CN106654369A - Gel polymer electrolyte membrane of vertical membrane surface of magnetic nanorod and preparation method thereof - Google Patents

Gel polymer electrolyte membrane of vertical membrane surface of magnetic nanorod and preparation method thereof Download PDF

Info

Publication number
CN106654369A
CN106654369A CN201710158191.8A CN201710158191A CN106654369A CN 106654369 A CN106654369 A CN 106654369A CN 201710158191 A CN201710158191 A CN 201710158191A CN 106654369 A CN106654369 A CN 106654369A
Authority
CN
China
Prior art keywords
pvdf
hfp
gel polymer
nanometer rods
polymer electrolyte
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710158191.8A
Other languages
Chinese (zh)
Other versions
CN106654369B (en
Inventor
杨文胜
汪杨
杨晨旭
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN201710158191.8A priority Critical patent/CN106654369B/en
Publication of CN106654369A publication Critical patent/CN106654369A/en
Application granted granted Critical
Publication of CN106654369B publication Critical patent/CN106654369B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01M2300/0085—Immobilising or gelification of 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to a gel polymer electrolyte membrane of a vertical membrane surface of a magnetic nanorod and a preparation method thereof, and belongs to the technical field of lithium ion battery electrolyte. The gel polymer electrolyte membrane is composed of a polyvinylidene fluoride-hexafluoropropylene PVDF-HFP copolymer and magnetic Fe3O4 nanorod inorganic fillers vertical to the membrane surface, wherein the mass fraction of the PVDF-HFP is 95-99%, the mass fraction of the Fe3O4 nanorod is 1-5%, the thickness of the membrane is 70-100 microns, and the aperture is 1-5 microns; and the molecular weight of the PVDF-HFP copolymer is 350000-450000 g/mol, the mass ratio of PVDF to HFP is 88:12, the diameter of the Fe3O4 nanorod is 80-100nm, and the length of the Fe3O4 nanorod is 600-800nm. The preparation method comprises the following steps: uniformly mixing the Fe3O4 nanorod in a matrix of the PVDF-HFP copolymer, applying a magnetic field vertical to the membrane surface to directionally arrange the Fe3O4 nanorod, and naturally drying the mixture in the air to form the membrane. The gel polymer electrolyte membrane has the advantages that the ionic conductivity is effectively improved, and an assembled gel polymer lithium ion battery has higher specific capacity and better rate performance.

