CN104393337A - 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
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- 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
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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 polymer gel electrolyte system (comprising gel electrolyte and diaphragm support skeleton) of multilevel hierarchy, particularly comprise the gel electrolyte system of the crosslinked polymer network of PVDF Electrospun nano-fibers, PVDF-HFP crosslinked polymer two grade network and in-situ polymerization.
Background technology
The advantages such as voltage is high, volume is little owing to having for lithium ion battery, lightweight, energy density is high and have extended cycle life, have obtained the leading position in market.
At present, the electrolyte of lithium ion battery is divided into liquid electrolyte and gel electrolyte.Wherein, the feature of liquid electrolyte is that stable electrochemical property is reliable, but the problem such as ubiquity poor stability, battery hardness is yielding not.By contrast, the solvent molecule of flowable state is fixed in high-molecular gel skeleton by gel electrolyte liquid system, because of do not exist or less there is free state solvent and reduce the risk of solution leakage, significantly reduce the flammability of battery system, and then improve the fail safe of battery; Meanwhile, because whole battery core is linked to be an entirety by macromolecular scaffold, be therefore conducive to reducing battery core distortion and expanding.So gel electrolyte liquid system has very bright application prospect.
Existing gel electrolyte generally adds polymerisable monomer and is prepared from liquid electrolyte, and the polymerisable monomer added dissolves in liquid electrolyte, and the polymer of generation also dissolves in liquid electrolyte.Due to when the concentration of polymerisable monomer is lower in gel electrolyte precursor, can be not enough to make liquid electrolyte be converted to gel electrolyte, therefore often need to add more polymerisable monomer; But when the concentration of polymerisable monomer is higher, the polymer concentration in the gel electrolyte generated is also higher, can cause lithium ion conduction difficulty again, so that occur that lithium ion conductivity is low, easily analyse a series of chemical property problems such as lithium.
In view of this, the necessary gel electrolyte of lithium ion battery providing a kind of mechanical property, chemical property and fail safe all good.
Summary of the invention
The object of the invention is to: the gel electrolyte of lithium ion battery that a kind of mechanical property, chemical property and fail safe are all good is provided; It is stronger that another object of the present invention is to obtain a kind of liquid measure of protecting by the design of multilevel hierarchy, the gel electrolyte of lithium ion battery that structure is more stable.
To achieve these goals, technical scheme of the present invention is as follows:
The invention provides a kind of lithium ion battery gel electrolyte of multilevel hierarchy, it comprises polymer network cross-linked scaffold and is present in the liquid electrolyte in network skeleton, wherein polymer network physical crosslinking skeleton is the primary structure of gel electrolyte, be 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; Crosslinked polymer main body is the macromolecule of the weight average molecular weight 10-100 ten thousand of Kynoar and hexafluoropropylene copolymerization (PVDF-HFP), and it is adsorbed between one-level skeleton, as gelatin polymer secondary structure; Polymethyl methacrylate (PMMA) the in-situ polymerization high-molecular gel network that three grades of skeletons are is fulcrum with the PVDF-HFP copolymerized macromolecule cross-linked network of secondary skeleton, mainly provides and keeps liquid electric liquid effect.
Advantage of the present invention is the structure distribution step by step of gel skeleton, on PE basement membrane, the mechanical strength of Electrospun nano-fibers is the highest, system intensity and support are mainly provided, the PVDF-HFP polymer be interspersed between nanofiber is gel cross-linkage main body, play and provide sectional interest intensity and the transition structure being connected macroscopical primary structure and microcosmic tertiary structure, tertiary structure PMMA in-situ polymerization structure plays the effect keeping small molecule solvent in liquid electrolyte and lithium ion salt.The high molecular crosslink system of this multilayered structure has mechanical strength high compared to conventional GPC system, and liquid-keeping property is strong, and network configuration porosity is large, and conductivity advantages of higher, has broad application prospects.
The preparation method of the lithium ion battery gel electrolyte of multilevel hierarchy, comprises the following steps:
(1) electrostatic spinning solution is prepared:
The polymer that will carry out electrostatic spinning is dissolved in corresponding organic solvent under temperature is 40 ~ 80 DEG C (preferably 50 DEG C), stirs (being generally 6 hours) and makes it mix, obtained polymer electrospun solution; The volumetric concentration of polymer in electrostatic spinning solution is 10% ~ 30%, and preferred volume concentration is 15%;
(2) electrostatic spinning prepares one-level skeleton structure:
It is in the device for storing liquid of the electrospinning device of 40 ~ 80 DEG C that electrostatic spinning solution step (1) prepared loads temperature, the piston of device for storing liquid is connected with syringe pump, device for storing liquid is connected with spinning head by teflon tube, the feeding rate of adjustment electrostatic spinning solution is 5 ~ 300 μ L/min, is preferably 20 ~ 150 μ L/min; Distance between the spinning head of electrospinning device and the gatherer of ground connection is 5 ~ 25cm, is preferably 7 ~ 20cm; Ambient temperature is 35 ~ 80 DEG C, is preferably 40 ~ 60 DEG C; The air velocity of environment is 0 ~ 8.5m
3/ h, is preferably 0.5 ~ 5m
3/ h; Lithium battery diaphragm is placed on gatherer, (electrostatic pressure is 1 ~ 60kV to open high voltage source, Appropriate is 15 ~ 20kV), open syringe pump, electrostatic spinning solution injection stream is ejected on lithium battery diaphragm, barrier film obtains polymer electrospun nanofiber rete, thus in formation polymer electrospun nanofiber primary structure;
(3) polymer-coated prepares secondary skeleton structure:
Apply containing on the barrier film of polymer electrospun nanofiber the HMW PVDF-HFP copolymer that molecular weight is 50 ~ 5,000,000 above-mentioned, coating post-drying, obtains the PVDF-HFP copolymer secondary skeleton be interspersed between polymer nanofiber; Apply the coating of available water-based, wherein the optional aqueous solvent of solvent is as deionized water; Coating also can apply by oiliness, and wherein solvent can choose oil-based solvent as acetone, dimethyl formamide (DMF); The mixed slurry concentration of coating is the speeds control position 0.5m/min ~ 15m/min of 20% ~ 50% (percentage of PVDF-HFP), coating, the wind speed 5000 ~ 1800rpm of oven dry, temperature 50 C ~ 200 DEG C;
(4) battery winding.
By the septum purge containing nanofiber and PVDF-HFP, dry, evacuation storage, and be wound in battery;
(5) electrolyte performed polymer fluid injection:
In conventional electrolysis liquid, add the macromolecule performed polymer of polymetylmethacrylate, add initator dibenzoyl peroxide (BPO), crosslinking agent triethylamine, inject battery with after electrolyte stirring at normal temperature 12h;
(6) high-temp in-situ polymerization, preparation PMMA gelatin polymer three grades of skeleton structures:
Leave standstill under battery after fluid injection being carried out high temperature, make its in-situ polymerization, obtain nanofiber interts between PVDF-HFP secondary skeleton crosslinked PMMA tri-grades of crosslinked polymer network configurations; Wherein, lithium ion battery dwell temperature is 50 DEG C ~ 150 DEG C, and time of repose is 5min ~ 12h.
Cross-linked network structure launches at different scale scope internal classification, can improve guarantor's fluidity and the mechanical stability of crosslinked polymer network configuration greatly, thus improves 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 has following advantage:
Due to the multi-stratification of its structure, each level structure has supporting role to gel electrolyte in different range scales, under large scale, nanofiber is as supportive body, under micro-scale, PMMA polymer three-dimensional cross-linked network is as the main body keeping electric liquid, gel batteries prepared by the present invention is compared to conventional gel battery, its liquid-keeping property is stronger, the mechanical strength of gel electricity liquid is higher, the security performance of gel batteries is better, Electrospun nano-fibers rete porosity is higher, the conductivity of gel electrolyte entirety is improved, cycle performance also has larger lifting, gel batteries for future new era has opened up new direction.
Accompanying drawing explanation
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, between PVDF nanofiber network, super high molecular weight PVDF-HFP and PMMA crosslinked polymer network SEM schemes;
Fig. 4, gel electrolyte secondary structure and tertiary structure, the crosslinked polymer network SEM of PVDF nanofiber surface absorption schemes;
Fig. 5, polymer electrospun process schematic.
Embodiment
Lithium ion battery gel electrolyte structure of the present invention as shown in Figure 1, it comprises polymer network cross-linked scaffold and is present in the liquid electrolyte in network skeleton, wherein polymer network physical crosslinking skeleton is the primary structure 1 of gel electrolyte, be 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; Crosslinked polymer main body is the macromolecule of the weight average molecular weight 10-100 ten thousand of PVDF-HFP copolymerization, and it is adsorbed between one-level skeleton, as gelatin polymer secondary structure 2; The polymetylmethacrylate in-situ polymerization high-molecular gel network that three grades of skeletons 3 are is fulcrum with the PVDF-HFP copolymerized macromolecule cross-linked network of secondary skeleton, mainly provides and keeps liquid electric liquid effect.
Embodiment 1
1). preparation electrostatic spinning solution.The polymer (Kynoar) that will carry out electrostatic spinning is dissolved in N at 50 DEG C, in dinethylformamide, stirring 6h makes it mix, and obtained polymer electrospun solution, wherein the volumetric concentration of polymer in electrostatic spinning solution is 15% (g/mL).
(2) electrostatic spinning prepares one-level skeleton structure:
Process as shown in Figure 5, by step 1) to load temperature be in the device for storing liquid of the electrospinning device of 50 DEG C for the electrostatic spinning solution for preparing, the piston of device for storing liquid is connected with syringe pump, device for storing liquid is connected with spinning head by teflon tube, spinning head is fixed, and metal plate is placed nonwoven fabrics as gatherer.The distance between spinning head and collecting board is regulated to be 15cm; The ambient temperature of spinning is 50 DEG C, and comprise the temperature of electrostatic spinning solution and the temperature of collecting board in device for storing liquid and be 50 DEG C, the air velocity in environment controls at 0.5 ~ 0.8m
3/ h; Open high voltage source, regulation voltage is to 15kV, the feeding rate of electrostatic spinning solution is 60 μ L/min, open syringe pump, electrostatic spinning solution injection stream is ejected on lithium battery diaphragm, barrier film obtains polymer electrospun nanofiber rete, thus in formation polymer electrospun nanofiber primary structure.Average fibre diameter is 500nm, and polymer electrospun nanofiber thicknesses of layers is 40 μm (the SEM figure of polymer electrospun nanofiber rete is shown in Fig. 2).
(3) polymer-coated prepares secondary skeleton structure:
Be about the HMW PVDF-HFP copolymer of 50w containing polymer electrospun nano fiber diaphragm applying molecular weight (product is being purchased from Arkema, model is LBG), coating post-drying, obtains the PVDF-HFP copolymer secondary skeleton be interspersed between polymer nanofiber.Coating uses oiliness coating, 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 oven dry, temperature 90 DEG C.
(4) battery winding.
Barrier film containing nanofiber and PVDF-HFP is used ethanol purge, dry, evacuation storage, and be wound in battery.
(5) electrolyte performed polymer fluid injection:
Allotment electrolyte ethylene carbonate (EC), dimethyl carbonate (DEC), methyl ethyl carbonate (EMC) proportioning is 1:1:1, and the molar concentration of lithium hexafluoro phosphate is 1.0mol/L.Add the macromolecule performed polymer of polymetylmethacrylate in the electrolytic solution, add initiator B PO, crosslinking agent triethylamine, wherein in electric liquid, the percentage composition of PMMA is 10%, the percentage composition of BPO is 0.1%, the percentage composition of triethylamine be 1% with electrolyte stirring at normal temperature 12h after inject battery.
(6) high-temp in-situ polymerization, preparation PMMA gelatin polymer three grades of skeleton structures:
Leave standstill under battery after fluid injection being carried out high temperature, make its in-situ polymerization, obtain nanofiber interts between PVDF-HFP secondary skeleton crosslinked PMMA tri-grades of crosslinked polymer network configurations.Wherein, lithium ion battery dwell temperature is 80 DEG C, and time of repose is 24h.
Gel electrolyte secondary structure and tertiary structure, between PVDF nanofiber network, super high molecular weight PVDF-HFP and PMMA crosslinked polymer network SEM figure is shown in Fig. 3.Gel electrolyte secondary structure and tertiary structure, the crosslinked polymer network SEM figure of PVDF nanofiber surface absorption is shown in Fig. 4.
Embodiment 2
1). preparation electrostatic spinning solution.The polymer (Kynoar) that will carry out electrostatic spinning is dissolved in N at 50 DEG C, in dinethylformamide, stirring 6h makes it mix, and obtained polymer electrospun solution, wherein the volumetric concentration of polymer in electrostatic spinning solution is 15% (g/mL).
(2) electrostatic spinning prepares one-level skeleton structure:
By step 1) to load temperature be in the device for storing liquid of the electrospinning device of 50 DEG C for the electrostatic spinning solution for preparing, the piston of device for storing liquid is connected with syringe pump, device for storing liquid is connected with spinning head by teflon tube, spinning head is fixed, and metal plate is placed nonwoven fabrics as gatherer.The distance between spinning head and collecting board is regulated to be 15cm; The ambient temperature of spinning is 50 DEG C, and comprise the temperature of electrostatic spinning solution and the temperature of collecting board in device for storing liquid and be 50 DEG C, the air velocity in environment controls at 0.5 ~ 0.8m
3/ h; Open high voltage source, regulation voltage is to 15kV, the feeding rate of electrostatic spinning solution is 60 μ L/min, open syringe pump, electrostatic spinning solution injection stream is ejected on lithium battery diaphragm, barrier film obtains polymer electrospun nanofiber rete, thus in formation polymer electrospun nanofiber primary structure.Average fibre diameter is 500nm, and polymer electrospun nanofiber thicknesses of layers is 40 μm (the SEM figure of polymer electrospun nanofiber rete is shown in Fig. 2).
(3) polymer-coated prepares secondary skeleton structure:
Be about the HMW PVDF-HFP copolymer of 45w containing polymer nanofiber barrier film applying molecular weight (product is being purchased from Su Wei company, model 21216, wherein HFP copolymerization ratios is higher), coating post-drying, obtains the PVDF-HFP copolymer secondary skeleton be interspersed between polymer nanofiber.Coating uses oiliness coating, 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 oven dry, temperature 90 DEG C.
(4) battery winding.
Barrier film containing nanofiber and PVDF-HFP is used ethanol purge, dry, evacuation storage, and be wound in battery.
(5) electrolyte performed polymer fluid injection:
Allotment electrolyte ethylene carbonate (EC), dimethyl carbonate (DEC), methyl ethyl carbonate (EMC) proportioning is 1:1:1, and the molar concentration of lithium hexafluoro phosphate is 1.0mol/L.Add the macromolecule performed polymer of polymetylmethacrylate in the electrolytic solution, add initiator B PO, crosslinking agent triethylamine, wherein in electric liquid, the percentage composition of PMMA is 10%, the percentage composition of BPO is 0.1%, the percentage composition of triethylamine be 1% with electrolyte stirring at normal temperature 12h after inject battery.
(6) high-temp in-situ polymerization, preparation PMMA gelatin polymer three grades of skeleton structures:
Leave standstill under battery after fluid injection being carried out high temperature, make its in-situ polymerization, obtain nanofiber interts between PVDF-HFP secondary skeleton crosslinked PMMA tri-grades of crosslinked polymer network configurations.Wherein, lithium ion battery dwell temperature is 80 DEG C, and time of repose is 24h.
Embodiment 3
1). preparation electrostatic spinning solution.The polymer (Kynoar) that will carry out electrostatic spinning is dissolved in N at 50 DEG C, in dinethylformamide, stirring 6h makes it mix, and obtained polymer electrospun solution, wherein the volumetric concentration of polymer in electrostatic spinning solution is 15% (g/mL).
(2) electrostatic spinning prepares one-level skeleton structure:
By step 1) to load temperature be in the device for storing liquid of the electrospinning device of 50 DEG C for the electrostatic spinning solution for preparing, the piston of device for storing liquid is connected with syringe pump, device for storing liquid is connected with spinning head by teflon tube, spinning head is fixed, and metal plate is placed nonwoven fabrics as gatherer.The distance between spinning head and collecting board is regulated to be 15cm; The ambient temperature of spinning is 50 DEG C, and comprise the temperature of electrostatic spinning solution and the temperature of collecting board in device for storing liquid and be 50 DEG C, the air velocity in environment controls at 0.5 ~ 0.8m
3/ h; Open high voltage source, regulation voltage is to 15kV, the feeding rate of electrostatic spinning solution is 60 μ L/min, open syringe pump, electrostatic spinning solution injection stream is ejected on lithium battery diaphragm, barrier film obtains polymer electrospun nanofiber rete, thus in formation polymer electrospun nanofiber primary structure.Average fibre diameter is 500nm, and polymer electrospun nanofiber thicknesses of layers is 40 μm (the SEM figure of polymer electrospun nanofiber rete is shown in Fig. 2).
(3) polymer-coated prepares secondary skeleton structure:
Be about the HMW PVDF-HFP copolymer of 50w containing polymer nanofiber barrier film applying molecular weight (product is being purchased from Arkema, model is 8500, this is Arkema is a fluoro containing polymers adhesive of gel electrolyte exploitation specially), coating post-drying, obtains the PVDF-HFP copolymer secondary skeleton be interspersed between polymer nanofiber.Coating uses oiliness coating, 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 oven dry, temperature 90 DEG C.
(4) battery winding.
Barrier film containing nanofiber and PVDF-HFP is used ethanol purge, dry, evacuation storage, and be wound in battery.
(5) electrolyte performed polymer fluid injection:
Allotment electrolyte ethylene carbonate (EC), dimethyl carbonate (DEC), methyl ethyl carbonate (EMC) proportioning is 1:1:1, and the molar concentration of lithium hexafluoro phosphate is 1.0mol/L.Add the macromolecule performed polymer of polymetylmethacrylate in the electrolytic solution, add initiator B PO, crosslinking agent triethylamine, wherein in electric liquid, the percentage composition of PMMA is 10%, the percentage composition of BPO is 0.1%, the percentage composition of triethylamine be 1% with electrolyte stirring at normal temperature 12h after inject battery.
(6) high-temp in-situ polymerization, preparation PMMA gelatin polymer three grades of skeleton structures:
Leave standstill under battery after fluid injection being carried out high temperature, make its in-situ polymerization, obtain nanofiber interts between PVDF-HFP secondary skeleton crosslinked PMMA tri-grades of crosslinked polymer network configurations.Wherein, lithium ion battery dwell temperature is 80 DEG C, and time of repose is 24h.
Embodiment 4
1). preparation electrostatic spinning solution.The polymer (Kynoar) that will carry out electrostatic spinning is dissolved in dimethylacetylamide DMAc at 70 DEG C, stirring 6h makes it mix, obtained polymer electrospun solution, wherein the volumetric concentration of polymer in electrostatic spinning solution is 15% (g/mL).
(2) electrostatic spinning prepares one-level skeleton structure:
By step 1) to load temperature be in the device for storing liquid of the electrospinning device of 50 DEG C for the electrostatic spinning solution for preparing, the piston of device for storing liquid is connected with syringe pump, device for storing liquid is connected with spinning head by teflon tube, spinning head is fixed, and metal plate is placed nonwoven fabrics as gatherer.The distance between spinning head and collecting board is regulated to be 15cm; The ambient temperature of spinning is 50 DEG C, and comprise the temperature of electrostatic spinning solution and the temperature of collecting board in device for storing liquid and be 50 DEG C, the air velocity in environment controls at 0.5 ~ 0.8m
3/ h; Open high voltage source, regulation voltage is to 15kV, the feeding rate of electrostatic spinning solution is 60 μ L/min, open syringe pump, electrostatic spinning solution injection stream is ejected on lithium battery diaphragm, barrier film obtains polymer electrospun nanofiber rete, thus in formation polymer electrospun nanofiber primary structure.Average fibre diameter is 500nm, and polymer electrospun nanofiber thicknesses of layers is 40 μm (the SEM figure of polymer electrospun nanofiber rete is shown in Fig. 2).
(3) polymer-coated prepares secondary skeleton structure:
Be about the HMW PVDF-HFP copolymer of 50w containing polymer nanofiber barrier film applying molecular weight (product is being purchased from Arkema, model is LBG), coating post-drying, obtains the PVDF-HFP copolymer secondary skeleton be interspersed between polymer nanofiber.Coating uses oiliness coating, 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 oven dry, temperature 90 DEG C.
(4) battery winding.
Barrier film containing nanofiber and PVDF-HFP is used ethanol purge, dry, evacuation storage, and be wound in battery.
(5) electrolyte performed polymer fluid injection:
Allotment electrolyte ethylene carbonate (EC), dimethyl carbonate (DEC), methyl ethyl carbonate (EMC) proportioning is 1:1:1, and the molar concentration of lithium hexafluoro phosphate is 1.0mol/L.Add the macromolecule performed polymer of polyacrylic acid PAA in the electrolytic solution, add initiator B PO, crosslinking agent triethylamine, wherein in electric liquid, the percentage composition of PAA is 10%, the percentage composition of BPO is 0.1%, the percentage composition of triethylamine be 1% with electrolyte stirring at normal temperature 12h after inject battery.
(6) high-temp in-situ polymerization, preparation PAA gelatin polymer three grades of skeleton structures:
Leave standstill under battery after fluid injection being carried out high temperature, make its in-situ polymerization, obtain nanofiber interts between PVDF-HFP secondary skeleton crosslinked PAA tri-grades of crosslinked polymer network configurations.Wherein, lithium ion battery dwell temperature is 80 DEG C, and time of repose is 24h.
Embodiment 5
1). preparation electrostatic spinning solution.The polymer (Kynoar) that will carry out electrostatic spinning is dissolved in acetone at 55 DEG C, stirring 6h makes it mix, obtained polymer electrospun solution, wherein the volumetric concentration of polymer in electrostatic spinning solution is 15% (g/mL).
(2) electrostatic spinning prepares one-level skeleton structure:
By step 1) to load temperature be in the device for storing liquid of the electrospinning device of 50 DEG C for the electrostatic spinning solution for preparing, the piston of device for storing liquid is connected with syringe pump, device for storing liquid is connected with spinning head by teflon tube, spinning head is fixed, and metal plate is placed nonwoven fabrics as gatherer.The distance between spinning head and collecting board is regulated to be 15cm; The ambient temperature of spinning is 50 DEG C, and comprise the temperature of electrostatic spinning solution and the temperature of collecting board in device for storing liquid and be 50 DEG C, the air velocity in environment controls at 0.5 ~ 0.8m
3/ h; Open high voltage source, regulation voltage is to 15kV, the feeding rate of electrostatic spinning solution is 60 μ L/min, open syringe pump, electrostatic spinning solution injection stream is ejected on lithium battery diaphragm, barrier film obtains polymer electrospun nanofiber rete, thus in formation polymer electrospun nanofiber primary structure.Average fibre diameter is 500nm, and polymer electrospun nanofiber thicknesses of layers is 40 μm (the SEM figure of polymer electrospun nanofiber rete is shown in Fig. 2).
(3) polymer-coated prepares secondary skeleton structure:
Be about the HMW PVDF-HFP copolymer of 50w containing polymer nanofiber barrier film applying molecular weight (product is being purchased from Arkema, model is LBG), coating post-drying, obtains the PVDF-HFP copolymer secondary skeleton be interspersed between polymer nanofiber.Coating uses oiliness coating, 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 oven dry, temperature 90 DEG C.
(4) battery winding.
Barrier film containing nanofiber and PVDF-HFP is used ethanol purge, dry, evacuation storage, and be wound in battery.
(5) electrolyte performed polymer fluid injection:
Allotment electrolyte ethylene carbonate (EC), dimethyl carbonate (DEC), methyl ethyl carbonate (EMC) proportioning is 1:1:1, and the molar concentration of lithium hexafluoro phosphate is 1.0mol/L.Add pyromellitic trimethylsilyl chloride macromolecule performed polymer in the electrolytic solution, add crosslinking agent piperazine, catalyst of triethylamine, wherein in electric liquid, the percentage composition of pyromellitic trimethylsilyl chloride is 10%, the percentage composition of piperazine is 10%, the percentage composition of triethylamine is 1%, injects battery with after electrolyte stirring at normal temperature 12h.
(6) high-temp in-situ polymerization, prepare polyamide gels polymer three grades of skeleton structures:
Leave standstill under battery after fluid injection being carried out high temperature, make its in-situ polymerization, obtain nanofiber interts between PVDF-HFP secondary skeleton crosslinked polyamide three grades of crosslinked polymer network configurations.Wherein, lithium ion battery dwell temperature is 80 DEG C, and time of repose is 24h.
Embodiment 6
1). preparation electrostatic spinning solution.The polymer (Kynoar) that will carry out electrostatic spinning is dissolved in acetone and DMF (N at 60 DEG C, dinethylformamide) ratio is in the mixed solvent of 7:3, stirring 6h makes it mix, obtained polymer electrospun solution, wherein the volumetric concentration of polymer in electrostatic spinning solution is 15% (g/mL).
(2) electrostatic spinning prepares one-level skeleton structure:
By step 1) to load temperature be in the device for storing liquid of the electrospinning device of 50 DEG C for the electrostatic spinning solution for preparing, the piston of device for storing liquid is connected with syringe pump, device for storing liquid is connected with spinning head by teflon tube, spinning head is fixed, and metal plate is placed nonwoven fabrics as gatherer.The distance between spinning head and collecting board is regulated to be 15cm; The ambient temperature of spinning is 50 DEG C, and comprise the temperature of electrostatic spinning solution and the temperature of collecting board in device for storing liquid and be 50 DEG C, the air velocity in environment controls at 0.5 ~ 0.8m
3/ h; Open high voltage source, regulation voltage is to 15kV, the feeding rate of electrostatic spinning solution is 60 μ L/min, open syringe pump, electrostatic spinning solution injection stream is ejected on lithium battery diaphragm, barrier film obtains polymer electrospun nanofiber rete, thus in formation polymer electrospun nanofiber primary structure.Average fibre diameter is 500nm, and polymer electrospun nanofiber thicknesses of layers is 40 μm (the SEM figure of polymer electrospun nanofiber rete is shown in Fig. 2).
(3) polymer-coated prepares secondary skeleton structure:
Be about the HMW PVDF-HFP copolymer of 50w containing polymer nanofiber barrier film applying molecular weight (product is being purchased from Arkema, model is LBG), coating post-drying, obtains the PVDF-HFP copolymer secondary skeleton be interspersed between polymer nanofiber.Coating uses oiliness coating, 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 oven dry, temperature 90 DEG C.
(4) battery winding.
Barrier film containing nanofiber and PVDF-HFP is used ethanol purge, dry, evacuation storage, and be wound in battery.
(5) electrolyte performed polymer fluid injection:
Allotment electrolyte propene carbonate (PC), dimethyl carbonate (DEC), methyl ethyl carbonate (EMC) proportioning is 1:1:1, and the molar concentration of lithium hexafluoro phosphate is 1.0mol/L.Add the macromolecule performed polymer of polymetylmethacrylate in the electrolytic solution, add initiator B PO, crosslinking agent triethylamine, wherein in electric liquid, the percentage composition of PMMA is 10%, the percentage composition of BPO is 0.1%, the percentage composition of triethylamine be 1% with electrolyte stirring at normal temperature 12h after inject battery.
(6) high-temp in-situ polymerization, preparation PMMA gelatin polymer three grades of skeleton structures:
Leave standstill under battery after fluid injection being carried out high temperature, make its in-situ polymerization, obtain nanofiber interts between PVDF-HFP secondary skeleton crosslinked PMMA tri-grades of crosslinked polymer network configurations.Wherein, lithium ion battery dwell temperature is 80 DEG C, and time of repose is 24h.
Claims (7)
1. the lithium ion battery gel electrolyte of a multilevel hierarchy, it is characterized in that, it comprises polymer network cross-linked scaffold and is present in the liquid electrolyte in network skeleton, wherein polymer network physical crosslinking skeleton is the primary structure of gel electrolyte, be be 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 main body is the macromolecule of the weight average molecular weight 10-100 ten thousand of Kynoar and hexafluoropropylene copolymerization, and it is adsorbed between primary structure, as gelatin polymer secondary structure; The polymethyl methacrylate in-situ polymerization high-molecular gel network that tertiary structure is is fulcrum with the Kynoar of secondary structure and hexafluoropropylene copolymerized macromolecule cross-linked network.
2. a preparation method for the lithium ion battery gel electrolyte of multilevel hierarchy as claimed in claim 1, is characterized in that, carries out according to following steps:
(1) electrostatic spinning solution is prepared:
The polymer that will carry out electrostatic spinning is dissolved in corresponding organic solvent at temperature is 40 ~ 80 DEG C, stirs and makes it mix in 5.5-6.5 hour, obtained polymer electrospun solution; The volumetric concentration of polymer in electrostatic spinning solution is 10% ~ 30%;
(2) electrostatic spinning prepares one-level skeleton structure:
It is in the device for storing liquid of the electrospinning device of 40 ~ 80 DEG C that electrostatic spinning solution step (1) prepared loads temperature, the piston of device for storing liquid is connected with syringe pump, device for storing liquid is connected with spinning head by teflon tube, and the feeding rate of adjustment electrostatic spinning solution is 5 ~ 300 μ L/min; Distance between the spinning head of electrospinning device and the gatherer of ground connection is 5 ~ 25cm; Ambient temperature is 35 ~ 80 DEG C; The air velocity of environment is 0 ~ 8.5m
3/ h; Lithium battery diaphragm is placed on gatherer, open high voltage source, open syringe pump, electrostatic spinning solution injection stream is ejected on lithium battery diaphragm, barrier film obtains polymer electrospun nanofiber rete, thus in formation polymer electrospun nanofiber primary structure;
(3) polymer-coated prepares secondary skeleton structure:
Apply containing on the barrier film of polymer electrospun nanofiber HMW Kynoar and the hexafluoropropylene copolymer that molecular weight is 50 ~ 5,000,000 above-mentioned, coating post-drying, obtains the PVDF/HFP secondary skeleton be interspersed between polymer nanofiber; The mixed slurry concentration of coating is 20% ~ 50%, the speeds control position 0.5m/min ~ 15m/min of coating, the wind speed 5000 ~ 1800rpm of oven dry, temperature 50 C ~ 200 DEG C;
(4) battery winding:
By the septum purge containing nanofiber and PVDF-HFP, dry, evacuation storage, and be wound in battery;
(5) electrolyte performed polymer fluid injection:
In conventional electrolysis liquid, add the macromolecule performed polymer of polymetylmethacrylate, add initator dibenzoyl peroxide, crosslinking agent triethylamine, inject battery with after electrolyte stirring at normal temperature 12h;
(6) high-temp in-situ polymerization, preparation PMMA gelatin polymer three grades of skeleton structures:
Left standstill at 50 DEG C ~ 150 DEG C by battery after fluid injection, time of repose is 5min ~ 12h, makes its in-situ polymerization, obtains nanofiber interts between PVDF-HFP secondary skeleton crosslinked PMMA tri-grades of crosslinked polymer network configurations.
3. the preparation method of the lithium ion battery gel electrolyte of multilevel hierarchy according to claim 2, is characterized in that, the volumetric concentration of described step (1) polymer in electrostatic spinning solution is 15%.
4. the preparation method of the lithium ion battery gel electrolyte of multilevel hierarchy according to claim 2, is characterized in that, in described step (2), the feeding rate of adjustment electrostatic spinning solution is 20 ~ 150 μ L/min.
5. the preparation method of the lithium ion battery gel electrolyte of multilevel hierarchy according to claim 2, is characterized in that, the distance between the spinning head of the middle electrospinning device of described step (2) and the gatherer of ground connection is 7 ~ 20cm.
6. the preparation method of the lithium ion battery gel electrolyte of multilevel hierarchy according to claim 2, is characterized in that, in described step (2), ambient temperature is 40 ~ 60 DEG C; The air velocity of environment is 0.5 ~ 5m
3/ h.
7. the preparation method of the lithium ion battery gel electrolyte of multilevel hierarchy according to claim 2, is characterized in that, in described step (3), coating use applies or applies by oiliness, and aqueous solvent deionized water chosen by water-based coating solvent; Oiliness coating solvent chooses oil-based solvent acetone or dimethyl formamide.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107959049A (en) * | 2017-11-23 | 2018-04-24 | 南开大学 | Preparation method, gel electrolyte and the lithium ion battery of gel electrolyte |
| CN108623826A (en) * | 2018-05-18 | 2018-10-09 | 北京大学 | A kind of dual network ionic gel with stimulating responsive and self-repairability |
| CN109713198A (en) * | 2018-12-27 | 2019-05-03 | 四川理工学院 | MOFs/PMMA/PVDF three-phase composite battery diaphragm and preparation method thereof |
| CN111411403A (en) * | 2020-03-04 | 2020-07-14 | 扬州大学 | Electrostatic spinning preparation device of nanofiber filter screen and working method of electrostatic spinning preparation device |
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Citations (7)
| 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 |
| US20060286446A1 (en) * | 2003-06-17 | 2006-12-21 | Samshin Creation Co., Ltd. | Complex membrane for electrochemical device, manufacturing method and electrochemical device having the 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 nanofiber 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 |
-
2014
- 2014-12-10 CN CN201410750614.1A patent/CN104393337B/en active Active
Patent Citations (7)
| 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 |
| US20060286446A1 (en) * | 2003-06-17 | 2006-12-21 | Samshin Creation Co., Ltd. | Complex membrane for electrochemical device, manufacturing method and electrochemical device having the 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 nanofiber 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 |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111670273A (en) * | 2017-10-09 | 2020-09-15 | 斯柏博科技有限公司 | Method and apparatus for protein fiber production |
| US11618976B2 (en) | 2017-10-09 | 2023-04-04 | Spiber Technologies Ab | Method and device for protein fiber production |
| CN107959049A (en) * | 2017-11-23 | 2018-04-24 | 南开大学 | Preparation method, gel electrolyte and the lithium ion battery of gel electrolyte |
| CN107959049B (en) * | 2017-11-23 | 2021-01-29 | 南开大学 | Preparation method of gel electrolyte, gel electrolyte and lithium ion battery |
| CN108623826A (en) * | 2018-05-18 | 2018-10-09 | 北京大学 | A kind of dual network ionic gel with stimulating responsive and self-repairability |
| CN108623826B (en) * | 2018-05-18 | 2020-06-26 | 北京大学 | Double-network ionic gel with stimulus responsiveness and self-repairability |
| CN109713198A (en) * | 2018-12-27 | 2019-05-03 | 四川理工学院 | MOFs/PMMA/PVDF three-phase composite battery diaphragm and preparation method thereof |
| CN111411403A (en) * | 2020-03-04 | 2020-07-14 | 扬州大学 | Electrostatic spinning preparation device of nanofiber filter screen and working method of electrostatic spinning preparation device |
| CN117457996A (en) * | 2023-12-25 | 2024-01-26 | 安徽盟维新能源科技有限公司 | Double-crosslinking composite electrolyte membrane and preparation method and application thereof |
| 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 |
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