CN107154513A - Gel-form solid polymer electrolyte film, preparation method and sodium-ion battery - Google Patents
Gel-form solid polymer electrolyte film, preparation method and sodium-ion battery Download PDFInfo
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- CN107154513A CN107154513A CN201710347759.0A CN201710347759A CN107154513A CN 107154513 A CN107154513 A CN 107154513A CN 201710347759 A CN201710347759 A CN 201710347759A CN 107154513 A CN107154513 A CN 107154513A
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- 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
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- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- 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
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- 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
Abstract
The invention discloses a kind of preparation method of gel-form solid polymer electrolyte film, comprise the following steps：S1, polyethyleneglycol diglycidylether, polyetheramine and solvent are mixed, precursor solution is obtained；S2, the precursor solution is applied on porous membrane, and heating response obtains the polymer film of porous membrane support；S3, the polymer film that the porous membrane is supported is immersed in liquid electrolyte, adsorbs electrolyte, and the gel-form solid polymer electrolyte film of porous membrane support is made.The present invention prepares gel-form solid polymer electrolyte film good mechanical stability, and ionic conductivity is high, good with metallic sodium interface compatibility.The present invention also provides a kind of gel-form solid polymer electrolyte film as made from the preparation method, and a kind of sodium rechargeable battery using the gel-form solid polymer electrolyte film.
Description
Technical field
The present invention relates to sodium rechargeable battery material, more particularly to a kind of gel-form solid polymer electrolyte film, preparation method
And sodium-ion battery.
Background technology
In the energy storage device currently researched and developed, lithium ion battery is in portable equipments such as mobile phone, notebook computer and electronic
More and more important effect is just being played in the vehicles such as bicycle, electric automobile.The consumption of lithium ion battery increases year by year,
In particular, synthesis positive electrode is required for the presoma containing lithium of significant proportion, and the resource of lithium is extremely limited, with
The Quick Extended of lithium ion battery applications scope, the lithium salts situation that supply falls short of demand necessarily occurs.It is contemplated that lithium-ion electric
The pond cost of raw material is difficult to be greatly reduced, and it is restricted in the application of extensive energy storage (such as energy-accumulating power station).Many institute's weeks
Know, metal sodium element in the earth's crust reserves relative abundance and distributed areas extensively simultaneously sodium it is similar with the physicochemical properties of lithium and
De-/embedding mechanism is similar, therefore the research and development of sodium-ion battery are expected to a certain extent alleviate because lithium resource shortage is drawn
The energy-storage battery development limitation problem of hair.Commercialized anode material of lithium-ion battery is expected at present for hard carbon, and its needs passes through
High temperature cabonization is obtained, different according to its different cost of carbon source, generally speaking will height compared with lithium cell negative pole material graphite.Its specific capacity is about
For 300mAhg-1, and metallic sodium negative pole theoretical specific capacity need not be calcined up to 1166mAhg-1, and metallic sodium, cost of manufacture
It is very cheap.It is sodium-sulphur battery that commercialization is had been carried out at present using the battery of metallic sodium, and its operating temperature is about up to 300 DEG C,
Require the expenditure of energy and it is heated to maintain operating temperature.And realize the metallic sodium electrode worked at room temperature and there is problems with still
Do not solved effectively：(1) although the liquid state organic electrolyte commonly used under normal temperature is with higher electrical conductivity, due to metal
Sodium has higher activity, constantly can occur side reaction with metallic sodium during circulating battery, constantly consume electrolyte,
Passivating film is formed, is continuously increased the internal resistance of cell, the capacity of battery is constantly decayed；(2) sodium ion is in the uneven of electrode surface
Deposition causes electrode surface to produce a large amount of dendrite, and the dendrite of continued propagation, which can penetrate the hole of battery diaphragm and positive contact, to be caused
Battery short circuit, triggers a series of cells burst even safety problems such as blast.
Current research of the gel polymer electrolyte in sodium-ion battery is still less.Gel polymer electrolyte has good
Good machining property and film forming, and stable interface is easily formed with sodium metal, the leakage of liquid electrolyte can be avoided,
It is safe；In addition, the sufficiently high polymer of mechanical property can prevent the infiltration of metallic sodium.However, gel polymer electrolyte
Mechanical performance is easily greatly reduced after matter is soaked in liquid electrolyte, can seriously damage the security and cycle performance of battery；
The shortcoming is easily caused battery and internal short-circuit easily occurs in assembling and application process, causes potential safety hazard.And be chemically crosslinked
Although gelatin polymer possesses good heat endurance, dimensional stability and outstanding mechanical property, but the gel of crosslinking gathers
Compound is highly brittle, and pliability is poor, it is difficult to meet actual operation requirements.For the mechanical strength of the gelatin polymer that strengthens crosslinking,
Also the polyalkene diaphragm for commonly using micropore is used as mechanical support matrix.Although the crosslinking GPE of MIcroporous polyolefin film support shows to fill
The mechanical property of foot, but the porosity of polyalkene diaphragm is relatively low, high temperature dimensional stability is poor, ionic conductivity is low.
The content of the invention
It is a primary object of the present invention to overcome the deficiencies in the prior art, there is provided a kind of gel-form solid polymer electrolyte film, system
Preparation Method and sodium-ion battery.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of gel-form solid polymer electrolyte film, methods described comprises the following steps：
S1, polyethyleneglycol diglycidylether, polyetheramine and solvent are mixed, precursor solution is obtained；
S2, the precursor solution is applied on porous membrane, and heating response obtains the polymer of porous membrane support
Film；
S3, the polymer film that the porous membrane is supported is immersed in liquid electrolyte, is adsorbed electrolyte, is preferably adsorbed to
Saturation, is made the gel-form solid polymer electrolyte film of porous membrane support.
Further：
The polyethyleneglycol diglycidylether and the polyetheramine account for the mass percent difference of the precursor solution
For 1~3%, 2~6%.
The number-average molecular weight of the polyethyleneglycol diglycidylether is 500,1000,2000 or 6000Da；The polyethers
The number-average molecular weight of amine is 230,400,1000,2000 or 4000Da.
The solvent is in acetone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE
It is a kind of.
The porous membrane is one kind in micropore polyolefin barrier diaphragm, glass fibre, Kapton or cellulose membrane.
In step S2, first the porous membrane is placed in a diameter of 6~12cm Teflon mould, added described
Precursor solution, is put into constant temperature convection oven after standing a period of time, after ring-opening polymerization occurs for heating for a period of time, obtains
The polymer film supported to the porous membrane of thermal polymerization.
In step S2, the precursor solution heated at constant temperature is reacted, it is preferable that temperature is 60~120 DEG C, and the time is 8
~48h.
Before in the polymer film immersion liquid electrolyte that the porous membrane is supported, also comprise the following steps：First will
The polymer film of the porous membrane support of above-mentioned thermal polymerization is washed three times with absolute ethyl alcohol, with except the monomer that is remained in striping and molten
Agent, then the polymer film of washing is placed in drying in vacuum drying oven.
The liquid electrolyte includes sodium salt and plasticizer, and the sodium salt includes double trifluoromethanesulfonimide sodium, hexafluoro
One or more in sodium phosphate, sodium tetrafluoroborate or double fluorine sulfimide sodium.
The concentration of sodium salt is 0.6~1.2mol/L in the liquid electrolyte.
The plasticizer include ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate,
One or more in propene carbonate, trimethyl phosphate, glycol dimethyl ether.
A kind of gel-form solid polymer electrolyte film of porous membrane support, the polymer gel electrolyte of the porous membrane support
Plasma membrane is as obtained by the preparation method of described gel-form solid polymer electrolyte film.
A kind of sodium rechargeable battery, the sodium rechargeable battery includes the gel-form solid polymer electrolyte that described porous membrane is supported
Film.
Beneficial effects of the present invention：
The preparation method for the gel-form solid polymer electrolyte film that the present invention is provided utilizes epoxide group ring-opening polymerization mechanism, will be poly-
Ethylene glycol diglycidylether and polyetheramine react the three-dimensional crosslinked network to be formed and permeated in the network of porous membrane, its height
The polymer network structure of crosslinking provides polymer film excellent mechanical stability.The polymer gel prepared in the inventive method
Containing abundant PEO, PPO unit in dielectric film, not only there are good compatibility, adsorbable a large amount of electrolysis with liquid electrolyte
Liquid, it is to avoid the leakage of electrolyte, can also provide the passage of conducts sodium ions, can quick conducts sodium ions.The inventive method system
The conductivity at room temperature of the gel-form solid polymer electrolyte film of standby porous membrane support is up to 2.18 × 10-3Scm-1, with liquid
In the same order of magnitude, (ionic conductivity is 4.72 × 10 to the room-temperature conductivity of electrolyte cooperation glass fibre-3Scm-1).The present invention
The gel-form solid polymer electrolyte film and the good interface compatibility of metallic sodium for the porous membrane support that method is prepared, it is thermally-stabilised
Property and dimensionally stable are outstanding.What the gel-form solid polymer electrolyte film for the porous membrane support that the inventive method is prepared was assembled into
The Symmetrical cells of metallic sodium/metallic sodium have more stable interface impedance and lower polarizing voltage in cyclic process.
The gel-form solid polymer electrolyte film good mechanical stability of porous membrane support prepared by the present invention, ionic conductivity
Height is good with metallic sodium interface compatibility.The polymer gel of porous membrane support in sodium rechargeable battery using the present invention is electric
Plasma membrane is solved, the security performance and charge-discharge performance of sodium rechargeable battery can be effectively improved, the quality of sodium rechargeable battery is lifted.
Brief description of the drawings
Polyethyleneglycol diglycidylether (PEGDE) and polyetheramine (D2000) is anti-in Fig. 1 better embodiments of the present invention
Answer schematic diagram.
The surface Scanning Electron microscope figure for the polymer film that Fig. 2 supports for porous membrane made from embodiment 1.
The ionic conductivity and temperature for the gel-form solid polymer electrolyte film that Fig. 3 supports for porous membrane made from embodiment 1
Graph of relation.
The stress-strain curve for the gel-form solid polymer electrolyte film that Fig. 4 supports for porous membrane made from embodiment 1.
The thermogravimetric curve figure for the gel-form solid polymer electrolyte film that Fig. 5 supports for porous membrane made from embodiment 1.
The electrochemical stability window figure for the gel-form solid polymer electrolyte film that Fig. 6 supports for porous membrane made from embodiment 1.
The gel-form solid polymer electrolyte film and liquid electrolyte that Fig. 7 supports for porous membrane made from embodiment 1 are assembled into
Vanadium phosphate sodium/cycle performance figure of the metal sode cell at 25 DEG C.
The gel-form solid polymer electrolyte film and liquid electrolyte that Fig. 8 supports for porous membrane made from embodiment 1 are assembled into
High rate performance figure of the vanadium phosphate sodium/metal sode cell at 25 DEG C.
The gel-form solid polymer electrolyte film and liquid electrolyte that Fig. 9 supports for porous membrane made from embodiment 1 are assembled into
Vanadium phosphate sodium/cycle performance figure of the metal sode cell at 60 DEG C.
The gel-form solid polymer electrolyte film and liquid electrolyte that Figure 10 supports for porous membrane made from embodiment are assembled into
Metallic sodium/polarization curve of the metallic sodium Symmetrical cells at 25 DEG C.
Embodiment
Embodiments of the present invention are elaborated below.It is emphasized that what the description below was merely exemplary,
The scope being not intended to be limiting of the invention and its application.
Referring to Fig. 1, in one embodiment, a kind of preparation method of gel-form solid polymer electrolyte film, the porous membrane
The gel-form solid polymer electrolyte film of support is mainly used in sodium-ion battery, and it comprises the following steps：
Step S1, a certain amount of polyethyleneglycol diglycidylether, polyetheramine and solvent are mixed, presoma is obtained molten
Liquid.
Specifically, polyethyleneglycol diglycidylether and polyetheramine are added in solvent, is uniformly mixed, obtains colourless
Transparent precursor solution.
The solvent is in acetone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE
It is a kind of.
The mass percent that the polyethyleneglycol diglycidylether and the polyetheramine account for solution is respectively 1~3% and 2
~6%.The number-average molecular weight of the polyethyleneglycol diglycidylether is 500,1000,2000 or 6000Da.The polyetheramine
Number-average molecular weight be 230,400,1000,2000 or 4000Da.
Step S2, above-mentioned precursor solution is added in porous membrane, heated constant temperature reaction a period of time, obtains porous thin
The three-dimensional crosslinked network polymer film of film support.
Specifically, first porous membrane is placed in a diameter of 6~12cm Teflon mould, pours into presoma molten
Liquid, is put into constant temperature convection oven after standing a period of time, after ring-opening polymerization occurs for heating for a period of time, obtains thermal polymerization
Porous membrane support polymer film.
Wherein, the temperature of precursor solution heated constant temperature reaction is 60~120 DEG C, and the time is 8~48h.
Step S3, the polymer film that above-mentioned porous membrane is supported is immersed in liquid electrolyte, is adsorbed to saturation, is made many
The gel-form solid polymer electrolyte film of hole film support.
Further, before in the polymer film immersion liquid electrolyte that the porous membrane is supported, in addition to it is as follows
Step：The polymer film that first porous membrane of above-mentioned thermal polymerization is supported is washed three times with absolute ethyl alcohol, with except residual in striping
Monomer and solvent, then by the polymer film of washing be placed in vacuum drying oven dry.
Wherein, the temperature dried in vacuum drying oven is 60 DEG C, and the time is 12h.The liquid electrolyte is by sodium salt and increasing
Agent composition is moulded, the sodium salt includes but is not limited to double trifluoromethanesulfonimide sodium, sodium hexafluoro phosphate, sodium tetrafluoroborate or double fluorine
One or more in sulfimide sodium.The concentration of sodium salt is 0.6~1.2mol/L in the liquid electrolyte.The plasticizer
Including but not limited to ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, propylene carbonate
One or more in ester, trimethyl phosphate, glycol dimethyl ether.
The preparation method of the gel-form solid polymer electrolyte film of the porous membrane support, according to epoxide group ring-opening polymerisation machine
Reason, reacts the three-dimensional crosslinked network to be formed by polyethyleneglycol diglycidylether and polyetheramine and permeates network in porous membrane
In, its highly cross-linked polymer network structure provides polymer film good mechanical stability；Prepared in the inventive method
Containing abundant PEO, PPO unit in the gel-form solid polymer electrolyte film of porous membrane support, can quick conducts sodium ions, and with
Liquid electrolyte has good compatibility, adsorbable a large amount of electrolyte, it is to avoid the leakage of electrolyte；And the skeleton being crosslinked provides excellent
Elegant mechanical property, fine and close three-dimensional crosslinked network causes gel electrolyte membrane to have excellent mechanical stability.
Below by specific embodiment, the present invention will be further described.
Embodiment 1
The present embodiment is related to a kind of preparation method of the gel-form solid polymer electrolyte film of porous membrane support, methods described bag
Include following steps：
(1) 4.0g DMF is added in 25ml beaker, the contracting of 0.4g polyethylene glycol two is then weighed
Water glycerin ether (Mn=500) and 0.88g polyetheramines (Mn=2000) are added in beaker, and stirring 2h is well mixed.Will be porous thin
Film, which is placed in clean Teflon mould, pours into above-mentioned solution, is positioned over after standing a period of time in constant temperature convection oven
Ring-opening polymerisation 24h under 80 DEG C of constant temperature, the polymer film for the porous membrane support being heating and curing；
(2) polymer film of the porous membrane support prepared by is washed three times with absolute ethyl alcohol, with residual except containing in striping
Remaining monomer and solvent, is then placed in the dry 12h of 60 DEG C of vacuum drying oven by polymer film, then moves to afterwards in glove box,
Liquid electrolyte (concentration of sodium salt is 1.0mol/L in liquid electrolyte) [increasing added in electrolyte of 1.0M sodium hexafluoro phosphates
Modeling agent is ethylene carbonate:Dimethyl carbonate=1:1 (volume ratio)] in immersion 12h to saturation, you can porous membrane support is made
Gel-form solid polymer electrolyte film.
The room-temperature conductivity of the gel-form solid polymer electrolyte film for the porous membrane support that the present embodiment is prepared is 2.18
×10-3Scm-1。
The gel-form solid polymer electrolyte film that porous membrane made from the present embodiment is supported is applied in secondary sode cell, side
Method is as follows：
In secondary sode cell with addition 20wt%Super P in vanadium phosphate sodium positive electrode powder as conductive agent,
(the PVDF/NMP solution that PVDF is the 0.05g/mL prepared, NMP is N- crassitudes to 10wt%PVDF (Kynoar)
Ketone) as binding agent, after stirring, it is coated on aluminium foil, is put into after being dried in 80 DEG C of baking oven, is 5 in pressure
MPa pressure lower sheeting after, be washed into pole piece with 12 millimeters of drift of diameter, be put into 120 DEG C of vacuum drying oven dry 8 hours.
Vanadium phosphate sodium positive plate is transferred in argon gas glove box, using metallic sodium piece as negative pole, the polymer gel of porous membrane support
Dielectric film is electrolyte membrance, is assembled into CR2032 button cells, and in LAND battery test systems, (the blue electric electronics in Wuhan is limited
Company provide) on carry out constant current charge-discharge performance test, charging and discharging currents density be 0.25mAcm-2, discharge and recharge blanking voltage
Relative to Na/Na+For 2.5~3.8V.
Polyethyleneglycol diglycidylether and polyetheramine reaction equation are as shown in Figure 1 in the present embodiment.
Surface topography such as Fig. 2 institutes of the obtained gel-form solid polymer electrolyte film for obtaining porous membrane support of the present embodiment
Show, as seen from the figure, prepared gel-form solid polymer electrolyte film surface shows comparatively dense cross-linked network, and is not present
Obvious micropore.
The ionic conductivity of three-dimensional crosslinked network gel-form solid polymer electrolyte film made from the present embodiment is bent with temperature relation
Line chart is as shown in figure 3, its room-temperature conductivity is 2.18 × 10-3Scm-1。
The load-deformation curve such as Fig. 4 institutes for the gel-form solid polymer electrolyte film that porous membrane made from the present embodiment is supported
Show, the polymer film shows excellent mechanical strength and toughness.
The thermogravimetric curve such as Fig. 5 for the gel-form solid polymer electrolyte film that porous membrane made from the present embodiment is supported.By Fig. 5
Understand, polymer film initial decomposition temperature is 150 DEG C or so, and this shows that the polymer film has good heat endurance, can meet
Use requirement on sodium rechargeable battery.
Gel-form solid polymer electrolyte membrane electrochemical stability window figure such as Fig. 6 institutes that porous membrane made from the present embodiment is supported
Show, using stainless steel as working electrode, metallic sodium piece is to electrode and reference electrode, the polymer dielectric film of porous membrane support
Centre is sandwiched in, as seen from the figure, its electrochemical stability window is 5.0V.
The gel-form solid polymer electrolyte film and liquid electrolyte for the porous membrane support that the present embodiment is prepared are assembled into
Cycle performance of the vanadium phosphate sodium/metal sode cell at 25 DEG C and high rate performance respectively as shown in Figure 7 and Figure 8, at 60 DEG C
Cycle performance it is as shown in Figure 9.It follows that the gel-form solid polymer electrolyte film of porous membrane support has than liquid electrolyte
More excellent cyclical stability and high rate performance.
The gel-form solid polymer electrolyte film and liquid electrolyte for the porous membrane support that the present embodiment is prepared are assembled into
Metallic sodium/25 DEG C of metallic sodium Symmetrical cells at polarization curve as shown in Figure 10, as seen from the figure, porous membrane support polymerization
Thing gel electrolyte membrane has lower polarizing voltage and more stable interface performance.
Embodiment 2
The present embodiment is related to a kind of preparation method of the gel-form solid polymer electrolyte film of porous membrane support, methods described bag
Include following steps：
(1) 0.2g polyethyleneglycol diglycidylethers (Mn=500) and 0.4g polyetheramines (Mn are added in 25ml beaker
=2000) be added in beaker, stirring 2h is well mixed.With Kapton is placed in clean Teflon mould
In, above-mentioned solution is poured into, the ring-opening polymerisation 24h under 80 DEG C of constant temperature is positioned in constant temperature convection oven after standing a period of time, obtains
To the polymer film for the porous membrane support being heating and curing；
(2) polymer film of the porous membrane support prepared by is washed three times with absolute ethyl alcohol, with residual except containing in striping
Remaining monomer and solvent, is then placed in the dry 12h of 60 DEG C of vacuum drying oven by polymer film, then moves to afterwards in glove box,
Liquid electrolyte (concentration of sodium salt is 1.0mol/L in liquid electrolyte) [increasing added in electrolyte of 1.0M sodium hexafluoro phosphates
Modeling agent is ethylene carbonate:Dimethyl carbonate=1:1 (volume ratio)] in immersion 12h to saturation, you can porous membrane support is made
Gel-form solid polymer electrolyte film.
The room-temperature conductivity of the gel-form solid polymer electrolyte film for the porous membrane support that the present embodiment is prepared is 1.96
×10-3Scm-1。
The gel-form solid polymer electrolyte film that porous membrane made from the present embodiment is supported is applied in secondary sode cell, institute
Battery is more close with battery performance that embodiment 1 is obtained.
Embodiment 3
The present embodiment is related to a kind of preparation method of the gel-form solid polymer electrolyte film of porous membrane support, methods described bag
Include following steps：
(1) 0.1g polyethyleneglycol diglycidylethers (Mn=1000) and 0.4g polyetheramines are added in 25ml beaker
(Mn=4000) it is added in beaker, stirring 2h is well mixed.With polyolefin film is placed in clean Teflon mould
In, above-mentioned solution is poured into, the ring-opening polymerisation 48h under 60 DEG C of constant temperature is positioned in constant temperature convection oven after standing a period of time, obtains
To the polymer film for the porous membrane support being heating and curing；
(2) polymer film of the porous membrane support prepared by is washed three times with absolute ethyl alcohol, with residual except containing in striping
Remaining monomer and solvent, is then placed in the dry 12h of 60 DEG C of vacuum drying oven by polymer film, then moves to afterwards in glove box,
Liquid electrolyte (concentration of sodium salt is 1.0mol/L in liquid electrolyte) [increasing added in electrolyte of 1.0M sodium hexafluoro phosphates
Modeling agent is ethylene carbonate:Dimethyl carbonate=1:1 (volume ratio)] in immersion 12h to saturation, you can porous membrane support is made
Gel-form solid polymer electrolyte film.
The room-temperature conductivity of the gel-form solid polymer electrolyte film of the porous membrane support prepared is 1.68 × 10-3Scm-1。
The gel-form solid polymer electrolyte film that porous membrane made from the present embodiment is supported is applied in secondary sode cell, institute
Battery is more close with battery performance that embodiment 1 is obtained.
Embodiment 4
The present embodiment is related to the preparation method of the gel-form solid polymer electrolyte film of porous membrane support, and methods described is included such as
Lower step：
(1) 0.1g polyethyleneglycol diglycidylethers (Mn=500) and 0.2g polyetheramines (Mn are added in 25ml beaker
=2000) be added in beaker, stirring 2h is well mixed.It is placed in by cellophane in clean Teflon mould,
Above-mentioned solution is poured into, the ring-opening polymerisation 24h under 80 DEG C of constant temperature is positioned in constant temperature convection oven after standing a period of time, is added
The polymer film of the porous membrane support of heat cure；
(2) polymer film of the porous membrane support prepared by is washed three times with absolute ethyl alcohol, with residual except containing in striping
Remaining monomer and solvent, is then placed in the dry 12h of 60 DEG C of vacuum drying oven by polymer film, then moves to afterwards in glove box,
Liquid electrolyte (concentration of sodium salt is 1.0mol/L in liquid electrolyte) [increasing added in electrolyte of 1.0M sodium hexafluoro phosphates
Modeling agent is ethylene carbonate:Dimethyl carbonate=1:1 (volume ratio)] in immersion 12h to saturation, you can porous membrane support is made
Gel-form solid polymer electrolyte film.
The room-temperature conductivity for the three-dimensional crosslinked network gel-form solid polymer electrolyte film that the present embodiment is prepared be 3.56 ×
10-3Scm-1。
The gel-form solid polymer electrolyte film that porous membrane made from the present embodiment is supported is applied in secondary sode cell, institute
Battery is more close with battery performance that embodiment 1 is obtained.
Above content is to combine specific/preferred embodiment made for the present invention be further described, it is impossible to recognized
The specific implementation of the fixed present invention is confined to these explanations.For general technical staff of the technical field of the invention,
Without departing from the inventive concept of the premise, it can also make some replacements or modification to the embodiment that these have been described,
And these are substituted or variant should all be considered as belonging to protection scope of the present invention.
Claims (10)
1. a kind of preparation method of gel-form solid polymer electrolyte film, it is characterised in that methods described comprises the following steps：
S1, polyethyleneglycol diglycidylether, polyetheramine and solvent are mixed, precursor solution is obtained；
S2, the precursor solution is applied on porous membrane, and heating response obtains the polymer film of porous membrane support；
S3, the polymer film that the porous membrane is supported is immersed in liquid electrolyte, is adsorbed electrolyte, is preferably adsorbed to full
With the gel-form solid polymer electrolyte film of obtained porous membrane support.
2. the preparation method of gel-form solid polymer electrolyte film as claimed in claim 1, it is characterised in that：The polyethylene glycol two
The mass percent that glycidol ether and the polyetheramine account for the precursor solution is respectively 1~3%, 2~6%；Preferably,
The number-average molecular weight of the polyethyleneglycol diglycidylether is 500,1000,2000 or 6000Da；The number of the polyetheramine is equal
Molecular weight is 230,400,1000,2000 or 4000Da.
3. the preparation method of gel-form solid polymer electrolyte film as claimed in claim 1 or 2, it is characterised in that：The solvent is
One kind in acetone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.
4. the preparation method of the gel-form solid polymer electrolyte film as described in any one of claims 1 to 3, it is characterised in that：It is described
Porous membrane is one kind in micropore polyolefin barrier diaphragm, glass fibre, Kapton or cellulose membrane.
5. the preparation method of the gel-form solid polymer electrolyte film as described in any one of Claims 1-4, it is characterised in that：Step
In S2, first the porous membrane is placed in a diameter of 6~12cm Teflon mould, the precursor solution is added,
It is put into after standing a period of time in constant temperature convection oven, after ring-opening polymerization occurs for heating for a period of time, obtains thermal polymerization
The polymer film of porous membrane support.
6. the preparation method of the gel-form solid polymer electrolyte film as described in any one of claim 1 to 5, it is characterised in that：Step
In S2, the precursor solution heated at constant temperature is reacted, it is preferable that temperature is 60~120 DEG C, the time is 8~48h.
7. the preparation method of the gel-form solid polymer electrolyte film as described in any one of claim 1 to 6, it is characterised in that：Institute
Before stating in the polymer film immersion liquid electrolyte of porous membrane support, also comprise the following steps：First by above-mentioned thermal polymerization
The polymer film of porous membrane support wash three times with absolute ethyl alcohol, with except the monomer and solvent that are remained in striping, then will be washed
Polymer film be placed in vacuum drying oven dry.
8. the preparation method of the gel-form solid polymer electrolyte film as described in any one of claim 1 to 7, it is characterised in that：It is described
Liquid electrolyte includes sodium salt and plasticizer, and the sodium salt includes double trifluoromethanesulfonimide sodium, sodium hexafluoro phosphate, tetrafluoro boron
One or more in sour sodium or double fluorine sulfimide sodium；Preferably, in the liquid electrolyte concentration of sodium salt for 0.6~
1.2mol/L；Preferably, the plasticizer includes ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, carbon
One or more in sour dipropyl, propene carbonate, trimethyl phosphate, glycol dimethyl ether.
9. a kind of gel-form solid polymer electrolyte film of porous membrane support, it is characterised in that：The polymerization of the porous membrane support
Thing gel electrolyte membrane is as obtained by the preparation method of the gel-form solid polymer electrolyte film described in any one of claim 1 to 8.
10. a kind of sodium rechargeable battery, it is characterised in that：The sodium rechargeable battery is included as the porous membrane described in claim 9
The gel-form solid polymer electrolyte film of support.
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| CN108598569A (en) * | 2018-05-10 | 2018-09-28 | 浙江大学山东工业技术研究院 | A kind of three-dimensional network gel polymer electrolyte material and its preparation method and application |
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| CN114791454A (en) * | 2021-01-26 | 2022-07-26 | 清华大学 | Measuring device and measuring method for electrolyte oxidation potential |
| CN114790278A (en) * | 2021-01-26 | 2022-07-26 | 清华大学 | Glyceryl ether epoxy resin and preparation method thereof |
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| TWI837456B (en) | 2021-01-26 | 2024-04-01 | 鴻海精密工業股份有限公司 | Glyceryl ether epoxy resin and method for making the same |
| CN113851710A (en) * | 2021-11-02 | 2021-12-28 | 浙江钠创新能源有限公司 | Sodium ion bifunctional gel polymer electrolyte, and preparation method and application thereof |
| CN113851710B (en) * | 2021-11-02 | 2023-09-15 | 浙江钠创新能源有限公司 | Sodium ion difunctional gel polymer electrolyte, preparation method and application thereof |
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