electrolyte is weak, easily cause battery liquid leakage, and above-mentioned two gellikes polyeletrolyte with
Interelectrode interface resistance is big, it is impossible to stablize compatible with electrode.
In order to overcome Kynoar and the above-mentioned of vinylidene-hexafluoropropylene copolymer gel polymer electrolyte to lack
Point, there is above-mentioned two classes material is modified using polymethyl methacrylate.Such as Chinese patent literature CN102013516A
Disclose a kind of porous fiber gel polymer electrolyte and preparation method thereof, by Kynoar, polymethyl methacrylate,
Nano silicon and liquid electrolyte blending composition, are made using method of electrostatic spinning and obtained.Gelatin polymer in the technology
Electrolyte ion conductivity is high, good mechanical property, receives the ability of electrolyte and simple with the compatibility of electrode compared with gathers
Vinylidene material tool improves；But due to the gel polymer electrolyte be still using Kynoar as matrix, its
Receive electrolyte ability and still inadequate with the compatibility of electrode, and the gel polymer electrolyte in above-mentioned technology is being used
Serious problem of phase separation can occur after a period of time, causing the performance of battery reduces.
Due to above-mentioned using Kynoar or vinylidene-hexafluoropropylene copolymer as the gel polymer electrolyte of matrix
Have the shortcomings that to receive electrolyte ability low and with electrode poor compatibility, thus there is researcher to be considered as brand-new material body
It is the electrolyte ingredient as lithium ion battery.Because the conventional electrolyte of polyacrylate material and lithium ion battery has
Similar functional group, it 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 polymers are used as lithium
The research of ion battery gel polymer electrolyte matrix is interesting.As Chinese patent literature CN1317512A discloses one kind
The preparation method of gel-state lithium ion polymer electrolyte and battery, using series of acrylate derivative as monomer, itself and
Crosslinking agent thermal initiator initiation under by thermochemical crosslinking method formation polyacrylate, polyacrylate further with electrolysis
Liquid formation polyacrylate gel gel polymer electrolyte, can be used as the electrolyte of lithium ion battery.
Above-mentioned technology successfully using polyacrylate polymers as lithium ion battery gel polymer electrolyte base
Body is used, and overcomes this area all the time using Kynoar or vinylidene-hexafluoropropylene copolymer as gelatin polymer
During electrolyte matrix, existing receives electrolyte ability low and shortcoming with electrode poor compatibility；But it is due to above-mentioned technology
In polyacrylate gel polymer electrolyte body impedance it is higher, ionic conductivity is low, causes battery to be filled in high magnification
Polarity effect under discharge scenario is big, and the performance of battery is low.
Body impedance for how to reduce polyacrylate gel polymer electrolyte, so as to improve with polyacrylic acid
Ester is used as this technical problem of the performance of the lithium ion battery of gel polymer electrolyte matrix, art technology
Personnel can not find suitable solution always.
The content of the invention
The technical problems to be solved by the invention are that polyacrylate gel polymer electrolyte body impedance is higher, are led
The performance for sending a telegraph pond is low, and those skilled in the art can not find suitable method and go to reduce polyacrylate always
The impedance of gel polymer electrolyte；And a kind of impedance of present invention proposition is low, ionic conductivity is high porous certainly by high porosity
The porous self-cross linking type gel polymer electrolyte that crosslinking polymer film is obtained.
On this basis, the invention also provides the high rate capability using porous self-cross linking type gel polymer electrolyte
Good lithium ion battery.
In order to solve the above technical problems, the invention provides a kind of porous self-cross linking type polymer film, by pure-acrylic emulsion and
Polyethylene oxide solutions are mixed, are cross-linked to form；The porosity of the porous self-cross linking type polymer film is 60-90%.
By the pure-acrylic emulsion and polyethylene oxide solutions mixing after electrostatic spinning and be crosslinked obtain.
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 oxide is 50,000-800 ten thousand g/mol.
The weight average molecular weight of the polyethylene glycol oxide is 100,000-400 ten thousand g/mol.
The weight average molecular weight of the polyethylene glycol oxide is 200,000-200 ten thousand g/mol.
The solid content of polyethylene oxide solutions is 1-50wt%, and the solid content of the pure-acrylic emulsion is 40-60wt%, described pure
The solid weight of acrylic emulsion and the solid weight ratio of polyethylene oxide solutions are 1：（0.1-5）.
The solid weight of the pure-acrylic emulsion and the solid weight ratio of polyethylene oxide solutions are 1：（0.5-3）.
The solid content of the polyethylene oxide solutions is 2-20wt%.
Film thickness is 0.01-110 μm.
The porous self-cross linking type gel polymer electrolyte obtained by the porous self-cross linking type polymer film, by it is porous from
Crosslinking polymer film contact electrolyte is obtained.
The electrical conductivity of the porous self-cross linking type gel polymer electrolyte is 7-10mS/cm.
The preparation method of the porous self-cross linking type polymer film, comprises the following steps,
(1) pure-acrylic emulsion is uniformly mixed with polyethylene oxide solutions, forms mixed solution；
(2) uncrosslinked film is formed in electrode surface electrostatic spinning with the mixed solution；
(3) the uncrosslinked film is toasted at 20-50 DEG C, forms porous self-cross linking type polymer film.
Step（3）In baking time be 0.01-24h, baking temperature be 30-50 DEG C.
Described porous self-cross linking type method for preparing gel polymer electrolyte, by the porous self-crosslinking after vacuum drying
Type gelatin polymer film is soaked in electrolyte under an inert atmosphere, taking-up.
Vacuum drying temperature is 30-50 DEG C, the time is 10-30h；The time being soaked in electrolyte is no less than 24h.