Description

The gel polymer electrolyte film and preparation method of the vertical face of magnetic Nano rod
Technical field
The invention belongs to lithium ion battery electrolyte technical field, more particularly to a kind of magnetic ferroferric oxide Fe3O4Receive Kynoar-hexafluoropropene PVDF-HFP base gel polymer electrolytes of the vertical face of rice rod and preparation method thereof.
Background technology
Lithium ion battery has the advantages that operating voltage is high, energy density is big and service life cycle is long, portable It is used widely in electronic product, in fields such as electric motor cars wide application prospect is also presented.But conventional lithium ion battery Using liquid electrolyte, the danger such as electrolyte leakage and blast are easily caused in high temperature or when working long hours.Using gel polymerisation The polymer Li-ion battery of thing electrolyte can preferably overcome the above-mentioned safety issue of conventional lithium ion battery, and Can be more flexible in battery appearance design.
Gel polymer electrolyte is the important component part for determining polymer Li-ion battery performance, in order to improve gel The performance of polymer dielectric, the method that addition inorganic nano-filler can be adopted.Inorganic nano-filler is to gelatin polymer electricity The effect of solution matter is embodied in following aspect：One is that inorganic nano-filler interacts with the anion in lithium salts, reduces lithium salts Effect between zwitterion, increased the number of carrier；Two be inorganic nano-filler with polymer segment in anion phase Interaction, alleviates constraint of the anion to lithium ion in segment；Three to be that inorganic nano-filler has upset polymer architecture regular Property, its degree of crystallinity is reduced, enhance the sub-chain motion of polymer.Such as in document (1) Journal of Membrane Science,2009,326(2):In 582-588, Osinska et al. researchs find, add in gel polymer electrolyte and receive Rice SiO2The pick up and ionic conductivity of gel polymer electrolyte can be improved, so as to lift the performance of lithium ion battery. But in the document reported, typically inorganic nano material is disorderly added in gel polymer electrolyte film, to gel The lifting of electrolyte performance is limited.
The content of the invention
It is an object of the invention to provide a kind of new magnetic Fe3O4The PVDF-HFP base gels of the vertical face of nanometer rods Polymer dielectric film, inorganic filler Fe3O4 nanometer rods align the effect that can give full play to inorganic filler, effectively carry High ionic conductivity, the gel polymer lithium ion battery of the gel polymer electrolyte film assembling prepared by the present invention has Higher specific capacity and good high rate performance.
The gel polymer electrolyte film of the present invention is by PVDF-HFP copolymers and the Fe perpendicular to face3O4Nanometer rods Inorganic filler is constituted, and the mass fraction of PVDF-HFP is 95～99%, Fe3O4The mass fraction of nanometer rods is 1～5%, film thickness For 70～100 μm, aperture is 1～5 μm；Wherein, the molecular weight of PVDF-HFP copolymers is 350000～450000g/mol, The mass ratio of PVDF and HFP is 88:12, Fe3O480～100nm of nanorod diameter, 600～800nm of length.
Present invention also offers one kind prepares above-mentioned Fe3O4The PVDF-HFP bases gelatin polymer electricity of the vertical face of nanometer rods The method of solution plasma membrane, it is characterised in that comprise the steps：
(1) by FeCl3·6H2O is dissolved in deionized water the FeCl for being configured to that concentration is 0.48～0.5mol/L3Solution, Then according to FeCl3Solution and 1,2- propane diamine C3H10N2Volume ratio is 1:0.9～1.1 the two is well mixed obtain mixing it is molten Liquid；Mixed solution is proceeded in hydrothermal reaction kettle and the 50%～80% of reactor volume is accounted for, react 20 at 200～240 DEG C～ 24h；The suspension obtained after reaction is filtered, then deionized water cyclic washing to pH=7～8 will be deposited in 60～100 DEG C vacuum drying 8～12h, that is, obtain α-Fe2O3Nanometer rods；
(2) under reducing atmosphere, the α-Fe that will be prepared in step (1)2O3Nanometer rods are with the ramp of 5～10 DEG C/min To 300～450 DEG C of 1～6h of roasting, that is, obtain Fe3O4Nanometer rods；Wherein described reducing atmosphere is H2Or H2In/Ar gaseous mixtures One kind, and H2H in/Ar gaseous mixtures2Volume fraction be 10%～15%；
(3) according to Fe3O4Nanometer rods account for PVDF-HFP and Fe3O4The ratio of the 1%～5% of gross mass mixes the two, so In being scattered in the DMF DMF solvent of 4～5 times of PVDF-HFP mass afterwards, 12～18h of stirring obtains stable slurry Material, is then coated onto on smooth substrate, and it is applied perpendicular to the magnetic that the magnetic field intensity of substrate is 0.3～0.5T , 6～12h is spontaneously dried in the air that relative humidity is 20%～40%, then 6～12h is vacuum dried at 60～80 DEG C, Obtain Fe of the present invention3O4The PVDF-HFP base gel polymer electrolyte films of the vertical face of nanometer rods；Wherein, the substrate is One kind in smooth glass plate or polyfluortetraethylene plate.
The Fe prepared using preceding method3O4ESEM (SEM) test result of nanometer rods is as shown in Figure 1, it is seen that Fe3O4Nanometer rods size uniformity；Fig. 2 is Fe3O4The XRD test spectrograms of nanometer rods, with Fe3O4Standard spectrogram JCPDS#19-0629 It is consistent, and crystal formation is good；Fig. 3 is Fe3O4The hysteresis curve of nanometer rods, test result shows Fe prepared by the inventive method3O4Magnetic Property is stronger；The SEM test results of gel polymer electrolyte film prepared by the inventive method are as shown in Figure 4, it is seen that the present invention is produced Product surface is presented abundant and uniform pore structure；The SEM of gel polymer electrolyte film section prepared by the inventive method is surveyed Test result is as shown in Figure 5, it is seen that interiors of products of the present invention still suffers from abundant and uniform hole；Fig. 6 is the survey of ESEM power spectrum Test result, wherein white portion are Fe elements, show Fe in gel polymer electrolyte film prepared by the inventive method3O4Nanometer Rod is arranged perpendicular to face.
Fe prepared by the inventive method3O4The PVDF-HFP Ji Ningjiaojuhewu electricity Xie Zhimochong of the vertical face of nanometer rods Into the disk of a diameter of 16.5mm, in the glove box (H full of argon gas2O content<1ppm, O2Content<In 1ppm), in 1.0mol/L Hexafluoro phosphatization lithium LiPF6(volume ratio is 1 to-ethylene carbonate EC/ dimethyl carbonate DMC/ methyl ethyl carbonate EMC:1:1) electrolyte Middle immersion 20min, then siphons away the electrolyte of excess surface with filter paper, obtains gel polymer electrolyte.By spinelle mangaic acid Lithium LiMn2O4(PVDF is dissolved in 1-METHYLPYRROLIDONE for positive electrode, acetylene black conductor and Kynoar PVDF binding agents The solution that mass fraction is 3% is formed in NMP) in mass ratio it is 8:1:1 ratio mixing, stirring forms uniform sizing material, then It is coated onto on aluminium foil, 100 DEG C of drying obtain positive pole, with metal Li pieces as negative pole, assembles in the glove box full of argon gas Electrochemical property test is carried out into button cell.High rate performance test result is as shown in fig. 7, by inventive gel polymer electrolytic The gel polymer lithium ion battery of plasma membrane assembling has higher specific capacity and good high rate performance.
Used as control, we adopt and prepare the similar method of gel electrolyte membrane with above-mentioned, simply in the mistake of coating slurry Apply the magnetic field for parallel to the magnetic field intensity of substrate being 0.3～0.5T in journey, then obtain Fe3O4 nanometer rods parallel to face PVDF-HFP base gel polymer electrolyte films；If not applying magnetic field during coating slurry, Fe3O4 nanometers are obtained The disorderly arranged PVDF-HFP base gel polymer electrolyte films of rod.Main electrification based on the gel electrolyte of above-mentioned three kinds of films Learn the performance test results as shown in table 1, wherein 1.0C=120mA/g.
The main electrochemical property test result of the sample segment of table 1
Sample Ionic conductivity Specific capacity under 0.1C electric currents Specific capacity under 1.0C electric currents
Embodiment 1 3.09x10-3S/cm 115.4mAh/g 84.1mAh/g
Comparative example 1 2.22x10-3S/cm 111.1mAh/g 74.9mAh/g
Comparative example 2 2.83x10-3S/cm 114.0mAh/g 77.5mAh/g
The present invention distinguishing feature and advantage be：The invention provides a kind of new Fe3O4The vertical face of nanometer rods PVDF-HFP base gel polymer electrolyte films, aligning for inorganic filler Fe3O4 nanometer rods can give full play to inorganic filling out The effect of material, improves ionic conductivity, the gel polymer lithium ion electricity assembled by inventive gel polymer dielectric film Pond has higher specific capacity and good high rate performance.
Description of the drawings
Fig. 1 is the Fe that the embodiment of the present invention 1 is provided3O4The SEM photograph of nanometer rods.
Fig. 2 is the Fe that the embodiment of the present invention 1 is provided3O4The XRD spectra of nanometer rods；Wherein, abscissa be the θ of angle 2, unit： Degree (°), ordinate is diffracted intensity, unit：Absolute unit (a.u.).
Fig. 3 is the Fe that the embodiment of the present invention 1 is provided3O4The hysteresis curve test result figure of nanometer rods.Wherein, abscissa is Magnetic field intensity, unit：Oersted (Oe), ordinate is the intensity of magnetization, unit：Gauss (Gs).
Fig. 4 is the Fe that the embodiment of the present invention 1 is provided3O4The PVDF-HFP base gel polymer electrolytes of the vertical face of nanometer rods The SEM photograph of plasma membrane.
Fig. 5 is the Fe that the embodiment of the present invention 1 is provided3O4The PVDF-HFP base gel polymer electrolytes of the vertical face of nanometer rods The SEM photograph of plasma membrane section.
Fig. 6 is power spectrum test result corresponding with the SEM of Fig. 5 figures, and wherein white portion is Fe elements.
Fig. 7 is the gel polymer lithium ion battery of the gel polymer electrolyte film assembling that the embodiment of the present invention 1 is provided High rate performance figure；Wherein, numeral is discharge-rate in figure, 1.0C=120mA/g, and abscissa is cycle-index, unit：It is secondary (times), ordinate is specific discharge capacity, unit：MAh/g (mAh/g).
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, below in conjunction with accompanying drawing and it is embodied as Example, the present invention will be described in further detail, but the present invention is not limited only to this.
Embodiment 1
(1) by the FeCl of 4.05g3·6H2O is dissolved in 28mL deionized waters and is configured to FeCl3Solution, is subsequently adding The 1,2- propane diamine C of 30mL3H10N2It is well mixed；Solution is proceeded in the static hydrothermal reactor that volume is 100mL, 220 DEG C reaction 20h；The suspension obtained after reaction is filtered, then deionized water cyclic washing to pH=7 will be deposited in 60 DEG C Lower vacuum drying 12h, that is, obtain α-Fe2O3Nanometer rods.
(2) in H2/ Ar gaseous mixture (H2H in/Ar gaseous mixtures2Volume fraction under 10%) atmosphere, will system in step (1) Standby α-Fe2O3With 5 DEG C/min ramps to 350 DEG C of roasting 4h, that is, obtain Fe3O4Nanometer rods.
(3) Fe of 0.18g is added in the PVDF-HFP powder of 6g3O4Nanometer rods, in being dissolved in the DMF solvent of 24g, stir Mix 12h and obtain stable slurry；Slurry is coated on smooth glass plate using automatic film applicator, and is applied in coating procedure Plus perpendicular to glass substrate magnetic field intensity for 0.35T magnetic field, spontaneously dry 6h in the air that relative humidity is 30%, so It is vacuum dried 6h at 60 DEG C afterwards, that is, obtains Fe3O4Perpendicular to the PVDF-HFP base gel polymer electrolyte films of face.
Fe manufactured in the present embodiment3O4The SEM photograph of nanometer rods is as shown in Figure 1, it is seen that Fe3O4Nanometer rods size uniformity；Figure 2 is Fe3O4The XRD test spectrograms of nanometer rods, with Fe3O4Standard spectrogram JCPDS#19-0629 is consistent, and crystal formation is good；Fig. 3 is Fe3O4The hysteresis curve of nanometer rods, test result shows its relatively high magnetism；Gel polymer electrolyte film manufactured in the present embodiment SEM photograph it is as shown in Figure 4, it is seen that its surface is presented abundant and uniform pore structure；The gel polymer electrolyte film is cutd open The SEM test results in face are as shown in Figure 5, it is seen that abundant and uniform hole is still suffered from inside it；Fig. 6 is right with the SEM of Fig. 5 figures The power spectrum test result answered, wherein white portion are Fe elements, in showing gel polymer electrolyte film manufactured in the present embodiment Fe3O4Nanometer rods are arranged perpendicular to face.
By Fe manufactured in the present embodiment3O4The PVDF-HFP base gel polymer electrolyte films of the vertical face of nanometer rods are washed into The disk of a diameter of 16.5mm, in the glove box (H full of argon gas2O content<1ppm, O2Content<In 1ppm), in 1.0mol/L LiPF6(volume ratio is 1 to-EC/DMC/EMC:1:1) 20min is soaked in electrolyte, the electrolysis of excess surface is then siphoned away with filter paper Liquid, obtains gel polymer electrolyte；By spinelle LiMn2O4Positive electrode, acetylene black conductor and PVDF binding agent (PVDF The solution for forming that mass fraction is 3% is dissolved in NMP) in mass ratio it is 8:1:1 ratio mixing, stirring is formed and is homogenized Material, is then coated onto on aluminium foil, and 100 DEG C of drying obtain positive pole, with metal Li pieces as negative pole, in the glove box full of argon gas In be assembled into button cell and carry out electrochemical property test.High rate performance test result by inventive gel as shown in fig. 7, be polymerized The gel polymer lithium ion battery of thing dielectric film assembling has higher specific capacity and good high rate performance.
Embodiment 2
(1) by the FeCl of 4.0g3·6H2O is dissolved in 27mL deionized waters and is configured to FeCl3Solution, is subsequently adding 29mL 1,2- propane diamine C3H10N2It is well mixed；Solution is proceeded in the static hydrothermal reactor that volume is 100mL, it is anti-at 200 DEG C Answer 24h；The suspension obtained after reaction is filtered, deionized water cyclic washing to pH=7, it is then that product is true at 100 DEG C Sky is dried 10h, that is, obtain α-Fe2O3Nanometer rods.
(2) in H2/ Ar gaseous mixture (H2H in/Ar gaseous mixtures2Volume fraction under 10%) atmosphere, will system in step (1) Standby α-Fe2O3With 5 DEG C/min ramps to 300 DEG C of roasting 5h, that is, obtain Fe3O4Nanometer rods.
(3) Fe of 0.06g is added in the PVDF-HFP powder of 6g3O4Nanometer rods, in being dissolved in the DMF solvent of 24g, stir Mix 16h and obtain stable slurry；Slurry is coated on smooth glass substrate, and in coating procedure using automatic film applicator Apply, perpendicular to the magnetic field that the magnetic field intensity of glass substrate is 0.3T, in the air that relative humidity is 20% 8h to be spontaneously dried, Then 12h is vacuum dried at 60 DEG C, that is, obtains Fe3O4Perpendicular to the PVDF-HFP base gel polymer electrolyte films of face.
Embodiment 3
(1) by the FeCl of 4.2g3·6H2O is dissolved in 30mL deionized waters and is configured to FeCl3Solution, is subsequently adding 31mL 1,2- propane diamine C3H10N2It is well mixed；Solution is proceeded in the static hydrothermal reactor that volume is 100mL, it is anti-at 240 DEG C Answer 20h；The suspension obtained after reaction is filtered, then deionized water cyclic washing to pH=8 will be deposited in 80 DEG C of vacuum 8h is dried, that is, obtains α-Fe2O3Nanometer rods.
(2) in H2Under atmosphere, the α-Fe that will be prepared in step (1)2O3With 10 DEG C/min ramps to 400 DEG C of roasting 3h, Obtain Fe3O4Nanometer rods.
(3) Fe of 0.3g is added in the PVDF-HFP powder of 6g3O4Nanometer rods, in being dissolved in the DMF solvent of 30g, stirring 18h obtains stable slurry；Slurry is coated on smooth ptfe substrate, and coated using automatic film applicator Apply magnetic field of the magnetic field intensity perpendicular to ptfe substrate for 0.5T in journey, in the air that relative humidity is 40% from 12h is so dried, then 10h is vacuum dried at 80 DEG C, that is, obtains Fe3O4Perpendicular to the PVDF-HFP bases gelatin polymer electricity of face Solution plasma membrane.
Comparative example 1
(1) by the FeCl of 4.05g3·6H2O is dissolved in 28mL deionized waters and is configured to FeCl3Solution, is subsequently adding The 1,2- propane diamine C of 30mL3H10N2It is well mixed；Solution is proceeded in the static hydrothermal reactor that volume is 100mL, 220 DEG C reaction 20h；The suspension obtained after reaction is filtered, then deionized water cyclic washing to pH=7 will be deposited in 60 DEG C Vacuum drying 12h, that is, obtain α-Fe2O3Nanometer rods.
(2) in H2/ Ar gaseous mixture (H2H in/Ar gaseous mixtures2Volume fraction under 10%) atmosphere, will system in step (1) Standby α-Fe2O3With 5 DEG C/min ramps to 350 DEG C of roasting 4h, that is, obtain Fe3O4Nanometer rods.
(3) Fe of 0.18g is added in the PVDF-HFP powder of 6g3O4Nanometer rods, in being dissolved in the DMF solvent of 24g, stir Mix 12h and obtain stable slurry；Slurry is coated on smooth glass substrate, and in coating procedure using automatic film applicator Apply the magnetic field for parallel to the magnetic field intensity of glass substrate being 0.35T, in the air that relative humidity is 30% 6h spontaneously dried, Then 6h is vacuum dried at 60 DEG C, that is, obtains the PVDF-HFP base gel polymer electrolyte films parallel to face.
Comparative example 2
(1) by the FeCl of 4.05g3·6H2O is dissolved in 28mL deionized waters and is configured to FeCl3Solution, is subsequently adding The 1,2- propane diamine C of 30mL3H10N2It is well mixed；Solution is proceeded in the static hydrothermal reactor that volume is 100mL, 220 DEG C reaction 20h；The suspension obtained after reaction is filtered, then deionized water cyclic washing to pH=7 will be deposited in 60 DEG C Vacuum drying 12h, that is, obtain α-Fe2O3Nanometer rods.
(2) in H2/ Ar gaseous mixture (H2H in/Ar gaseous mixtures2Volume fraction under 10%) atmosphere, will system in step (1) Standby α-Fe2O3With 5 DEG C/min ramps to 350 DEG C of roasting 4h, that is, obtain Fe3O4Nanometer rods.
(3) Fe of 0.18g is added in the PVDF-HFP powder of 6g3O4Nanometer rods, in being dissolved in the DMF solvent of 24g, stir Mix 12h and obtain stable slurry；Slurry is coated on smooth glass substrate, in coating procedure not using automatic film applicator Magnetic field is applied to slurry, in the air that relative humidity is 30% 6h is spontaneously dried, be then vacuum dried 6h at 60 DEG C, that is, obtained Fe3O4The disorderly arranged PVDF-HFP base gel polymer electrolyte films of nanometer rods.
Examples detailed above is the citing of the present invention, although disclosing highly preferred embodiment of the present invention and attached for the purpose of illustration Figure, but the present invention is not intended to limit, any those of ordinary skill in the art, without departing from right of the invention and appended In the spirit and scope of requirement, various replacements, to change and modifications all be possible.Therefore, the present invention should not be limited to optimal reality Apply example and accompanying drawing disclosure of that.

Claims (4)

1. a kind of gel polymer electrolyte film of the vertical face of magnetic Nano rod, it is characterised in that the gel polymer electrolyte Plasma membrane is by Kynoar-hexafluoropropene PVDF-HFP copolymers and the magnetic Fe_3O_4 nanometer rods inorganic filler perpendicular to face Constitute, the mass fraction of PVDF-HFP is 95～99%, Fe3O4The mass fraction of nanometer rods be 1～5%, film thickness be 70～ 100 μm, aperture is 1～5 μm；Wherein, the molecular weight of PVDF-HFP copolymers is 350000～450000g/mol, PVDF and HFP Mass ratio be 88:12, Fe3O480～100nm of nanorod diameter, 600～800nm of length.
2. a kind of method for preparing the gel polymer electrolyte film of the vertical face of magnetic Nano rod described in claim 1, it is special Levy and be, comprise the steps：
(1) by FeCl3·6H2O is dissolved in deionized water the FeCl for being configured to that concentration is 0.48～0.5mol/L3Solution, then According to FeCl3Solution and 1,2- propane diamine C3H10N2Volume ratio is 1:The two is well mixed and obtains mixed solution by 0.9～1.1；Will Mixed solution is proceeded in hydrothermal reaction kettle and accounts for the 50%～80% of reactor volume, little in 200～240 DEG C of reactions 20～24 When；The suspension obtained after reaction is filtered, then deionized water cyclic washing to pH=7～8 will be deposited in 60～100 DEG C vacuum drying 8～12 hours, that is, obtain α-Fe2O3Nanometer rods；
(2) under reducing atmosphere, the α-Fe that will be prepared in step (1)2O3Nanometer rods with 5～10 DEG C/min of ramp extremely 300～450 DEG C of roastings 1～6 hour, that is, obtain Fe3O4Nanometer rods；
(3) according to Fe3O4Nanometer rods account for PVDF-HFP and Fe3O4The ratio of the 1%～5% of gross mass mixes the two, Ran Houfen Dissipate in the DMF DMF solvent of 4～5 times of PVDF-HFP mass, stirring obtains stable slurry in 12～18 hours Material, is then coated onto on smooth substrate, and it is applied perpendicular to the magnetic that the magnetic field intensity of substrate is 0.3～0.5T , in the air that relative humidity is 20%～40% spontaneously dry 6～12 hours, then 60～80 DEG C be vacuum dried 6～ 12 hours, that is, obtain Fe3O4The PVDF-HFP base gel polymer electrolyte films of the vertical face of nanometer rods.
3. preparation method according to claim 2, it is characterised in that in step (2), the reducing atmosphere is H2Or H2/ One kind in Ar gaseous mixtures；Wherein, H2H in/Ar gaseous mixtures2Volume fraction be 10%～15%.
4. preparation method according to claim 2, it is characterised in that in step (3), the substrate is smooth glass One kind in plate or polyfluortetraethylene plate.
CN201710158191.8A 2017-03-16 2017-03-16 The gel polymer electrolyte film and preparation method of the vertical film surface of magnetic Nano stick Active CN106654369B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710158191.8A CN106654369B (en) 2017-03-16 2017-03-16 The gel polymer electrolyte film and preparation method of the vertical film surface of magnetic Nano stick

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710158191.8A CN106654369B (en) 2017-03-16 2017-03-16 The gel polymer electrolyte film and preparation method of the vertical film surface of magnetic Nano stick

Publications (2)

Publication Number Publication Date
CN106654369A true CN106654369A (en) 2017-05-10
CN106654369B CN106654369B (en) 2019-03-29

Family

ID=58848392

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710158191.8A Active CN106654369B (en) 2017-03-16 2017-03-16 The gel polymer electrolyte film and preparation method of the vertical film surface of magnetic Nano stick

Country Status (1)

Country Link
CN (1) CN106654369B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107394108A (en) * 2017-07-14 2017-11-24 上海应用技术大学 A kind of method for preparing high-capacity lithium ion cell anode pole piece
CN112563666A (en) * 2020-12-18 2021-03-26 芯科众联新材料(常州)有限公司 Mixed amphiprotic agent of small-particle alumina powder and large-particle alumina powder and process flow
CN114085479A (en) * 2021-12-09 2022-02-25 郑州大学 Polyvinylidene fluoride-hexafluoropropylene magnetic porous piezoelectric composite film and preparation method and application thereof
CN115483432A (en) * 2022-09-28 2022-12-16 哈尔滨工业大学 Composite solid electrolyte and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101153084A (en) * 2006-09-28 2008-04-02 万向电动汽车有限公司 Polyalcohol microporous barrier for high ratio polyalcohol lithium ion power cell
CN103224638A (en) * 2013-05-03 2013-07-31 中国科学院上海硅酸盐研究所 Filler-textured polymer matrix composite material with high thermal conductivity and preparation method thereof
CN103779089A (en) * 2012-10-26 2014-05-07 海洋王照明科技股份有限公司 Gel polymer dielectric and preparation method for the same, super capacitor and application thereof
CN103840201A (en) * 2012-11-26 2014-06-04 海洋王照明科技股份有限公司 P(VDF-HFP) (Polyvinylidene Fluoride-Hexafluoropropylene)-based gel polymer electrolyte membrane, and preparation method thereof and lithium ion battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101153084A (en) * 2006-09-28 2008-04-02 万向电动汽车有限公司 Polyalcohol microporous barrier for high ratio polyalcohol lithium ion power cell
CN103779089A (en) * 2012-10-26 2014-05-07 海洋王照明科技股份有限公司 Gel polymer dielectric and preparation method for the same, super capacitor and application thereof
CN103840201A (en) * 2012-11-26 2014-06-04 海洋王照明科技股份有限公司 P(VDF-HFP) (Polyvinylidene Fluoride-Hexafluoropropylene)-based gel polymer electrolyte membrane, and preparation method thereof and lithium ion battery
CN103224638A (en) * 2013-05-03 2013-07-31 中国科学院上海硅酸盐研究所 Filler-textured polymer matrix composite material with high thermal conductivity and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107394108A (en) * 2017-07-14 2017-11-24 上海应用技术大学 A kind of method for preparing high-capacity lithium ion cell anode pole piece
CN107394108B (en) * 2017-07-14 2020-03-20 上海应用技术大学 Method for preparing high-capacity lithium ion battery positive pole piece
CN112563666A (en) * 2020-12-18 2021-03-26 芯科众联新材料(常州)有限公司 Mixed amphiprotic agent of small-particle alumina powder and large-particle alumina powder and process flow
CN114085479A (en) * 2021-12-09 2022-02-25 郑州大学 Polyvinylidene fluoride-hexafluoropropylene magnetic porous piezoelectric composite film and preparation method and application thereof
CN114085479B (en) * 2021-12-09 2022-10-28 郑州大学 Polyvinylidene fluoride-hexafluoropropylene magnetic porous piezoelectric composite film and preparation method and application thereof
CN115483432A (en) * 2022-09-28 2022-12-16 哈尔滨工业大学 Composite solid electrolyte and preparation method thereof
CN115483432B (en) * 2022-09-28 2024-01-09 哈尔滨工业大学 Composite solid electrolyte and preparation method thereof

Also Published As

Publication number Publication date
CN106654369B (en) 2019-03-29

Similar Documents

Publication Publication Date Title
CN109256543B (en) A kind of modified nickel cobalt manganese lithium aluminate cathode material and preparation method thereof
CN109980219A (en) Full gradient nickel cobalt manganese anode material, ruthenium-oxide covering material and preparation method thereof
CN106654369B (en) The gel polymer electrolyte film and preparation method of the vertical film surface of magnetic Nano stick
CN106058215B (en) Dodecahedron porous C o3The preparation method of ZnC/C composite materials and the application in lithium ion battery
Xiang et al. Improved electrochemical performance of 0.5 Li2MnO3· 0.5 LiNi0. 5Mn0. 5O2 cathode materials for lithium ion batteries synthesized by ionic-liquid-assisted hydrothermal method
CN113942990A (en) Lithium manganese iron phosphate precursor, lithium manganese iron phosphate positive electrode material, preparation method of lithium manganese iron phosphate positive electrode material, electrode and lithium ion battery
CN108288711A (en) A kind of quaternary lithium-ion battery positive electrode material and preparation method
CN103715424A (en) Core-shell structured cathode material and preparation method thereof
CN108400291A (en) A kind of lithium ion battery composite cathode material and preparation method thereof
CN103094558A (en) Zinc-ferrite-based nanometer composite as well as preparation method and application thereof
CN102544481A (en) Lithium ion battery and cathode material thereof
CN107256961B (en) A kind of preparation method and applications of lithium titanate hierarchical structure microballoon
CN105470482A (en) Preparation method of aluminum-coated spherical lithium nickel cobalt aluminum oxide cathode material for lithium-ion battery
CN105226267B (en) Three dimensional carbon nanotubes modification spinel nickel lithium manganate material and its preparation method and application
CN105932248B (en) A kind of modification lithium-ion battery lithium-rich manganese-based anode material and preparation method thereof
CN110364716B (en) Magnesium-based MOF spherical magnesium oxide coated lithium ion battery ternary positive electrode material and preparation method thereof
CN107394123A (en) Lithium-rich manganese-based hollow nano-sphere positive electrode that thin slice is wound in and preparation method thereof
CN106356510B (en) A kind of ion cathode material lithium FeVO4The preparation method of/C
CN106058186B (en) A kind of preparation method and application of codope lithium titanate composite material
CN104979541A (en) Lithium titanate composite material and preparation method thereof
CN108269980A (en) A kind of method for preparing high-performance di-iron trioxide/zinc ferrite combination electrode material
CN108011095B (en) Preparation method of NCA (negative polarity anodic oxidation) cathode material with high cycle stability suitable for power type lithium ion battery
CN110098387A (en) A kind of tertiary cathode material and its preparation method and application of lithium phosphate cooperation conductive carbon material cladding
CN102456877B (en) Cathode material precursor, preparation method thereof, cathode material and lithium battery
CN106532108B (en) Lithium iron phosphate/carbon nanotube complex microsphere with porous structure and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant