CN104393337B - Lithium ion battery gel electrolyte with multi-stage structure and preparation method thereof - Google Patents
Lithium ion battery gel electrolyte with multi-stage structure and preparation method thereof Download PDFInfo
- Publication number
- CN104393337B CN104393337B CN201410750614.1A CN201410750614A CN104393337B CN 104393337 B CN104393337 B CN 104393337B CN 201410750614 A CN201410750614 A CN 201410750614A CN 104393337 B CN104393337 B CN 104393337B
- Authority
- CN
- China
- Prior art keywords
- polymer
- electrostatic spinning
- electrolyte
- gel electrolyte
- lithium ion
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
Abstract
The invention discloses lithium ion battery gel electrolyte with a multi-stage structure and a preparation method thereof. The lithium ion battery gel electrolyte with the multi-stage structure comprises a polymer network cross-linking framework and a liquid electrolyte in the network framework, wherein the polymer network physical cross-linking framework is composed of nano fibers of PVDF (Polyvinylidene Fluoride) electrostatic spinning, and the cross-linking framework is adsorbed to two sides of a base PE (Poly Ethylene) film. The preparation method comprises the following steps: 1) preparing an electrostatic spinning solution; 2) preparing a first-level framework structure by electrostatic spinning; 3) coating a polymer so as to prepare a second-level framework structure; and 4) carrying out high-temperature in-situ polymerization so as to prepare a PMMA (Polymethyl Methacrylate) gel polymer three-level framework structure. The gel frameworks are distributed in a level-by-level structure, and compared with a conventional gel system, the macromolecule cross-linking system of the multi-level structure has the advantages of high mechanical intensity, high fluid protection capability, high porosity of the network structure, high conductivity and the like, and paves the way for the research of a new generation of gel electrolytes.
Description
Technical field
The present invention relates to the lithium ion battery of multilevel hierarchy with polymer gel electrolyte system (include gel electrolyte and
Diaphragm support skeleton), particularly to include PVDF Electrospun nano-fibers, PVDF-HFP crosslinked polymer two grade network and
The gel electrolyte system of the crosslinked polymer network of in-situ polymerization.
Background technology
Lithium ion battery is due to having the advantages that voltage height, small volume, lightweight, energy density is high and has extended cycle life,
Obtain the leading position in market.
At present, the electrolyte of lithium ion battery is divided into liquid electrolyte and gel electrolyte.Wherein, the spy of liquid electrolyte
The problems such as point is that stable electrochemical property is reliable, but generally existing security is poor, battery hardness is not yielding.Compare it
Under, the solvent molecule of flowable state is fixed in high-molecular gel skeleton gel electrolyte liquid system, because not existing or less presence
The solvent of free state and reduce the risk of solution leakage, significantly reduce the flammability of battery system, and then improve
The security of battery；Simultaneously as whole battery core is linked to be an entirety by macromolecular scaffold, it is thus advantageous to reduce battery core deformation
And expansion.So, gel electrolyte liquid system has very bright application prospect.
Existing gel electrolyte is usually to add polymerisable monomer in liquid electrolyte to be prepared from, and that is added can
Polymerized monomer dissolves in liquid electrolyte, and the polymer of generation also dissolves in liquid electrolyte.Due in gel electrolyte precursor
When the concentration of polymerisable monomer is relatively low, liquid electrolyte can be insufficient to allow to be converted to gel electrolyte, therefore generally require to add
More polymerisable monomer；But the polymer concentration when concentration of polymerisable monomer is higher, in the gel electrolyte being generated
Higher, lithium ion conduction can be caused difficult, so that a series of chemical properties such as low, the easy analysis lithium of lithium ion conductivity occur again
Problem.
In view of this, it is necessory to provide all good lithium of a kind of mechanical property, chemical property and security from
Sub- battery gel electrolyte.
Content of the invention
It is an object of the invention to：There is provided all good lithium of a kind of mechanical property, chemical property and security from
Sub- battery gel electrolyte；Further object is that it is higher to obtain a kind of liquid measure of protecting by the design of multilevel hierarchy,
The more stable gel electrolyte of lithium ion battery of structure.
To achieve these goals, the present invention technical scheme as follows:
The invention provides a kind of lithium ion battery gel electrolyte of multilevel hierarchy, it includes polymer network crosslinking bone
Frame and the liquid electrolyte being present in network skeleton, wherein polymer network cross-linked scaffold are the one-level knot of gel electrolyte
Structure, is to be made up of the nanofiber of Kynoar (PVDF) electrostatic spinning, cross-linked scaffold is adsorbed in the both sides of basement membrane PE film；Poly-
Compound crosslinking main body is the macromolecule of Kynoar and weight average molecular weight 10-100 ten thousand of hexafluoropropene copolymerization (PVDF-HFP),
It is adsorbed between one-level skeleton, as the secondary structure of gel electrolyte；Three-level skeleton is with the PVDF-HFP of two grades of skeletons
Copolymerized macromolecule cross-linked network is polymethyl methacrylate (PMMA) the in-situ polymerization high-molecular gel network of fulcrum, mainly carries
For keeping the electro-hydraulic effect of liquid.
It is an advantage of the invention that the structure distribution step by step of gel skeleton, the machinery of Electrospun nano-fibers on PE basement membrane
Intensity highest, main offer system intensity and support, the PVDF-HFP polymer being interspersed between nanofiber is gel cross-linkage
Main body, plays the transition structure providing sectional interest intensity and connecting macroscopical primary structure and microcosmic tertiary structure, tertiary structure
PMMA in-situ polymerization structure plays the effect of the small molecule solvent and lithium ion salt keeping in liquid electrolyte.This multilayered structure
High molecular crosslink system have high mechanical strength compared to conventional GPC system, liquid-keeping property is strong, and network structure porosity is big,
The advantages of electrical conductivity is high, has broad application prospects.
The preparation method of the lithium ion battery gel electrolyte of multilevel hierarchy, comprises the following steps：
(1) prepare electrostatic spinning solution：
Will carry out the polymer of electrostatic spinning temperature be dissolved under 40～80 DEG C (preferably 50 DEG C) organic accordingly molten
In agent, stirring (generally 6 hours about) makes it mix, prepared polymer electrospun solution；Polymer is in Static Spinning
Volumetric concentration in silk solution is 10%～30%, and preferred volume concentration is 15%；
(2) electrostatic spinning preparation one-level skeleton structure：
The electrostatic spinning solution that step (1) is prepared loads the device for storing liquid of the electrospinning device that temperature is 40～80 DEG C
In, the piston of device for storing liquid is connected with syringe pump, and device for storing liquid is connected with spinning head by polyfluortetraethylene pipe, adjusts electrostatic
The feeding rate of spinning solution is 5～300 μ L/min, preferably 20～150 μ L/min；The spinning head of electrospinning device with connect
The distance between the collector on ground is 5～25cm, preferably 7～20cm；Environment temperature is 35～80 DEG C, preferably 40～60
℃；The air velocity of environment is 0～8.5m3/ h, preferably 0.5～5m3/h；Lithium battery diaphragm is placed on collector, opens high
Voltage source (electrostatic pressure is 1～60kV, and Appropriate is 15～20kV), opens syringe pump, electrostatic spinning solution injection stream is sprayed
It is mapped on lithium battery diaphragm, polymer electrospun nanofiber film layer is obtained on barrier film, thus form polymeric electrostatic spinning
Silk nanofiber primary structure；
(3) polymer-coated prepares two grades of skeleton structures：
On the above-mentioned barrier film containing polymer electrospun nanofiber, coating molecular weight is 50～5,000,000 macromolecule
Amount PVDF-HFP copolymer, coats post-drying, obtains the two grades of bones of PVDF-HFP copolymer being interspersed between polymer nanofiber
Frame；Coating can use aqueous coating, the wherein optional aqueous solvent of solvent such as deionized water；Coating also can be coated with oiliness, wherein
Solvent can choose oil-based solvent such as acetone, dimethylformamide (DMF)；The mixed slurry concentration of coating is 20%～50%
(percentage of PVDF-HFP), the speeds control position 0.5m/min～15m/min of coating, the wind speed 5000～1800rpm of drying,
Temperature 50 C～200 DEG C；
(4) battery winding.
By the septum purge containing nanofiber and PVDF-HFP, it is dried, evacuation storage, and is wound in battery；
(5) electrolyte performed polymer fluid injection：
Add the macromolecule performed polymer of polymetylmethacrylate in conventional electrolysis liquid, add initiator peroxidating
Dibenzoyl (BPO), in injection battery after crosslinking agent triethylamine, with electrolyte stirring at normal temperature 12h；
(6) high-temp in-situ polymerization, prepares PMMA gelatin polymer three-level skeleton structure：
Battery after fluid injection is carried out standing under high temperature and, so as to in-situ polymerization, obtains bis- grades of PVDF-HFP on nanofiber
Interspersed crosslinked PMMA three-level crosslinked polymer network structure between skeleton；Wherein, lithium ion battery dwell temperature is 50 DEG C～150
DEG C, time of repose is 5min～12h.
Cross-linked network structure launches in different scale scope internal classification, can greatly improve crosslinked polymer network structure
Guarantor's fluidity and mechanical stability, thus improving lithium ion battery safety performance and cycle performance.
Compared with prior art, the gel electrolyte of lithium ion battery containing multilevel hierarchy of the present invention have following excellent
Point：
Due to the multi-stratification of its structure, each level structure has support to make in different range scales to gel electrolyte
With under large scale, as supportive body, under micro-scale, PMMA polymer three-dimensional crosslinked network is electro-hydraulic as holding for nanofiber
Main body so that the present invention preparation gel batteries compared to conventional gel battery, its liquid-keeping property is higher, the electro-hydraulic machine of gel
Tool intensity is higher, the security performance of gel batteries more preferably, Electrospun nano-fibers film layer porosity higher so that gel electrolyte
The overall conductivity of liquid improves, and cycle performance also has larger lifting, be future new era gel batteries opened up new
Direction.
Brief description
Fig. 1, gel electrolyte multilevel hierarchy schematic diagram；
Fig. 2, gel electrolyte primary structure, PVDF Nanofiber Network structural scan electron microscope (SEM) figure；
Fig. 3, gel electrolyte secondary structure and tertiary structure, super high molecular weight PVDF- between PVDF Nanofiber Network
HFP and PMMA polymer cross-linked network SEM schemes；
Fig. 4, gel electrolyte secondary structure and tertiary structure, the crosslinked polymer network of PVDF nanofiber surface absorption
SEM schemes；
Fig. 5, polymer electrospun process schematic.
Specific embodiment
Lithium ion battery gel electrolyte structure of the present invention is as shown in figure 1, it includes polymer network cross-linked scaffold and deposits
It is the liquid electrolyte in network skeleton, wherein polymer network is physical crosslinking the primary structure 1 that skeleton is gel electrolyte,
It is to be made up of the nanofiber of Kynoar (PVDF) electrostatic spinning, cross-linked scaffold is adsorbed in the both sides of basement membrane PE film 4；Polymerization
Thing crosslinking main body is the macromolecule of weight average molecular weight 10-100 ten thousand of PVDF-HFP copolymerization, and it is adsorbed between one-level skeleton, makees
For gelatin polymer secondary structure 2；Three-level skeleton 3 is with the PVDF-HFP copolymerized macromolecule cross-linked network of two grades of skeletons as fulcrum
Polymetylmethacrylate in-situ polymerization high-molecular gel network, main offer keep the electro-hydraulic effect of liquid.
Embodiment 1
1). prepare electrostatic spinning solution.The polymer (Kynoar) that electrostatic spinning will be carried out is dissolved at 50 DEG C
In DMF, stirring 6h makes it mix, prepared polymer electrospun solution, and wherein polymer is in electrostatic
Volumetric concentration in spinning solution is 15% (g/mL).
(2) electrostatic spinning preparation one-level skeleton structure：
Process is as shown in figure 5, by step 1) electrostatic spinning solution for preparing loads the electrospinning device that temperature is 50 DEG C
Device for storing liquid in, the piston of device for storing liquid is connected with syringe pump, device for storing liquid pass through polyfluortetraethylene pipe and spinning head phase
Even, spinning head is fixed, and metal plate is placed non-woven fabrics as collector.Adjusting the distance between spinning head and collecting board is
15cm；The environment temperature of spinning is 50 DEG C, and the temperature including electrostatic spinning solution in device for storing liquid and the temperature of collecting board are
50 DEG C, the air velocity in environment controls in 0.5～0.8m3/h；Open high voltage power supply, adjust voltage to 15kV, electrostatic spinning
The feeding rate of solution is 60 μ L/min, opens syringe pump, electrostatic spinning solution injection stream is ejected on lithium battery diaphragm,
Polymer electrospun nanofiber film layer is obtained on barrier film, thus forming polymer electrospun nanofiber one-level knot
Structure.Average fibre diameter is 500nm, and polymer electrospun nanofiber thicknesses of layers is 40 μm, and (polymer electrospun is received
The SEM figure of rice fiber film layer is shown in Fig. 2).
(3) polymer-coated prepares two grades of skeleton structures：
In the HMW PVDF-HFP being about 50w containing coating molecular weight on polymer electrospun nano fiber diaphragm
Copolymer (product is purchased from Arkema, model LBG), coats post-drying, obtains being interspersed between polymer nanofiber
Two grades of skeletons of PVDF-HFP copolymer.Coating is coated using oiliness, and wherein oil-based solvent acetone chosen by solvent.The mixing slurry of coating
Material concentration is 20%, the speeds control position 1m/min of coating, the wind speed 5000rpm of drying, 90 DEG C of temperature.
(4) battery winding.
Barrier film containing nanofiber and PVDF-HFP is used ethanol purge, is dried, evacuation storage, and is wound in electricity
Chi Zhong.
(5) electrolyte performed polymer fluid injection：
Allotment electrolyte ethylene carbonate (EC), dimethyl carbonate (DEC), methyl ethyl carbonate (EMC) proportioning is 1：1：1,
The molar concentration of lithium hexafluoro phosphate is 1.0mol/L.Add the macromolecule pre-polymerization of polymetylmethacrylate in the electrolytic solution
Body, adds initiator B PO, crosslinking agent triethylamine, and the percentage composition of wherein electro-hydraulic middle PMMA is that the percentage composition of 10%, BPO is
0.1%, the percentage composition of triethylamine is in injection battery after 1% and electrolyte stirring at normal temperature 12h.
(6) high-temp in-situ polymerization, prepares PMMA gelatin polymer three-level skeleton structure：
Battery after fluid injection is carried out standing under high temperature and, so as to in-situ polymerization, obtains bis- grades of PVDF-HFP on nanofiber
Interspersed crosslinked PMMA three-level crosslinked polymer network structure between skeleton.Wherein, lithium ion battery dwell temperature is 80 DEG C, standing
Time is 24h.
Gel electrolyte secondary structure and tertiary structure, between PVDF Nanofiber Network super high molecular weight PVDF-HFP with
PMMA polymer cross-linked network SEM figure is shown in Fig. 3.Gel electrolyte secondary structure and tertiary structure, PVDF nanofiber surface is inhaled
Attached crosslinked polymer network SEM figure is shown in Fig. 4.
Embodiment 2
1). prepare electrostatic spinning solution.The polymer (Kynoar) that electrostatic spinning will be carried out is dissolved at 50 DEG C
In DMF, stirring 6h makes it mix, prepared polymer electrospun solution, and wherein polymer is in electrostatic
Volumetric concentration in spinning solution is 15% (g/mL).
(2) electrostatic spinning preparation one-level skeleton structure：
By step 1) to load temperature be in 50 DEG C of the device for storing liquid of electrospinning device for the electrostatic spinning solution for preparing, storage
The piston of liquid device is connected with syringe pump, and device for storing liquid is connected with spinning head by polyfluortetraethylene pipe, and spinning head is fixed, gold
Belong to and non-woven fabrics is placed on flat board as collector.Adjusting the distance between spinning head and collecting board is 15cm；The environment temperature of spinning
Spend for 50 DEG C, the temperature including electrostatic spinning solution in device for storing liquid and the temperature of collecting board are 50 DEG C, the air in environment
Flow control is in 0.5～0.8m3/h；Open high voltage power supply, adjust voltage to 15kV, the feeding rate of electrostatic spinning solution is 60
μ L/min, opens syringe pump, electrostatic spinning solution injection stream is ejected on lithium battery diaphragm, obtains polymer on barrier film
Electrospun nano-fibers film layer, thus forming polymer electrospun nanofiber primary structure.Average fibre diameter is
500nm, polymer electrospun nanofiber thicknesses of layers is 40 μm of (SEM figures of polymer electrospun nanofiber film layer
See Fig. 2).
(3) polymer-coated prepares two grades of skeleton structures：
In the HMW PVDF-HFP copolymer being about 45w containing coating molecular weight on polymer nanofiber barrier film
(product is purchased from Su Wei company, model 21216, and wherein HFP copolymerization ratios are higher), coats post-drying, obtains being interspersed in polymer
Two grades of skeletons of PVDF-HFP copolymer between nanofiber.Coating is coated using oiliness, and wherein oil-based solvent acetone chosen by solvent.
The mixed slurry concentration of coating is 20%, the speeds control position 1m/min of coating, the wind speed 5000rpm of drying, 90 DEG C of temperature.
(4) battery winding.
Barrier film containing nanofiber and PVDF-HFP is used ethanol purge, is dried, evacuation storage, and is wound in electricity
Chi Zhong.
(5) electrolyte performed polymer fluid injection：
Allotment electrolyte ethylene carbonate (EC), dimethyl carbonate (DEC), methyl ethyl carbonate (EMC) proportioning is 1：1：1,
The molar concentration of lithium hexafluoro phosphate is 1.0mol/L.Add the macromolecule pre-polymerization of polymetylmethacrylate in the electrolytic solution
Body, adds initiator B PO, crosslinking agent triethylamine, and the percentage composition of wherein electro-hydraulic middle PMMA is that the percentage composition of 10%, BPO is
0.1%, the percentage composition of triethylamine is in injection battery after 1% and electrolyte stirring at normal temperature 12h.
(6) high-temp in-situ polymerization, prepares PMMA gelatin polymer three-level skeleton structure：
Battery after fluid injection is carried out standing under high temperature and, so as to in-situ polymerization, obtains bis- grades of PVDF-HFP on nanofiber
Interspersed crosslinked PMMA three-level crosslinked polymer network structure between skeleton.Wherein, lithium ion battery dwell temperature is 80 DEG C, standing
Time is 24h.
Embodiment 3
1). prepare electrostatic spinning solution.The polymer (Kynoar) that electrostatic spinning will be carried out is dissolved at 50 DEG C
In DMF, stirring 6h makes it mix, prepared polymer electrospun solution, and wherein polymer is in electrostatic
Volumetric concentration in spinning solution is 15% (g/mL).
(2) electrostatic spinning preparation one-level skeleton structure：
By step 1) to load temperature be in 50 DEG C of the device for storing liquid of electrospinning device for the electrostatic spinning solution for preparing, storage
The piston of liquid device is connected with syringe pump, and device for storing liquid is connected with spinning head by polyfluortetraethylene pipe, and spinning head is fixed, gold
Belong to and non-woven fabrics is placed on flat board as collector.Adjusting the distance between spinning head and collecting board is 15cm；The environment temperature of spinning
Spend for 50 DEG C, the temperature including electrostatic spinning solution in device for storing liquid and the temperature of collecting board are 50 DEG C, the air in environment
Flow control is in 0.5～0.8m3/h；Open high voltage power supply, adjust voltage to 15kV, the feeding rate of electrostatic spinning solution is 60
μ L/min, opens syringe pump, electrostatic spinning solution injection stream is ejected on lithium battery diaphragm, obtains polymer on barrier film
Electrospun nano-fibers film layer, thus forming polymer electrospun nanofiber primary structure.Average fibre diameter is
500nm, polymer electrospun nanofiber thicknesses of layers is 40 μm of (SEM figures of polymer electrospun nanofiber film layer
See Fig. 2).
(3) polymer-coated prepares two grades of skeleton structures：
In the HMW PVDF-HFP copolymer being about 50w containing coating molecular weight on polymer nanofiber barrier film
(product is purchased from Arkema, model 8500, this fluorine-containing height developed for Arkema exclusively for gel electrolyte
Molecule adhesive), coat post-drying, obtain the two grades of skeletons of PVDF-HFP copolymer being interspersed between polymer nanofiber.Apply
Cover and coated using oiliness, wherein oil-based solvent acetone chosen by solvent.The mixed slurry concentration of coating is 20%, the speed control of coating
Position 1m/min processed, the wind speed 5000rpm of drying, 90 DEG C of temperature.
(4) battery winding.
Barrier film containing nanofiber and PVDF-HFP is used ethanol purge, is dried, evacuation storage, and is wound in electricity
Chi Zhong.
(5) electrolyte performed polymer fluid injection：
Allotment electrolyte ethylene carbonate (EC), dimethyl carbonate (DEC), methyl ethyl carbonate (EMC) proportioning is 1：1：1,
The molar concentration of lithium hexafluoro phosphate is 1.0mol/L.Add the macromolecule pre-polymerization of polymetylmethacrylate in the electrolytic solution
Body, adds initiator B PO, crosslinking agent triethylamine, and the percentage composition of wherein electro-hydraulic middle PMMA is that the percentage composition of 10%, BPO is
0.1%, the percentage composition of triethylamine is in injection battery after 1% and electrolyte stirring at normal temperature 12h.
(6) high-temp in-situ polymerization, prepares PMMA gelatin polymer three-level skeleton structure：
Battery after fluid injection is carried out standing under high temperature and, so as to in-situ polymerization, obtains bis- grades of PVDF-HFP on nanofiber
Interspersed crosslinked PMMA three-level crosslinked polymer network structure between skeleton.Wherein, lithium ion battery dwell temperature is 80 DEG C, standing
Time is 24h.
Embodiment 4
1). prepare electrostatic spinning solution.The polymer (Kynoar) that electrostatic spinning will be carried out is dissolved at 70 DEG C
In dimethylacetylamide DMAc, stirring 6h makes it mix, prepared polymer electrospun solution, and wherein polymer is in electrostatic
Volumetric concentration in spinning solution is 15% (g/mL).
(2) electrostatic spinning preparation one-level skeleton structure：
By step 1) to load temperature be in 50 DEG C of the device for storing liquid of electrospinning device for the electrostatic spinning solution for preparing, storage
The piston of liquid device is connected with syringe pump, and device for storing liquid is connected with spinning head by polyfluortetraethylene pipe, and spinning head is fixed, gold
Belong to and non-woven fabrics is placed on flat board as collector.Adjusting the distance between spinning head and collecting board is 15cm；The environment temperature of spinning
Spend for 50 DEG C, the temperature including electrostatic spinning solution in device for storing liquid and the temperature of collecting board are 50 DEG C, the air in environment
Flow control is in 0.5～0.8m3/h；Open high voltage power supply, adjust voltage to 15kV, the feeding rate of electrostatic spinning solution is 60
μ L/min, opens syringe pump, electrostatic spinning solution injection stream is ejected on lithium battery diaphragm, obtains polymer on barrier film
Electrospun nano-fibers film layer, thus forming polymer electrospun nanofiber primary structure.Average fibre diameter is
500nm, polymer electrospun nanofiber thicknesses of layers is 40 μm of (SEM figures of polymer electrospun nanofiber film layer
See Fig. 2).
(3) polymer-coated prepares two grades of skeleton structures：
In the HMW PVDF-HFP copolymer being about 50w containing coating molecular weight on polymer nanofiber barrier film
(product is purchased from Arkema, model LBG), coats post-drying, obtains the PVDF- being interspersed between polymer nanofiber
Two grades of skeletons of HFP copolymer.Coating is coated using oiliness, and wherein oil-based solvent acetone chosen by solvent.The mixed slurry of coating is dense
Spend for 20%, the speeds control position 1m/min of coating, the wind speed 5000rpm of drying, 90 DEG C of temperature.
(4) battery winding.
Barrier film containing nanofiber and PVDF-HFP is used ethanol purge, is dried, evacuation storage, and is wound in electricity
Chi Zhong.
(5) electrolyte performed polymer fluid injection：
Allotment electrolyte ethylene carbonate (EC), dimethyl carbonate (DEC), methyl ethyl carbonate (EMC) proportioning is 1：1：1,
The molar concentration of lithium hexafluoro phosphate is 1.0mol/L.Add the macromolecule performed polymer of polyacrylic acid PAA in the electrolytic solution, addition is drawn
Send out agent BPO, crosslinking agent triethylamine, the percentage composition of wherein electro-hydraulic middle PAA is the percentage composition of 10%, BPO is 0.1%, three second
The percentage composition of amine is in injection battery after 1% and electrolyte stirring at normal temperature 12h.
(6) high-temp in-situ polymerization, prepares PAA gelatin polymer three-level skeleton structure：
Battery after fluid injection is carried out standing under high temperature and, so as to in-situ polymerization, obtains bis- grades of PVDF-HFP on nanofiber
Interspersed crosslinked PAA three-level crosslinked polymer network structure between skeleton.Wherein, lithium ion battery dwell temperature is 80 DEG C, standing
Time is 24h.
Embodiment 5
1). prepare electrostatic spinning solution.The polymer (Kynoar) that electrostatic spinning will be carried out is dissolved at 55 DEG C
In acetone, stirring 6h makes it mix, prepared polymer electrospun solution, and wherein polymer is in electrostatic spinning solution
Volumetric concentration is 15% (g/mL).
(2) electrostatic spinning preparation one-level skeleton structure：
By step 1) to load temperature be in 50 DEG C of the device for storing liquid of electrospinning device for the electrostatic spinning solution for preparing, storage
The piston of liquid device is connected with syringe pump, and device for storing liquid is connected with spinning head by polyfluortetraethylene pipe, and spinning head is fixed, gold
Belong to and non-woven fabrics is placed on flat board as collector.Adjusting the distance between spinning head and collecting board is 15cm；The environment temperature of spinning
Spend for 50 DEG C, the temperature including electrostatic spinning solution in device for storing liquid and the temperature of collecting board are 50 DEG C, the air in environment
Flow control is in 0.5～0.8m3/h；Open high voltage power supply, adjust voltage to 15kV, the feeding rate of electrostatic spinning solution is 60
μ L/min, opens syringe pump, electrostatic spinning solution injection stream is ejected on lithium battery diaphragm, obtains polymer on barrier film
Electrospun nano-fibers film layer, thus forming polymer electrospun nanofiber primary structure.Average fibre diameter is
500nm, polymer electrospun nanofiber thicknesses of layers is 40 μm of (SEM figures of polymer electrospun nanofiber film layer
See Fig. 2).
(3) polymer-coated prepares two grades of skeleton structures：
In the HMW PVDF-HFP copolymer being about 50w containing coating molecular weight on polymer nanofiber barrier film
(product is purchased from Arkema, model LBG), coats post-drying, obtains the PVDF- being interspersed between polymer nanofiber
Two grades of skeletons of HFP copolymer.Coating is coated using oiliness, and wherein oil-based solvent acetone chosen by solvent.The mixed slurry of coating is dense
Spend for 20%, the speeds control position 1m/min of coating, the wind speed 5000rpm of drying, 90 DEG C of temperature.
(4) battery winding.
Barrier film containing nanofiber and PVDF-HFP is used ethanol purge, is dried, evacuation storage, and is wound in electricity
Chi Zhong.
(5) electrolyte performed polymer fluid injection：
Allotment electrolyte ethylene carbonate (EC), dimethyl carbonate (DEC), methyl ethyl carbonate (EMC) proportioning is 1：1：1,
The molar concentration of lithium hexafluoro phosphate is 1.0mol/L.Add pyromellitic trimethylsilyl chloride macromolecule performed polymer in the electrolytic solution, add and hand over
Connection agent piperazine, catalyst of triethylamine, the percentage composition of wherein electro-hydraulic middle pyromellitic trimethylsilyl chloride is 10%, and the percentage composition of piperazine is
10%, the percentage composition of triethylamine is in injection battery after 1%, with electrolyte stirring at normal temperature 12h.
(6) high-temp in-situ polymerization, prepares polyamide gels polymer three-level skeleton structure：
Battery after fluid injection is carried out standing under high temperature and, so as to in-situ polymerization, obtains bis- grades of PVDF-HFP on nanofiber
Interspersed crosslinked polyamide three-level crosslinked polymer network structure between skeleton.Wherein, lithium ion battery dwell temperature is 80 DEG C, quiet
Time of putting is 24h.
Embodiment 6
1). prepare electrostatic spinning solution.The polymer (Kynoar) that electrostatic spinning will be carried out is dissolved at 60 DEG C
Acetone and DMF (N,N-dimethylformamide) ratio are 7：In 3 mixed solvent, stirring 6h makes it mix, and polymerization is obtained
Thing electrostatic spinning solution, the wherein polymer volumetric concentration in electrostatic spinning solution is 15% (g/mL).
(2) electrostatic spinning preparation one-level skeleton structure：
By step 1) to load temperature be in 50 DEG C of the device for storing liquid of electrospinning device for the electrostatic spinning solution for preparing, storage
The piston of liquid device is connected with syringe pump, and device for storing liquid is connected with spinning head by polyfluortetraethylene pipe, and spinning head is fixed, gold
Belong to and non-woven fabrics is placed on flat board as collector.Adjusting the distance between spinning head and collecting board is 15cm；The environment temperature of spinning
Spend for 50 DEG C, the temperature including electrostatic spinning solution in device for storing liquid and the temperature of collecting board are 50 DEG C, the air in environment
Flow control is in 0.5～0.8m3/h；Open high voltage power supply, adjust voltage to 15kV, the feeding rate of electrostatic spinning solution is 60
μ L/min, opens syringe pump, electrostatic spinning solution injection stream is ejected on lithium battery diaphragm, obtains polymer on barrier film
Electrospun nano-fibers film layer, thus forming polymer electrospun nanofiber primary structure.Average fibre diameter is
500nm, polymer electrospun nanofiber thicknesses of layers is 40 μm of (SEM figures of polymer electrospun nanofiber film layer
See Fig. 2).
(3) polymer-coated prepares two grades of skeleton structures：
In the HMW PVDF-HFP copolymer being about 50w containing coating molecular weight on polymer nanofiber barrier film
(product is purchased from Arkema, model LBG), coats post-drying, obtains the PVDF- being interspersed between polymer nanofiber
Two grades of skeletons of HFP copolymer.Coating is coated using oiliness, and wherein oil-based solvent acetone chosen by solvent.The mixed slurry of coating is dense
Spend for 20%, the speeds control position 1m/min of coating, the wind speed 5000rpm of drying, 90 DEG C of temperature.
(4) battery winding.
Barrier film containing nanofiber and PVDF-HFP is used ethanol purge, is dried, evacuation storage, and is wound in electricity
Chi Zhong.
(5) electrolyte performed polymer fluid injection：
Allotment electrolyte propene carbonate (PC), dimethyl carbonate (DEC), methyl ethyl carbonate (EMC) proportioning is 1：1：1,
The molar concentration of lithium hexafluoro phosphate is 1.0mol/L.Add the macromolecule pre-polymerization of polymetylmethacrylate in the electrolytic solution
Body, adds initiator B PO, crosslinking agent triethylamine, and the percentage composition of wherein electro-hydraulic middle PMMA is that the percentage composition of 10%, BPO is
0.1%, the percentage composition of triethylamine is in injection battery after 1% and electrolyte stirring at normal temperature 12h.
(6) high-temp in-situ polymerization, prepares PMMA gelatin polymer three-level skeleton structure：
Battery after fluid injection is carried out standing under high temperature and, so as to in-situ polymerization, obtains bis- grades of PVDF-HFP on nanofiber
Interspersed crosslinked PMMA three-level crosslinked polymer network structure between skeleton.Wherein, lithium ion battery dwell temperature is 80 DEG C, standing
Time is 24h.
Claims (6)
1. a kind of gel electrolyte of lithium ion battery of multilevel hierarchy, is characterized in that, it include polymer network cross-linked scaffold and
It is present in the liquid electrolyte in network skeleton, wherein polymer network cross-linked scaffold is the primary structure of gel electrolyte, is
It is made up of the nanofiber of Kynoar electrostatic spinning, cross-linked scaffold is adsorbed in the both sides of basement membrane PE film；Crosslinked polymer master
Body is the macromolecule of weight average molecular weight 10-100 ten thousand of Kynoar and hexafluoropropene copolymerization, its be adsorbed in primary structure it
Between, as the secondary structure of gel electrolyte；Tertiary structure is high with hexafluoropropene copolymerization with the Kynoar of secondary structure
Molecule cross-link network is the polymethyl methacrylate in-situ polymerization high-molecular gel network of fulcrum.
2. a kind of preparation method of the gel electrolyte of lithium ion battery of multilevel hierarchy as claimed in claim 1, is characterized in that,
Follow the steps below：
(1) prepare electrostatic spinning solution：
The polymer that electrostatic spinning will be carried out is dissolved in corresponding organic solvent at temperature is 40～80 DEG C, stirs 5.5-
It is made to mix within 6.5 hours, prepared polymer electrospun solution；Volumetric concentration in electrostatic spinning solution for the polymer is
10%～30%；
(2) electrostatic spinning preparation one-level skeleton structure：
It is in 40～80 DEG C of the device for storing liquid of electrospinning device that the electrostatic spinning solution that step (1) is prepared loads temperature,
The piston of device for storing liquid is connected with syringe pump, and device for storing liquid is connected with spinning head by polyfluortetraethylene pipe, adjusts Static Spinning
The feeding rate of silk solution is 5～300 μ L/min；The spinning head of electrospinning device with the distance between the collector of ground connection is
5～25cm；Environment temperature is 35～80 DEG C；The air velocity of environment is 0～8.5m3/h；Lithium battery diaphragm is placed in collector
On, open high voltage power supply, open syringe pump, electrostatic spinning solution injection stream is ejected on lithium battery diaphragm, on barrier film
Obtain polymer electrospun nanofiber film layer, thus forming polymer electrospun nanofiber primary structure；
(3) polymer-coated prepares two grades of skeleton structures：
On the above-mentioned barrier film containing polymer electrospun nanofiber, coating molecular weight is 50～5,000,000 high-molecular-weight poly
Vinylidene and hexafluoropropylene copolymer, coat post-drying, the Kynoar obtaining being interspersed between polymer nanofiber with
Two grades of skeletons of hexafluoropropylene copolymer；Described coating coats with aqueous coating or with oiliness, and aqueous coating solvent is chosen aqueous molten
Agent deionized water；Oiliness coating solvent chooses oil-based solvent acetone or dimethylformamide, and the mixed slurry concentration of coating is
20%～50%, the speeds control of coating is 0.5m/min～15m/min, the wind speed 5000～1800rpm of drying, temperature 50 C
～200 DEG C；
(4) battery winding：
By the septum purge containing nanofiber and PVDF/HFP, it is dried, evacuation storage, and rolls up
It is around in battery；
(5) electrolyte performed polymer fluid injection：
Add the macromolecule performed polymer of polymetylmethacrylate in conventional electrolysis liquid, add initiator diphenyl peroxide
Formyl, in injection battery after crosslinking agent triethylamine, with electrolyte stirring at normal temperature 12h；
(6) high-temp in-situ polymerization, prepares PMMA gelatin polymer three-level skeleton structure：
Battery after fluid injection is stood at 50 DEG C～150 DEG C, time of repose, is received so as to in-situ polymerization for 5min～12h
Interspersed crosslinked PMMA three-level crosslinked polymer network between two grades of skeletons of PVDF/HFP on rice fiber
Structure.
3. the preparation method of the gel electrolyte of lithium ion battery of multilevel hierarchy according to claim 2, is characterized in that, institute
Stating volumetric concentration in electrostatic spinning solution for step (1) polymer is 15%.
4. the preparation method of the gel electrolyte of lithium ion battery of multilevel hierarchy according to claim 2, is characterized in that, institute
The feeding rate stating adjustment electrostatic spinning solution in step (2) is 20～150 μ L/min.
5. the preparation method of the gel electrolyte of lithium ion battery of multilevel hierarchy according to claim 2, is characterized in that, institute
Stating the distance between collector of the spinning head of electrospinning device and ground connection in step (2) is 7～20cm.
6. the preparation method of the gel electrolyte of lithium ion battery of multilevel hierarchy according to claim 2, is characterized in that, institute
State environment temperature in step (2) and be 40～60 DEG C；The air velocity of environment is 0.5～5m3/h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410750614.1A CN104393337B (en) | 2014-12-10 | 2014-12-10 | Lithium ion battery gel electrolyte with multi-stage structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410750614.1A CN104393337B (en) | 2014-12-10 | 2014-12-10 | Lithium ion battery gel electrolyte with multi-stage structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104393337A CN104393337A (en) | 2015-03-04 |
| CN104393337B true CN104393337B (en) | 2017-02-22 |
Family
ID=52611199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410750614.1A Active CN104393337B (en) | 2014-12-10 | 2014-12-10 | Lithium ion battery gel electrolyte with multi-stage structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104393337B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3467164A1 (en) * | 2017-10-09 | 2019-04-10 | Spiber Technologies AB | Method and device for protein fiber production |
| CN107959049B (en) * | 2017-11-23 | 2021-01-29 | 南开大学 | Preparation method of gel electrolyte, gel electrolyte and lithium ion battery |
| CN108623826B (en) * | 2018-05-18 | 2020-06-26 | 北京大学 | Double-network ionic gel with stimulus responsiveness and self-repairability |
| CN109713198B (en) * | 2018-12-27 | 2021-08-31 | 四川理工学院 | MOFs (metal-organic frameworks)/PMMA (polymethyl methacrylate)/PVDF (polyvinylidene fluoride) three-phase composite battery diaphragm and preparation method thereof |
| CN111411403B (en) * | 2020-03-04 | 2021-03-05 | 扬州大学 | Electrostatic spinning preparation device of nanofiber filter screen and working method of electrostatic spinning preparation device |
| CN117457996B (en) * | 2023-12-25 | 2024-03-19 | 安徽盟维新能源科技有限公司 | Double-crosslinking composite electrolyte membrane and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5681357A (en) * | 1996-09-23 | 1997-10-28 | Motorola, Inc. | Gel electrolyte bonded rechargeable electrochemical cell and method of making same |
| CN101805454A (en) * | 2009-02-13 | 2010-08-18 | 中国科学院理化技术研究所 | Polyvinylidene fluoride and vinylidene fluoride-hexafluoropropylene copolymer blended nanofibre polymer electrolyte membrane and preparation method thereof |
| CN102231431A (en) * | 2011-05-06 | 2011-11-02 | 浙江大东南集团有限公司 | Compound nanofiber diaphragm for lithium ion power battery and manufacturing method |
| CN103700797A (en) * | 2012-09-27 | 2014-04-02 | 比亚迪股份有限公司 | Polymer electrolyte, its preparation method and battery comprising the same |
| CN103904271A (en) * | 2014-04-23 | 2014-07-02 | 深圳市星源材质科技股份有限公司 | Preparation method of high-performance composite diaphragm and composite diaphragm |
| CN103972452A (en) * | 2014-05-21 | 2014-08-06 | 天津工业大学 | Preparation method of one-way enhanced electrostatic-spinning lithium ion battery diaphragm |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4593566B2 (en) * | 2003-06-17 | 2010-12-08 | ナノフィル カンパニー リミテッド | COMPOSITE MEMBRANE FOR ELECTROCHEMICAL DEVICE, PROCESS FOR PRODUCING THE SAME AND ELECTROCHEMICAL DEVICE HAVING THE SAME |
-
2014
- 2014-12-10 CN CN201410750614.1A patent/CN104393337B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5681357A (en) * | 1996-09-23 | 1997-10-28 | Motorola, Inc. | Gel electrolyte bonded rechargeable electrochemical cell and method of making same |
| CN101805454A (en) * | 2009-02-13 | 2010-08-18 | 中国科学院理化技术研究所 | Polyvinylidene fluoride and vinylidene fluoride-hexafluoropropylene copolymer blended nanofibre polymer electrolyte membrane and preparation method thereof |
| CN102231431A (en) * | 2011-05-06 | 2011-11-02 | 浙江大东南集团有限公司 | Compound nanofiber diaphragm for lithium ion power battery and manufacturing method |
| CN103700797A (en) * | 2012-09-27 | 2014-04-02 | 比亚迪股份有限公司 | Polymer electrolyte, its preparation method and battery comprising the same |
| CN103904271A (en) * | 2014-04-23 | 2014-07-02 | 深圳市星源材质科技股份有限公司 | Preparation method of high-performance composite diaphragm and composite diaphragm |
| CN103972452A (en) * | 2014-05-21 | 2014-08-06 | 天津工业大学 | Preparation method of one-way enhanced electrostatic-spinning lithium ion battery diaphragm |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104393337A (en) | 2015-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104393337B (en) | Lithium ion battery gel electrolyte with multi-stage structure and preparation method thereof | |
| CN104393336B (en) | A kind of nano-composite fiber enhancing gel polymer electrolyte and preparation method thereof | |
| Xu et al. | High-strength internal cross-linking bacterial cellulose-network-based gel polymer electrolyte for dendrite-suppressing and high-rate lithium batteries | |
| CN105720224B (en) | A kind of lithium ion battery separator and preparation method thereof of nano-cellulose improvement | |
| Li et al. | Superior thermally stable and nonflammable porous polybenzimidazole membrane with high wettability for high-power lithium-ion batteries | |
| Zhang et al. | Renewable and superior thermal-resistant cellulose-based composite nonwoven as lithium-ion battery separator | |
| Guo et al. | Thermally stable and green cellulose-based composites strengthened by styrene-co-acrylate latex for lithium-ion battery separators | |
| CN105709619B (en) | A kind of positively charged nanofiltration membranes and preparation method thereof | |
| CN106159173A (en) | Composite membrane of polymer prepared by a kind of composite membrane of polymer and preparation method thereof, the method, gel electrolyte, lithium ion battery | |
| CN101388441B (en) | Electrolyte film and porous substrate and preparation thereof, lithium ion secondary battery | |
| Pi et al. | Separators with biomineralized zirconia coatings for enhanced thermo-and electro-performance of lithium-ion batteries | |
| CN107474270B (en) | Preparation method of polymer electrolyte membrane | |
| CN104140545B (en) | A kind of ionic liquid/polymer electrolyte film and preparation method thereof | |
| CN109786627A (en) | A kind of preparation method of super close electrolyte lithium battery diaphragm | |
| Hu et al. | A separator based on cross-linked nano-SiO2 and cellulose acetate for lithium-ion batteries | |
| CN103840112B (en) | PVDF-HFP-based composite porous polymer diaphragm and preparation method thereof | |
| CN104183867A (en) | Preparation method and application of single ion conductor nano-particle reinforced lithium battery diaphragm or polymer electrolyte | |
| CN101552359A (en) | Micro-nano porous structure polymer electrolyte membrane used for lithium ion battery and method of producing the same | |
| CN102242464A (en) | Polymer-ceramic compound nanometer fibrous membrane as well as preparation method and application thereof | |
| Li et al. | Mini review on cellulose-based composite separators for lithium-ion batteries: recent progress and perspectives | |
| CN104466063A (en) | Polydopamine surface modified polyether sulfone nanofiber composite diaphragm and preparation method and applications | |
| Yu et al. | A novel high-performance 3D polymer binder for silicon anode in lithium-ion batteries | |
| Li et al. | Promising free-standing polyimide membrane via solution blow spinning for high performance lithium-ion batteries | |
| US10333176B2 (en) | Polymer electrolyte membranes for rechargeable batteries | |
| CN108134036A (en) | A kind of Organic-inorganic composite dielectric film, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230313 Address after: 300000 No.38 Haitai South Road, Huayuan Industrial Zone (outside the ring), High-tech Zone, Binhai New Area, Tianjin Patentee after: Tianjin Juyuan New Energy Technology Co.,Ltd. Address before: 300385 No. 38, Haitai South Road, Binhai high tech Industrial Development Zone (outer ring), Xiqing District, Tianjin Patentee before: TIANJIN LISHEN BATTERY JOINT-STOCK Co.,Ltd. |
|
| TR01 | Transfer of patent right |