Using the lithium ion battery of the porous self-cross linking type polymer film, including,
The battery case internal body portion is divided into positive pole conversion zone and negative reaction by battery cell body and barrier film, the barrier film
Region；
Positive pole, is arranged in the positive pole conversion zone；
Negative pole, is arranged in the negative reaction region；
Electrolyte, is filled in the positive pole conversion zone and negative reaction region；
The porous self-cross linking type polymer film is arranged between the positive pole and negative pole, and with the negative or positive electrode
At least one is in contact；
The positive pole, negative pole, barrier film and porous self-cross linking type polymer film are impregnated in the electrolyte.
Pure-acrylic emulsion used in the present invention is the emulsion for being generally used for making coating in the prior art, is by polypropylene
The emulsion using polyacrylate as main component that acid ester monomer, crosslinking agent, emulsifying agent and water mixing copolymerization are formed, 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 polymer film of the present invention, by glass transition temperature for -30-70 DEG C pure-acrylic emulsion and
Weight average molecular weight is the solution mixing of 50,000-800 ten thousand g/mol polyethylene glycol oxide formation, electrostatic spinning and is cross-linked to form；It is described
The porosity of porous self-cross linking type polymer film is 60-90%.Because pure-acrylic emulsion is not that solution can not carry out electrostatic to it in itself
Spinning, the application then can directly be entered by the way that pure-acrylic emulsion is mixed into successive soln phase with polyoxyethylene aqueous solution
Row electrostatic spinning is molded and is crosslinked, and finally gives the self-cross linking type polymer film with loose structure, the formation of its electrostatic spinning
Loose structure make it that the electrical conductivity of formed gel polymer electrolyte is greatly improved, impedance is substantially reduced, so that institute's group
The high rate performance of packed battery is greatly improved, it is to avoid polyacrylate gel polymer electrolyte body impedance in the prior art
It is higher, cause the performance of battery low, and also those skilled in the art can not find suitable method and go reduction poly- third always
The problem of olefin(e) acid esters gel polymer electrolyte impedance.
（2）Porous self-cross linking type polymer film of the present invention, the solid content of the polyethylene oxide solutions is 1-
50wt%, the solid content of the pure-acrylic emulsion is 40-60wt%, the solid weight of the pure-acrylic emulsion and polyethylene oxide solutions
Solid weight ratio is 1：（0.1-5）.The solution of above-mentioned solid content, the pure-acrylic emulsion of ratio and the formation of polyoxyethylene aqueous solution
It is more continuous, it is more prone to the self-cross linking type polymer film of electrostatic spinning formation loose structure, and obtained porous self-crosslinking
Type polymer film and electrolyte, electrode compatibility more preferably, further reduce the generation of battery leakage problem, further reduction
Impedance between interface between gel polymer electrolyte and electrode.
（3）Porous self-cross linking type polymer film of the present invention, porous self-cross linking type polymer film thickness of the present invention
For 0.01-110 μm, obtained porous self-cross linking type polymer film can form any thickness as needed, applied widely,
Available for the lithium ion battery for making existing any capacity.
（4）The preparation method of porous self-cross linking type polymer film of the present invention, will be formed in electrode surface electrostatic spinning
Uncrosslinked film toasted in a low temperature of 20-50 DEG C and can form porous self-crosslinking polymer film, without high-temperature process, formed
Porosity be up to 60-90%.
（5）In lithium ion battery of the present invention using porous self-cross linking type polymer film, porous self-cross linking type polymerization
Thing film can be set between a positive electrode and a negative electrode, and be in contact with the surface of at least one in negative or positive electrode.
Brief description of the drawings
In order that present disclosure is more easily understood, the present invention combines the drawings and specific embodiments to the present invention's
Content is further detailed；
Fig. 1 is the stereoscan photograph of porous self-cross linking type polymer film described in the embodiment of the present invention 2；
Embodiment
Embodiment 1
(1) g/ of weight average molecular weight 50,000 that the pure-acrylic emulsion A for being 40wt% by 100g solid contents is 1wt% with 400g solid contents
Mol polyoxyethylene aqueous solution is uniformly mixed, and forms mixed solution；
The pure-acrylic emulsion A is mixed by 50g P1040 and 50g P1005, and P1040 and P1005 are Shanghai love
The pure-acrylic emulsion product that high Chemical Co., Ltd. sells, through equipped with cryogenic system（FT100）METTLER DSC823e test,
P1040 and P1005 glass transition temperature is respectively 54 DEG C and -12 DEG C, and pure-acrylic emulsion A vitrifying temperature is calculated according to the following equation
Spend for 17 DEG C.
Wherein, the mass fraction that W1 is P1040 in pure-acrylic emulsion A, the mass fraction that W2 is P1005 in pure-acrylic emulsion A,
Tg1 is P1040 glass transition temperature（Kelvin degree）, Tg2 is P1005 glass transition temperature（Kelvin degree）, Tg is pure
Acrylic emulsion A glass transition temperature（Kelvin degree）.
(2) mixed solution is placed in syringe, with method of electrostatic spinning respectively with about 10mL mixed solutions in lithium
Spinning on ion battery positive plate, negative plate and aluminium foil, syringe needle used is 8#（External diameter is 0.56mm, and internal diameter is
0.46mm）, flow velocity is 0.8mL/min, and voltage is 10KV, syringe needle translational speed 5-6mm/s, and drum rotation speed is 300rpn, is received
Distance is 12cm, spinning duration 8h, the uncrosslinked film of formation；
(3) aluminium foil is cut into a diameter of 17mm disk together with film thereon, uncrosslinked film is peeled off from aluminium foil and is placed in
On PTFE plates, the uncrosslinked film comprising positive plate and negative plate is cut into a diameter of 13mm disk, then by positive plate, negative pole
Uncrosslinked film on piece and PTFE plates（Cut out disk）Toast 24h at 20 DEG C, formed porous self-cross linking type polymer film Ca1,
Cb1 and Cc1；
(4) by all porous self-cross linking type polymer films in 1x10-3Pa, at 20 DEG C after vacuum drying 30h, it is quickly transferred to
In glove box full of argon gas, and Cc1 is removed from PTFE plates it is soaked in 24h in electrolyte, the electrolyte liquid is by volume
Than for 1：1：After 1 EC/EMC/DMC mixing, 2.5wt%VC and 1mol/L LiPF is added6Composition, take out i.e. obtain it is porous from
Cross-linking type gel polymer electrolyte Mc1；
Keep apart the lithium piece negative electrode of the positive electrode and a diameter of 16mm that are covered with Ca1 in battery case body using barrier film, plus
Enter electrolyte and seal into 2016 type Li/LiCoO2Polymer Li-ion battery 1.
Embodiment 2
(1) weight average molecular weight 2,000,000 that the pure-acrylic emulsion B for being 60wt% by 100g solid contents is 50wt% with 600g solid contents
G/mol polyoxyethylene aqueous solution is uniformly mixed, and forms mixed solution；
The pure-acrylic emulsion B is mixed by 80g P1040 and 20g P1005, mixed pure-acrylic emulsion B glass
It is 38 DEG C to change temperature, product producer and temperature computation method be the same as Example 1.
(2) mixed solution is placed in syringe, with method of electrostatic spinning respectively with about 10mL mixed solutions in lithium
Spinning on ion battery positive plate, negative plate and aluminium foil, syringe needle used is 8#（External diameter is 0.56mm, and internal diameter is
0.46mm）, flow velocity is 0.8mL/min, and voltage is 10KV, syringe needle translational speed 5-6mm/s, and drum rotation speed is 300rpn, is received
Distance is 12cm, spinning duration 8h, the uncrosslinked film of formation；
(3) aluminium foil is cut into a diameter of 17mm disk together with film thereon, uncrosslinked film is peeled off from aluminium foil and is placed in
On PTFE plates, the uncrosslinked film comprising positive plate and negative plate is cut into a diameter of 13mm disk, then by positive plate, negative pole
Uncrosslinked film on piece and PTFE plates（Cut out disk）0.01h is toasted at 50 DEG C, porous self-cross linking type polymer film is formed
Ca2, Cb2 and Cc2, Cc2 structure are shown in Fig. 1；
(4) by all porous self-cross linking type polymer films in 1x10-3Pa, at 50 DEG C after vacuum drying 10h, it is quickly transferred to
In glove box full of argon gas, and Cc2 is removed from PTFE plates it is soaked in 24h in electrolyte, the electrolyte liquid is by volume
Than for 1：1：1 EC/EMC/DMC mixing after, add 2.5wt%VC and 1mol/L LiPF6 composition, take out i.e. obtain it is porous from
Cross-linking type gel polymer electrolyte Mc2；
(5) the lithium piece negative electrode of the positive electrode and a diameter of 16mm that are covered with Ca2 is kept apart in battery case body using barrier film,
Add electrolyte and seal into 2016 type Li/LiCoO2Polymer Li-ion battery 2.
Embodiment 3
(1) weight average molecular weight 8,000,000 that the pure-acrylic emulsion C for being 50wt% by 100g solid contents is 2wt% with 1250g solid contents
G/mol polyoxyethylene aqueous solution is uniformly mixed, and forms mixed solution；
The pure-acrylic emulsion C is P1040, and its glass transition temperature is 54 DEG C, product producer be the same as Example 1.
(2) mixed solution is placed in syringe, with method of electrostatic spinning respectively with about 10mL mixed solutions in lithium
Spinning on ion battery positive plate, negative plate and aluminium foil, syringe needle used is 8#（External diameter is 0.56mm, and internal diameter is
0.46mm）, flow velocity is 0.8mL/min, and voltage is 10KV, syringe needle translational speed 5-6mm/s, and drum rotation speed is 300rpn, is received
Distance is 12cm, spinning duration 8h, the uncrosslinked film of formation；
(3) aluminium foil is cut into a diameter of 17mm disk together with film thereon, uncrosslinked film is peeled off from aluminium foil and is placed in
On PTFE plates, the uncrosslinked film comprising positive plate and negative plate is cut into a diameter of 13mm disk, then by positive plate, negative pole
Uncrosslinked film on piece and PTFE plates（Cut out disk）Toast 10h at 30 DEG C, formed porous self-cross linking type polymer film Ca3,
Cb3 and Cc3；
(4) all porous self-cross linking type polymer films are dried in vacuo after 20h at 1x10-3Pa, 30 DEG C, rapid transfer
Into the glove box full of argon gas, and Cc3 is removed from PTFE plates it is soaked in 24h in electrolyte, the electrolyte liquid is by body
Product is than being 1：1：After 1 EC/EMC/DMC mixing, 2.5wt%VC and 1mol/L LiPF6 compositions are added, takes out and obtains porous
Self-cross linking type gel polymer electrolyte Mc3；
(5) the lithium piece negative electrode of the positive electrode and a diameter of 16mm that are covered with Ca3 is kept apart in battery case body using barrier film,
Add electrolyte and seal into 2016 type Li/LiCoO2 polymer Li-ion batteries 3.
Embodiment 4
(1) weight average molecular weight 4,000,000 that the pure-acrylic emulsion A for being 50wt% by 100g solid contents is 20wt% with 750g solid contents
G/mol polyoxyethylene aqueous solution is uniformly mixed, and forms mixed solution；
The pure-acrylic emulsion A is mixed by 50g P1040 and 50g P1005.Mixed pure-acrylic emulsion A glass
It is 17 DEG C to change temperature, product producer and temperature computation method be the same as Example 1.
(2) mixed solution is placed in syringe, with method of electrostatic spinning respectively with about 10mL mixed solutions in lithium
Spinning on ion battery positive plate, negative plate and aluminium foil, syringe needle used is 8#（External diameter is 0.56mm, and internal diameter is
0.46mm）, flow velocity is 0.8mL/min, and voltage is 10KV, syringe needle translational speed 5-6mm/s, and drum rotation speed is 300rpn, is received
Distance is 12cm, spinning duration 8h, the uncrosslinked film of formation；
(3) aluminium foil is cut into a diameter of 17mm disk together with film thereon, uncrosslinked film is peeled off from aluminium foil and is placed in
On PTFE plates, the uncrosslinked film comprising positive plate and negative plate is cut into a diameter of 13mm disk, then by positive plate, negative pole
Uncrosslinked film on piece and PTFE plates（Cut out disk）0.05h is toasted at 40 DEG C, porous self-cross linking type polymer film is formed
Ca4, Cb4 and Cc4；
(4) by all porous self-cross linking type polymer films in 1x10-3Pa, at 40 DEG C after vacuum drying 40h, it is quickly transferred to
In glove box full of argon gas, and Cc4 is removed from PTFE plates it is soaked in 36h in electrolyte, the electrolyte liquid is by volume
Than for 1：1：After 1 EC/EMC/DMC mixing, 2.5wt%VC and 1mol/L LiPF is added6Composition, take out i.e. obtain it is porous from
Cross-linking type gel polymer electrolyte Mc4；
(5) the lithium piece negative electrode of the positive electrode and a diameter of 16mm that are covered with Ca4 is kept apart in battery case body using barrier film,
Add electrolyte and seal into 2016 type Li/LiCoO2Polymer Li-ion battery 4.
Embodiment 5
(1) weight average molecular weight 200,000 that the pure-acrylic emulsion B for being 50wt% by 100g solid contents is 10wt% with 750g solid contents
G/mol polyoxyethylene aqueous solution is uniformly mixed, and forms mixed solution；
The pure-acrylic emulsion B is mixed by 80g P1040 and 20g P1005, mixed pure-acrylic emulsion B glass
It is 38 DEG C to change temperature, product producer and temperature computation method be the same as Example 1.
(2) mixed solution is placed in syringe, with method of electrostatic spinning respectively with about 10mL mixed solutions in lithium
Spinning on ion battery positive plate, negative plate and aluminium foil, syringe needle used is 8#（External diameter is 0.56mm, and internal diameter is
0.46mm）, flow velocity is 0.8mL/min, and voltage is 10KV, syringe needle translational speed 5-6mm/s, and drum rotation speed is 300rpn, is received
Distance is 12cm, spinning duration 8h, the uncrosslinked film of formation；
(3) aluminium foil is cut into a diameter of 17mm disk together with film thereon, uncrosslinked film is peeled off from aluminium foil and is placed in
On PTFE plates, the uncrosslinked film comprising positive plate and negative plate is cut into a diameter of 13mm disk, then by positive plate, negative pole
Uncrosslinked film on piece and PTFE plates（Cut out disk）Toast 6h at 35 DEG C, formed porous self-cross linking type polymer film Ca5,
Cb5 and Cc5；
(4) by all porous self-cross linking type polymer films in 1x10-3Pa, at 35 DEG C after vacuum drying 40h, it is quickly transferred to
In glove box full of argon gas, and Cc5 is removed from PTFE plates it is soaked in 24h in electrolyte, the electrolyte liquid is by volume
Than for 1：1：After 1 EC/EMC/DMC mixing, 2.5wt%VC and 1mol/L LiPF is added6Composition, take out i.e. obtain it is porous from
Cross-linking type gel polymer electrolyte Mc5；
(5) the lithium piece negative electrode of the positive electrode and a diameter of 16mm that are covered with Ca5 is kept apart in battery case body using barrier film,
Add electrolyte and seal into 2016 type Li/LiCoO2Polymer Li-ion battery 5.
Embodiment 6
(1) weight average molecular weight 100,000 that the pure-acrylic emulsion C for being 50wt% by 100g solid contents is 20wt% with 750g solid contents
G/mol polyoxyethylene aqueous solution is uniformly mixed, and forms mixed solution；
The pure-acrylic emulsion C is P1040, and its glass transition temperature is 54 DEG C, product producer be the same as Example 1.
(2) mixed solution is placed in syringe, with method of electrostatic spinning respectively with about 10mL mixed solutions in lithium
Spinning on ion battery positive plate, negative plate and aluminium foil, syringe needle used is 8#（External diameter is 0.56mm, and internal diameter is
0.46mm）, flow velocity is 0.8mL/min, and voltage is 10KV, syringe needle translational speed 5-6mm/s, and drum rotation speed is 300rpn, is received
Distance is 12cm, spinning duration 8h, the uncrosslinked film of formation；
(3) aluminium foil is cut into a diameter of 17mm disk together with film thereon, uncrosslinked film is peeled off from aluminium foil and is placed in
On PTFE plates, the uncrosslinked film comprising positive plate and negative plate is cut into a diameter of 13mm disk, then by positive plate, negative pole
Uncrosslinked film on piece and PTFE plates（Cut out disk）Toast 5h at 40 DEG C, formed porous self-cross linking type polymer film Ca6,
Cb6 and Cc6；
(4) by all porous self-cross linking type polymer films in 1x10-3Pa, at 40 DEG C after vacuum drying 40h, it is quickly transferred to
In glove box full of argon gas, and Cc6 is removed from PTFE plates it is soaked in 36h in electrolyte, the electrolyte liquid is by volume
Than for 1：1：1 EC/EMC/DMC mixing after, add 2.5wt%VC and 1mol/L LiPF6 composition, take out i.e. obtain it is porous from
Cross-linking type gel polymer electrolyte Mc6；
(5) the lithium piece negative electrode of the positive electrode and a diameter of 16mm that are covered with Ca6 is kept apart in battery case body using barrier film,
Add electrolyte and seal into 2016 type Li/LiCoO2Polymer Li-ion battery 6.
Embodiment 7
(1) weight average molecular weight 600,000 that the pure-acrylic emulsion B for being 50wt% by 100g solid contents is 10wt% with 750g solid contents
G/mol polyoxyethylene aqueous solution is uniformly mixed, and forms mixed solution；
The pure-acrylic emulsion B is mixed by 80g P1040 and 20g P1005, mixed pure-acrylic emulsion B glass
It is 38 DEG C to change temperature, product producer and temperature computation method be the same as Example 1.
(2) mixed solution is placed in syringe, with method of electrostatic spinning respectively with about 10mL mixed solutions in lithium
Spinning on ion battery positive plate, negative plate and aluminium foil, syringe needle used is 8#（External diameter is 0.56mm, and internal diameter is
0.46mm）, flow velocity is 0.8mL/min, and voltage is 10KV, syringe needle translational speed 5-6mm/s, and drum rotation speed is 300rpn, is received
Distance is 12cm, spinning duration 8h, the uncrosslinked film of formation；
(3) aluminium foil is cut into a diameter of 17mm disk together with film thereon, uncrosslinked film is peeled off from aluminium foil and is placed in
On PTFE plates, the uncrosslinked film comprising positive plate and negative plate is cut into a diameter of 13mm disk, then by positive plate, negative pole
Uncrosslinked film on piece and PTFE plates（Cut out disk）Toast 5h at 50 DEG C, formed porous self-cross linking type polymer film Ca7,
Cb7 and Cc7；
(4) by all porous self-cross linking type polymer films in 1x10-3Pa, at 50 DEG C after vacuum drying 40h, it is quickly transferred to
In glove box full of argon gas, and Cc7 is removed from PTFE plates it is soaked in 24h in electrolyte, the electrolyte liquid is by volume
Than for 1：1：After 1 EC/EMC/DMC mixing, 2.5wt%VC and 1mol/L LiPF is added6Composition, take out i.e. obtain it is porous from
Cross-linking type gel polymer electrolyte Mc7；
(5) the lithium piece negative electrode of the positive electrode and a diameter of 16mm that are covered with Ca7 is kept apart in battery case body using barrier film,
Add electrolyte and seal into 2016 type Li/LiCoO2Polymer Li-ion battery 7.
Comparative example 1
In the glove box full of argon gas and under room ambient conditions, according to the neighbour of 9wt% methyl methacrylate, 2.5wt%
Phthalic acid diethylene glycol diacrylate, 0.5wt% dibenzoyl peroxide and 88wt% concentration are 1M LiPF6Electrolyte
Ratio mix the mixed liquor to form transparence, good fluidity, be attached to mixed liquor using coating method in glove box
On positive electrode, negative electrode and PTFE plates, thermal polymerization is carried out at 85-90 DEG C after being sealed in glove box, the time is 15-
20min, is made gel polymer electrolyte Aa1, Ab1 and the Ac1 being supported on respectively on positive plate, negative plate and PTFE plates, and
Aa1, Ab1 for including positive plate and negative plate are cut into a diameter of 13mm disk, and will be stripped down from PTFE plates
Ac1 be cut into diameter 17mm disk, whole process is all carried out under an inert atmosphere.
Keep apart the positive electrode for being covered with Aa1 in battery case body using barrier film（Disk）With a diameter of 16mm lithium piece negative electricity
Pole, adds electrolyte and seals into 2016 type Li/LiCoO2 polymer Li-ion batteries P.
Comparative example 2
(1) weight average molecular weight 600,000 that the pure-acrylic emulsion C for being 50wt% by 100g solid contents is 10wt% with 750g solid contents
G/mol polyoxyethylene aqueous solution is uniformly mixed, and forms mixed solution；The pure-acrylic emulsion C is P1040, its vitrifying temperature
Spend for 54 DEG C, product producer be the same as Example 1.
(2) mixed solution is respectively coated on positive electrode, negative electrode and aluminium foil with 100 μ m thicks and forms uncrosslinked
Film；
(3) the uncrosslinked film comprising positive electrode and negative electrode is cut into diameter 13mm disk, and comprising aluminium foil not
The film of crosslinking is cut into a diameter of 17mm disk, then strips down film uncrosslinked on aluminium foil, is placed on PTFE plates, will wrap
Containing the uncrosslinked film on positive electrode, negative electrode and PTFE plates（Cut out disk）Vacuum bakeout 12h is crosslinked at 50 DEG C, that is, is obtained
Self-cross linking type polymer film Aa2, Ab2 and Ac2 on positive plate, negative plate and PTFE plates are supported on respectively；
(4) by all self-cross linking type polymer films in 1x10-3Pa, at 50 DEG C after vacuum drying 40h, it is quickly transferred to be full of
In the glove box of argon gas, and Ac2 is removed from PTFE plates it is soaked in 24h in electrolyte, the electrolyte liquid is by volume ratio
1：1：After 1 EC/EMC/DMC mixing, 2.5wt%VC and 1mol/L LiPF6 compositions are added, it is to obtain self-cross linking type to coagulate to take out
Xanthan polymer electrolyte Bc2.
Keep apart the lithium piece negative electrode of the positive electrode and a diameter of 16mm that are covered with Aa2 in battery case body using barrier film, plus
Enter electrolyte, the electrolyte liquid is 1 by volume ratio：1：After 1 EC/EMC/DMC mixing, add 2.5wt%VC's and 1mol/L
LiPF6Composition, seals into 2016 type Li/LiCoO2Polymer Li-ion battery Q.
Positive electrode in above-described embodiment and comparative example is by for the positive electrode and conductive agent of lithium ion battery, bonding
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, also wrap
Include other any positive electrodes available for lithium ion battery, 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 above-mentioned negative electrode can also be by will adjust for the negative material and conductive agent of lithium ion battery, binding agent
It is coated in metal foil and is made into slurry, negative material used includes any negative material available for lithium ion battery, such as stone
Ink, soft carbon, hard carbon etc..The metal foil includes arbitrarily playing the metal foil of electric action, such as copper foil, aluminium foil.
Barrier film in above-described embodiment and comparative example is the barrier film for being arbitrarily applicable to lithium ion battery, such as PP barrier films, PE
Barrier film and PE/PP/PE three-layer membranes etc..
In addition to the electrolyte in above-described embodiment and comparative example, the electrolyte can be made up of lithium salts and organic solvent,
Wherein the concentration of lithium salts is 0.8-1.5mol/L；The lithium salts can select lithium hexafluoro phosphate（LiPF6）, lithium perchlorate（LiClO4）
And LiBF4（LiBF4）Deng；Organic solvent can select ethylene carbonate（EC）, propene carbonate（PC）, dimethyl carbonate
（DMC）, methyl ethyl carbonate（EMC）And diethyl carbonate（DEC）, vinylene carbonate（VC）In one or more mixing.
In above-described embodiment, in addition to using the positive plate of porous self-cross linking type polymer film, lithium piece negative electrode is covered with,
It can be used as described below：Such as in the glove box full of argon gas with the general barrier film of lithium ion battery separate overlay film negative plate and
Lithium piece, adds electrolyte, seals into polymer Li-ion battery；In the glove box full of argon gas with lithium ion battery it is general every
Film separates the positive plate of overlay film and the negative plate of overlay film, adds electrolyte and seals into polymer Li-ion battery.
In addition, the pure-acrylic emulsion in above-described embodiment is in addition to two kinds of P1040 and P1005, it is of the prior art any pure
Acrylic emulsion is applied to the present invention.
Test case
（1）The thickness of porous self-cross linking type gelatin polymer film Cc1-Cc7 in embodiment 1-7 is determined, and is gathered in comparative example 2
Compound film Ac2 thickness, the results are shown in Table 1；
Table 1
As shown in Table 1, in embodiment 1-7 the thickness of porous self-cross linking type polymer film in 10.1-13.2 μ ms, this
Outside can also be as needed by film preparation into any thickness in 0.01-100 μ ms, therefore porous self-crosslinking of the present invention
The film of type gel polymer electrolyte formation is suitable to the lithium ion battery for making all size capacity.
（2）Determine Cc1-Cc7, Ac2 porosity：The radius r and thickness d of disc-shaped film are measured, mass M is weighed up0After soak
The 2h in n-butanol is steeped, the liquid that film surface is blotted with filter paper is then taken out and weighs mass M now, according to equation below
Porosity is calculated, 2 are the results are shown in Table；
（3）Determine Cc1-Cc7, Ac2 pick up：It is put into the glove box full of argon gas, claims after disc-shaped film is dried
24h in electrolyte is immersed in after good quality W, the liquid that film surface is blotted with filter paper is then taken out and weighs quality now
Wi, pick up is calculated according to the following equation, the results are shown in Table 2；
Table 2
| Porosity（%） | Pick up（%） | |
| Cc1 | 73 | 1084 |
| Cc2 | 76 | 1157 |
| Cc3 | 81 | 1203 |
| Cc4 | 85 | 1162 |
| Cc5 | 77 | 1191 |
| Cc6 | 73 | 1239 |
| Cc7 | 78 | 1189 |
| Ac2 | — | 725 |
As shown in Table 2, the porosity of porous self-cross linking type gelatin polymer film of the present invention, pick up are far above contrast
Gel polymer electrolyte in example, illustrates that Inventive polymers film has very high liquid storage capacity, and be full of electrolyte
Loose structure can improve the migration velocity of lithium ion.
（4）Determine Mc1-Mc7, Ac1 and Bc2 electrical conductivity：Disc-shaped film after enough electrolyte will be absorbed and be placed on two not
Become rusty steel（SS, Ф=1.6cm）Between electrode, 2016 type button cells are sealed in（The limited public affairs of the positive safe electromechanical equipment in Shenzhen East China
Department）Afterwards, ac impedance measurement is carried out using the CHI604b types electrochemical workstation of Shanghai Chen Hua, measures the body impedance R of film,
The electrical conductivity for obtaining film is calculated according to the following formula, the results are shown in Table 3：
σ=L/A·R
Wherein L represents thickness, and A is the real contact area of stainless steel electrode and film；
Table 3
As shown in Table 3, the electrical conductivity of porous self-cross linking type gel polymer electrolyte of the present invention is far above comparative example
In gel polymer electrolyte, meanwhile, the body impedance of porous self-cross linking type gel polymer electrolyte of the present invention is low
Gel polymer electrolyte in comparative example.
（5）Lithium ion battery 1-7, P and Q charge-discharge property are determined：Using BK6016 type performance of lithium ion batteries
Test cabinet（Guangzhou Lanqi Electronic Industrial Co., Ltd.）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 is 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, first
Discharge capacity/initial charge capacity × 100% of efficiency for charge-discharge=first, obtains specific capacity and first charge-discharge efficiency, as a result sees
Table 4；
Table 4
| Lithium ion battery | Specific capacity（mAh/g） | First charge-discharge efficiency（%） |
| 1 | 146 | 97.03 |
| 2 | 145 | 97.88 |
| 3 | 140 | 98.03 |
| 4 | 143 | 97.35 |
| 5 | 141 | 98.99 |
| 6 | 144 | 98.21 |
| 7 | 143 | 98.44 |
| P | 143 | 96.56 |
| Q | 145 | 95.11 |
As shown in Table 4, the first charge-discharge efficiency of porous self-cross linking type gel polymer electrolyte of the present invention is higher than
Comparative example.
（6）Lithium ion battery 1-7, P and Q multiplying power charging 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 first as battery rated capacity：I. first by battery 0.1C constant current constant voltages
4.2V is charged to, is shelved after 5min, 3.0V is discharged to 0.1C, 5min is shelved, then is filled respectively with 0.2C/0.5C/1C/3C constant currents
Electricity is to 4.2V, then constant-voltage charge at 4.2v, and cut-off current is 0.02C, records charging capacity under each multiplying power, the results are shown in Table 5；
Ii. by battery 0.1C constant-current charges to 4.2V, then constant-voltage charge at 4.2v, cut-off current is 0.02C, is put
5min is put, 3.0V is discharged to 0.2C/0.5C/1C/3C respectively, each multiplying power discharge capacity is recorded, the results are shown in Table 6；
Table 5
Table 6
From the lithium ion of table 5-6, the method for the invention porous self-cross linking type gel polymer electrolyte prepared
The charging of each multiplying power of battery and each multiplying power discharging property have compared with comparative example largely to be improved, this be due in the present invention it is porous from
The body impedance of cross-linking type gel polymer electrolyte reduces, and electrical conductivity is high, can reduce the polarization phenomena in charge and discharge process,
Be conducive to the migration of lithium ion.
Although the present invention has carried out detailed elaboration by above-mentioned specific embodiment to it, this specialty is common
Technical staff should be understood that any form without departing from claims made on this basis and the change of details
Change, belong to invention which is intended to be protected.
Claims (17)
1. a kind of porous self-cross linking type polymer film, it is characterised in that
By pure-acrylic emulsion and polyethylene oxide solutions mixing after electrostatic spinning and be crosslinked obtain；
The porosity of the porous self-cross linking type polymer film is 60-90%.
2. porous self-cross linking type polymer film according to claim 1, it is characterised in that the vitrifying of the pure-acrylic emulsion
Temperature is -30-70 DEG C.
3. porous self-cross linking type polymer film according to claim 2, it is characterised in that the vitrifying of the pure-acrylic emulsion
Temperature is -18-60 DEG C.
4. according to any described porous self-cross linking type polymer films of claim 1-3, it is characterised in that the polyethylene glycol oxide
Weight average molecular weight be 50,000-800 ten thousand g/mol.
5. porous self-cross linking type polymer film according to claim 4, it is characterised in that the weight of the polyethylene glycol oxide is equal
Molecular weight is 100,000-400 ten thousand g/mol.
6. porous self-cross linking type polymer film according to claim 5, it is characterised in that the weight of the polyethylene glycol oxide is equal
Molecular weight is 200,000-200 ten thousand g/mol.
7. the porous self-cross linking type polymer film according to claim 1,2,3,5 or 6, it is characterised in that polyethylene glycol oxide
The solid content of solution is 1-50wt%, and the solid content of the pure-acrylic emulsion is 40-60wt%, the solid weight of the pure-acrylic emulsion
Solid weight ratio with polyethylene oxide solutions is 1：(0.1-5).
8. porous self-cross linking type polymer film according to claim 7, it is characterised in that the solid weight of the pure-acrylic emulsion
The solid weight ratio of amount and polyethylene oxide solutions is 1：(0.5-3).
9. porous self-cross linking type polymer film according to claim 8, it is characterised in that the polyethylene oxide solutions
Solid content is 2-20wt%.
10. porous self-cross linking type polymer film according to claim 8 or claim 9, it is characterised in that film thickness is 0.01-110
μm。
11. the porous self-cross linking type gelatin polymer obtained by any porous self-cross linking type polymer films of claim 1-10
Electrolyte, it is characterised in that obtained by porous self-cross linking type polymer film contact electrolyte.
12. porous self-cross linking type gel polymer electrolyte according to claim 11, it is characterised in that it is described it is porous from
The electrical conductivity of cross-linking type gel polymer electrolyte is 7-10mS/cm.
13. the preparation method of any porous self-cross linking type polymer films of claim 1-10, comprises the following steps,
(1) pure-acrylic emulsion is uniformly mixed with polyethylene oxide solutions, forms mixed solution；
(2) uncrosslinked film is formed in electrode surface electrostatic spinning with the mixed solution；
(3) the uncrosslinked film is toasted at 20-50 DEG C, forms porous self-cross linking type polymer film.
14. the preparation method of porous self-cross linking type polymer film according to claim 13, it is characterised in that step (3)
In baking time be 0.01-24h, baking temperature be 30-50 DEG C.
15. the porous self-cross linking type method for preparing gel polymer electrolyte described in claim 11 or 12, will be dried in vacuo
Porous self-cross linking type polymer film afterwards is soaked in electrolyte under an inert atmosphere, taking-up.
16. porous self-cross linking type method for preparing gel polymer electrolyte according to claim 15, it is characterised in that
Vacuum drying temperature is 30-50 DEG C, the time is 10-30h；The time being soaked in electrolyte is no less than 24h.
17. usage right requires the lithium ion battery of any porous self-cross linking type polymer films of 1-10, including,
The battery case internal body portion is divided into positive pole conversion zone and negative reaction area by battery cell body and barrier film, the barrier film
Domain；
Positive pole, is arranged in the positive pole conversion zone；
Negative pole, is arranged in the negative reaction region；
Electrolyte, is filled in the positive pole conversion zone and negative reaction region；
The porous self-cross linking type polymer film is arranged between the positive pole and negative pole, and with the negative or positive electrode at least
One is in contact；
The positive pole, negative pole, barrier film and porous self-cross linking type polymer film are impregnated in the electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310754009.7A CN104752760B (en) | 2013-12-31 | 2013-12-31 | A kind of porous self-cross linking type gel polymer electrolyte, the electrolyte preparation method and its application in lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310754009.7A CN104752760B (en) | 2013-12-31 | 2013-12-31 | A kind of porous self-cross linking type gel polymer electrolyte, the electrolyte preparation method and its application in lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104752760A CN104752760A (en) | 2015-07-01 |
| CN104752760B true CN104752760B (en) | 2017-10-31 |
Family
ID=53592088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310754009.7A Active CN104752760B (en) | 2013-12-31 | 2013-12-31 | A kind of porous self-cross linking type gel polymer electrolyte, the electrolyte preparation method and its application in lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104752760B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107516724A (en) * | 2016-06-16 | 2017-12-26 | 宁德新能源科技有限公司 | Battery core and energy storage device |
| CN107516723A (en) * | 2016-06-16 | 2017-12-26 | 宁德新能源科技有限公司 | Battery core and energy storage device |
| CN110635133B (en) * | 2019-08-30 | 2021-08-06 | 东莞赣锋电子有限公司 | Quick-charging type lithium ion battery and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530750A (en) * | 2009-04-20 | 2009-09-16 | 浙江理工大学 | Preparation method of polytetrafluoroethylene superfine fiber porous membrane |
| CN101599557A (en) * | 2008-06-06 | 2009-12-09 | 比亚迪股份有限公司 | A kind of preparation method of polymer Li-ion battery |
| CN103441300A (en) * | 2013-08-23 | 2013-12-11 | 浙江地坤键新能源科技有限公司 | Gel polymer electrolyte containing natural high molecular material as well as preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10136255B4 (en) * | 2001-07-25 | 2005-05-04 | Helsa-Werke Helmut Sandler Gmbh & Co. Kg | Device for producing fibers with improved arrangement of the spray electrodes |
| KR101351897B1 (en) * | 2011-01-20 | 2014-01-17 | 주식회사 엘지화학 | Electrolyte for electrochemical device, the preparation method thereof and electrochemical device comprising the same |
-
2013
- 2013-12-31 CN CN201310754009.7A patent/CN104752760B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101599557A (en) * | 2008-06-06 | 2009-12-09 | 比亚迪股份有限公司 | A kind of preparation method of polymer Li-ion battery |
| CN101530750A (en) * | 2009-04-20 | 2009-09-16 | 浙江理工大学 | Preparation method of polytetrafluoroethylene superfine fiber porous membrane |
| CN103441300A (en) * | 2013-08-23 | 2013-12-11 | 浙江地坤键新能源科技有限公司 | Gel polymer electrolyte containing natural high molecular material as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Effects of crown ethers on the electrochemical properties of polymeric solid electrolytes consisting of poly(ethylene oxide)-grafted poly(methylmethacrylates)";Masayuki Morita等;《Solid State Ionics》;19961231;第86-88卷;第401～405页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104752760A (en) | 2015-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021057428A1 (en) | Secondary battery and battery module, battery pack and device containing same | |
| CN110265627B (en) | Positive electrode plate and lithium ion secondary battery | |
| CN107732293B (en) | The preparation method of class sandwich structure solid polymer electrolyte membrane and its application in solid lithium ion battery | |
| CN104868165B (en) | Preparation method of gel-state polymer lithium battery and battery | |
| CN109494349B (en) | Negative pole piece and secondary battery | |
| CN104134818B (en) | High-energy-density lithium ion battery and preparation method thereof | |
| CN102340027B (en) | Lithium ion battery with high energy density | |
| CN110265626B (en) | Positive pole piece, preparation method thereof and lithium ion secondary battery | |
| CN113273005A (en) | Secondary battery, device comprising same, method for producing secondary battery, and binder composition | |
| CN110808411B (en) | Electrolyte and lithium ion battery | |
| CN112635835B (en) | High-low temperature compatible non-aqueous electrolyte and lithium ion battery | |
| JP7520242B2 (en) | Binder compound and method for producing same | |
| CN101677139A (en) | Method of preparing gel polymer lithium ion battery | |
| CN101662046A (en) | Lithium ion battery | |
| CN102332600A (en) | Lithium ion battery | |
| CN104752760B (en) | A kind of porous self-cross linking type gel polymer electrolyte, the electrolyte preparation method and its application in lithium ion battery | |
| CN101826640A (en) | Pole core for lithium ion battery and lithium ion battery using pole core | |
| CN104752761B (en) | Porous self-cross linking type gel polymer electrolyte and its application in lithium ion battery | |
| CN115136357A (en) | Positive pole piece and lithium ion secondary battery comprising same | |
| CN115810797A (en) | Lithium ion battery, battery module, battery pack and electric device | |
| WO2021121222A1 (en) | Secondary battery | |
| CN104744722B (en) | 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 | |
| CN108630864A (en) | A kind of cathode and diaphragm integral structure and preparation method thereof and battery | |
| CN106207049A (en) | Ceramic diaphragm and application thereof in lithium ion battery | |
| CN107492660A (en) | Anode sizing agent, positive plate and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |