CN103665678B - Polymer film and preparation method thereof, electrolyte and battery with polymer film - Google Patents
Polymer film and preparation method thereof, electrolyte and battery with polymer film Download PDFInfo
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Abstract
The invention discloses a kind of polymer film, the copolymer at least including Kynoar and hexafluoropropene, polymer film also includes polymethyl methacrylate derivative, and the polymer film has porous spongy structure.Compared with prior art, the present invention passes through phase separation method, a kind of polymer film with loose structure is obtained using solvent/non-solvent, polymer film has ionic conductivity very high with stronger mechanical performance, to heat endurance and at room temperature, while the burning voltage window of up to 4.8V can be provided.Polymer film disclosed by the invention has considerable application prospect on commercialized polymer Li-ion battery and lithium-sulfur cell.
Description
Technical field
The present invention relates to a kind of polymer film.
The invention further relates to a kind of preparation method of polymer film.
The invention further relates to a kind of electrolyte with polymer film.
The invention further relates to a kind of battery of the electrolyte with polymer film.
Background technology
Used as a kind of high energy density cells of the prior art, by industry, personnel conduct extensive research lithium battery,
Wherein polymer Li-ion battery is due to that arbitrary shape and can be even more the extensive concern for having obtained people without leakage is dangerous.Polymerization
The critical material of thing lithium ion battery is electrolyte, and commercial polymerization thing lithium ion battery electrolyte is based on a kind of colloidal state
Organic micro film, wherein organic film are support frame, and electrolyte is then stored in micropore, and the conduction of lithium ion passes through polymer molecule
Sub-chain motion or the migration of the electrolyte being stored in micropore realize that whole polymer dielectric is in semi-solid structure.
Excellent polymer dielectric should possess that mechanical strength is big, stable electrochemical property, electronic isolation, ionic conduction
Rate is high, easily prepared and with conditions such as burning voltage windows wide.People were devoted to finding always meeting condition in recent years
Gel polymer and solid electrolyte.Research is concentrated mainly on polyacrylonitrile (PAN), and PEO (PEO) etc. is base
The polymer dielectric of matter, but because the conductivity at room temperature of these electrolyte is relatively low, electrolyte bad mechanical strength or polymerization
Thing matrix has an impact to the battery performance for preparing, and commercial applications are restricted.
Bellcore companies of the U.S. made a breakthrough in 1994 in terms of polymer Li-ion battery preparation, and successfully realized
Commercialization, the polymerization of microcellular structure is obtained with Kynoar-hexafluoropropene (PVDF-HFP) by plasticising/extraction process for they
Thing film, increased the pick up of polymer dielectric, and therefore improve the ionic conductivity of electrolyte and the high magnification of battery
Discharge performance.The weak point of the method is to extract plasticizer using extraction steps, thus improves battery production cost,
And the safety problem for thus bringing a large amount of organic plasticizers for the treatment of and occurring.
Therefore, prior art is necessary further raising in fact.
The content of the invention
Present invention offer is a kind of can be as electrolyte backing material with ionic conductivity high, voltage stabilization very wide
The polymer film of window.
The invention provides a kind of polymer film, the copolymer at least including Kynoar and hexafluoropropene is described poly-
Compound film also includes polymethyl methacrylate derivative.
Preferably, the polymethyl methacrylate derivative includes the poly-methyl methacrylate of trimethoxy silane substitution
Ester.
Preferably, the specific gravity range that the polymethyl methacrylate derivative accounts for the polymer film is 5-25%.
Preferably, the polymer film has porous spongy structure, and the aperture size of the polymer film is micron order
Or submicron order.
Preferably, the porosity ranges of the polymer film are 20-90%.
Preferably, polymer film ionic conductivity at room temperature is 4.7mS/cm.
Preferably, the burning voltage window of the polymer film is 4.8V.
Present invention also offers a kind of preparation method of polymer film, the preparation method comprises the following steps：
The copolymer of Kynoar and hexafluoropropene and polymethyl methacrylate derivative are dissolved in a solvent, machine
Ultrasonically treated, the homogeneous casting solution of formation is carried out after tool stirring；
To adding non-solvent in casting solution, until obtain homogeneous phase solution, homogeneous phase solution of casting treats solvent and non-to mechanical agitation
After solvent evaporation, polymer film is obtained；
Polymer film is dried treatment.
Preferably, the polymethyl methacrylate derivative is prepared to comprise the following steps：In 50-70 DEG C of temperature range
Under, by free based method, using azodiisobutyronitrile as thermal initiator, by methyl methacrylate and γ-metering system
Acryloxypropylethoxysilane trimethoxy silane polymerization generation polymethyl methacrylate derivative.
Preferably, the solvent includes acetone.
Preferably, the non-solvent includes the one kind in water, ethanol or methyl tertiary butyl ether(MTBE).
Preferably, the dried process is to carry out under vacuum, and the temperature range of the dried process is 50-80
DEG C, the time range of dried process is 5-12h.
Present invention also offers a kind of electrolyte, the electrolyte includes polymer film as described above.
Present invention also offers a kind of battery, including positive pole, negative pole and the electrolyte between positive pole and negative pole, institute
Stating electrolyte includes polymer film as described above.
Present invention also offers a kind of battery, including positive pole, negative pole and the electrolyte between positive pole and negative pole, institute
Stating positive pole at least includes participating in the positive electrode active materials of electrochemical reaction, and the positive electrode active materials contain sulfenyl material, described
Electrolyte includes polymer film as described above.
Compared with prior art, the present invention is prepared a kind of with loose structure by phase separation method using solvent/non-solvent
Polymer film, polymer film has stronger mechanical performance, there is ion very high to lead to heat endurance and at room temperature
Electric rate, at the same absorb liquid electrolyte polymer film have up to 4.8V burning voltage window, meet polymer lithium from
The application requirement of sub- battery and lithium-sulfur cell.
Brief description of the drawings
The invention will be further described with implementation method below in conjunction with the accompanying drawings.
Fig. 1 is the PMMA derivatives that embodiment 1 is provided1H nmr spectrums；
Fig. 2 is the thermal gravimetric analysis curve of the PMMA derivatives that embodiment 1 is provided；
Fig. 3 is the differential scanning calorimetric curve of the PMMA derivatives that embodiment 1 is provided；
Fig. 4 is the SEM figures of the polymer film that embodiment 1 is provided；
Fig. 5 is the linear scan cyclic voltammetry curve of lithium metal/gel polymer electrolyte/stainless steel；
Fig. 6 is the AC impedance figure of stainless steel/gel polymer electrolyte/stainless steel battery at room temperature；
Fig. 7 is the SEM figures of the polymer film that comparative example 1 is provided；
Fig. 8 is the TGA curves of the PVDF-HFP/PMMA polymer films for drying and absorbing electrolyte；
Fig. 9 is the relation curve of the ionic conductance with temperature of the PVDF-HFP/PMMA polymer films for absorbing electrolyte；
Figure 10 is the linear scan cyclic voltammogram of lithium metal/gel polymer electrolyte/stainless steel；
Figure 11 is the graph of a relation of the battery charging and discharging capacity that embodiment 2 is provided and voltage；
Figure 12 is the battery charging and discharging cycle performance figure that embodiment 2 is provided；
Figure 13 is the graph of a relation between the voltage of battery in embodiment 3 and discharge capacity；
Figure 14 is the battery charging and discharging cycle performance figure that embodiment 3 and comparative example 2 are provided；
Figure 15 is the graph of a relation of charge/discharge capacity and coulombic efficiency to cycle-index of battery in comparative example 3；
Figure 16 be embodiment 3, comparative example 2 and in comparative example 3 battery AC impedance figure；
Figure 17 is the graph of a relation of the battery charging and discharging discharge capacity that comparative example 4 is provided and voltage；
Figure 18 is the graph of a relation of the capability retention with cycle-index of the battery that comparative example 4 and comparative example 5 are provided；
Figure 19 is the graph of a relation of the coulombic efficiency with cycle-index of the battery that comparative example 4 and comparative example 5 are provided.
Specific embodiment
A kind of polymer film, can apply to electrochemical appliance, and electrochemical appliance includes but are not limited to battery.Using this
The battery of polymer film, can be applied to the such as field such as portable electron device, electric tool, electric automobile.
A kind of polymer film, the copolymer (PVDF- at least including Kynoar (PVDF) and hexafluoropropene (HFP)
HFP), polymethyl methacrylate (PMMA) derivative is also included in polymer film.
PVDF is a kind of functional fluoropolymer material of partially crystallizable, with mechanical strength higher, good heat resistance, mechanics
Performance, resistant to chemical etching and uvioresistant, ageing-resistant performance.In addition, PVDF stable chemical performances, can antioxidant, acid, alkali,
The corrosion of salt, halogen, aromatic hydrocarbons, fat and chlorinated solvent and swelling, has excellent uvioresistant and ageing-resistant performance concurrently.
The copolymer (PVDF-HFP) that PVDF and HFP is formed combines the performance of both polymer, i.e. the crystal structure of PVDF is caused
Copolymer has more excellent chemical stability, and unbodied HFP can improve the plasticity of copolymer, and this property is direct
It is related to the ionic conductivity of copolymer.
Construction unit is methyl methacrylate (MMA), the molecular backbone of PMMA in polymethyl methacrylate (PMMA)
Be saturated structures, side chain is polar ester groups, the ester group in the ester group of side chain and carbonate based organic solvent play the role of it is very strong, because
This can contain substantial amounts of liquid electrolyte, have good compatibility, the compound while PMMA birdss of the same feather flock together between liquid electrolyte
There is preferable interface stability with lithium electrode, the interface impedance with metal lithium electrode is low.
Further, PMMA derivatives are also included in polymer film, specifically, to introducing other functions in PMMA strands
Group, makes PMMA function dough.PMMA derivatives include but are not limited to the PMMA of trimethoxy silane substitution.Using containing vinyl
Organosiloxane, such as γ-methacryloxypropyl trimethoxy silane (MPTMS), by MPTMS and methyl methacrylate
Ester copolymerization, organosiloxane monomer is incorporated into the strand of polymethyl methacrylate, the PMMA obtained after function dough
Siloxane group hydrolyzes to form silanol in derivative molecular chain, and silanol occurs the network structure that condensation forms self-crosslinking, phase
Than in PMMA, the PMMA crosslinking degrees of trimethoxy silane substitution are higher, hole is more evenly distributed, good film-forming property, with more excellent
Different mechanical performance and thermal stability.
Polymer film in the present invention, including PVDF-HFP copolymers, polymethyl methacrylate (PMMA) derivative, its
In, the specific gravity range of PMMA derivatives is 5-25%.Polymer film has porous spongy structure, and distributing very evenly for hole gathers
The porosity ranges of compound film are 20-90%, and aperture size is micron order or submicron order.
The polymer film that the present invention is provided, on the basis of PVDF-HFP copolymers, further addition trimethoxy silane takes
The PMMA in generation, the polymer film for absorbing liquid electrolyte has ionic conductivity and chemical stability very high at room temperature.
Trimethoxy silane group is introduced on PMMA molecular side chains, a kind of PMMA derivatives of the functionalization containing flexible side chain are obtained,
And PMMA derivatives are incorporated into PVDF-HFP copolymers, can not only reduce the aperture chi of the apertured polymeric film of formation
It is very little, make pore size distribution more uniform such that it is able to preferably to accommodate liquid electrolyte, the chemical property of polymer film is improved, and
And can also further improve the mechanical performance of polymer film and to heat endurance.
Present invention further teaches a kind of preparation method of polymer film, polymer film at least includes Kynoar (PVDF)
With the copolymer p VDF-HFP of hexafluoropropene (HFP), polymethyl methacrylate (PMMA) derivative.
Specifically, preparation method is mainly using phase separation method to prepare polymer film.Phase separation method is to utilize casting solution
Solvent, non-solvent mass transfer are carried out with surrounding environment to exchange, the solution of script stable state is become unstable state and produce liquid-liquid phase point
From final curing forms membrane structure.The main structural form formed by liquid-liquid phase process of the performance of polymer film and polymerization
The phase in version solidification process of thing is determined.
The electrolyte of absorption can be inhaled as the ion conducting medium in polymer film, the polymer film prepared in the present invention
Substantial amounts of liquid electrolyte is received, this characteristic is very important for preparing the gel electrolyte of high-energy battery.In the present invention
The polymer film of preparation is transparent, without support, and is revealed without there is obvious liquid electrolyte.
A kind of preparation method of polymer film, preparation method comprises the following steps：
By copolymer and polymethyl methacrylate the derivative dissolving of Kynoar and hexafluoropropene in a solvent,
Ultrasonically treated, the homogeneous casting solution of formation is carried out after mechanical agitation；
To adding non-solvent in casting solution, until obtain homogeneous phase solution, homogeneous phase solution of casting treats solvent and non-to mechanical agitation
After solvent evaporation, polymer film is obtained；
Polymer film is dried treatment.
Polymer film is prepared by phase separation method (phase separation method), it is necessary first to prepare macromolecule
Solution, finds suitable solvent to dissolve during polymer, and it is close with the solubility parameters of polymer generally to follow solvent, solvent with
The principle such as the polarity of polymer is close and the lewis acid of solvent and polymer, alkalescence match.Specifically, solvent is acetone.
Non-solvent is the poor solvent of polymer, polymer solution is produced precipitation and is formed film, specifically, non-
Solvent can be selected from ether solvent, such as t-butyl methyl ether；Non-solvent can also be water or ethanol.
It is under stirring and ultrasonication, PVDF-HFP copolymers is uniform with polymethyl methacrylate derivative
Dissolving in a solvent, is then slowly added to non-solvent, and continues stirring, and mixing time scope is 3-5h.
Polymer film is finally dried treatment, so that further remove in polymer film may the solvent of residual and non-molten
Agent, specifically, dried process can be carried out under vacuum, the temperature range of dried process is 50-80 DEG C, dried process
Time range be 5-12h.
Polymethyl methacrylate derivative includes but are not limited to the PMMA of trimethoxy silane substitution, specifically, three
The preparation process of PMMA of methoxy silane substitution is：At 50-70 DEG C of temperature range, by free based method, using azo
Bis-isobutyronitrile is polymerized as thermal initiator by methyl methacrylate and γ-methacryloxypropyl trimethoxy silane
The PMMA of generation trimethoxy silane substitution.
In an implementation method for preparing polymer film, polymer film includes PVDF-HFP copolymers and trimethoxy silicon
The PMMA of alkane substitution, specific preparation process includes：At 70 DEG C, by free based method, using azodiisobutyronitrile as heat
Initiator, by MMA and γ-methacryloxypropyl trimethoxy silane (MPTMS) polymerization generation functional group fluidized polymer
That is the PMMA of trimethoxy silane substitution.Under stirring and ultrasound, PVDF-HFP copolymers and trimethoxy silane are replaced
PMMA compares 3 according to weight:1 mixes in acetone, forms homogeneous casting solution；Then to being slowly added to methyl- tert fourth in casting solution
Base ether, and continue stirring mixing 3h, on aluminium sheet, overnight evaporation solvent, obtains at room temperature for the homogeneous phase solution hand teeming for obtaining
Polymer film.In order to further remove the acetone and water of residual, polymer film is dried treatment, specifically, at 50 DEG C
Vacuum drying 5h.
When being added in casting solution as the ether of non-solvent, Precipitation is had, after a few hours are stirred, precipitation can again
Dissolving.When the amount of non-solvent is smaller, polymer can be completely dissolved, and casting solution is homogeneous phase solution；But when the amount of non-solvent increases
When big, polymer can be precipitated out, it is difficult to be redissolved be integrally formed.The formation mechenism of film is with typical dry method in this process
(typical dry phase inversion) masking mechanism is the same.Solvent and non-solvent can induce phase separation when volatilizing, when molten
When agent and non-solvent volatilize completely, that is, the polymer film with loose structure is obtained.
By using x-ray photoelectron spectroscopy (XRD), SEM (SEM) and synchronous solving (DSC-
TGA) can test and confirm the structure of polymer film of final molding, configuration of surface and to heat endurance.By the present invention
The polymer film that the preparation method of announcement is obtained is the porous spongy structure with micron order or submicron order, and pore size distribution is very
Uniformly, the porosity ranges of polymer film are have good connectedness between 20-90%, and Kong Yukong.In addition, with the addition of
The polymer film of PMMA derivatives has excellent heat endurance, liquid absorption capacity and ionic conductivity higher.
Present invention further teaches a kind of electrolyte, electrolyte includes polymer film, and polymer film includes being total to for PVDF-HFP
Polymers and PMMA derivatives.Polymer film constitutes electrolysis after liquid electrolyte is absorbed mainly as backing material, further
Matter.Liquid electrolyte includes salt and solvent, and salt includes but are not limited to lithium salts；Solvent includes but are not limited to organic solvent.
Lithium salts includes but are not limited to one or more in following material：LiSCN、LiBr、LiI、LiClO4、LiAsF6、
LiSO3CF3、LiSO3CH3、LiBF4、LiB(Ph)4、LiC(SO2CF3)3、LiPF6With LiN (SO2CF3)2.Can be adopted in organic solvent
The concentration range of lithium salts is 0.2-2.0M.Specifically, lithium salt is 0.5-1.5M.
Organic solvent can be the solvent of one-component or the mixed organic solvents of at least two components.Organic solvent bag
Include but be not limited only to one or more in following material：Dimethyl ether (DME), dimethyl carbonate (DMC), ethylene carbonate
(EC), carbonic acid diethyl ester (DEC), methyl ethyl carbonate alkene ester (EMC), propene carbonate (PC), methyl propyl carbonate (MPC), 1,3- bis-
Oxygen pentane (DIOX), ether, glyme, lactone, sulfone, sulfolane.
In a particular embodiment, by 1.0M LiPF6It is dissolved in organic solvent ethylene carbonate (EC), carbonic acid diethyl
Ester (DEC) (EC:DEC=1:As liquid electrolyte in 1v/v).Polymer film is immersed in liquid electrolyte and obtains semisolid
Gel electrolyte.Finally, treatment is dried to polymer film surface by filter paper, so as to the electrostrictive polymer of semisolid is obtained
Xie Zhi.
The polymer film of PMMA derivatives is introduced, and then polymer film is absorbed into liquid electrolyte and form gel electrolyte
Matter, on the one hand, can make the gel electrolyte there is liquid absorption and ionic conductivity high；On the other hand, gel electrolyte is improved
Matter and the interfacial characteristics of electrode, reduce the interface resistance and charge transfer resistance of electrode/electrolyte, and this is followed to improving battery
Ring performance and high rate performance have important meaning.
Polymer film with loose structure is a kind of organic micro film based on colloidal state, mainly as support frame, will
Liquid electrolyte is stored in micropore, and the ionic conducting property of electrolyte mainly passes through the sub-chain motion of polymer molecule or is stored in micro-
The migration of the ion in hole realizes that whole electrolyte is in semi-solid structure.The hole of polymer film enriches, and absorbs liquid electrolyte
Mass-energy power is strong, and the surface and the back side of film are all microcellular structure, so that ion transmission can run through whole polymer film so that polymerization
Thing electrolyte has ionic conductivity very high at room temperature, specifically, the electricity of the gel containing polymer film PVDF-HFP/PMMA
Solution matter ionic conductivity at room temperature is 3.37mS/cm, and provided in the present invention contain polymer film PVDF-HFP/PMMA
The gel electrolyte of derivative then has more excellent ionic conductivity, 4.7mS/cm.Simultaneously by cyclic voltammetry, this
Inventing the polymer dielectric for disclosing has electrochemical stability window very high, specifically, containing polymer film PVDF-HFP/
The electrochemical stability window of the gel electrolyte of PMMA be 4.5V, and in the present invention provide contain polymer film PVDF-HFP/
The electrochemical stability window of the gel electrolyte of function dough PMMA is then up to 4.8V.Therefore, by the electrostrictive polymer in the present invention
There is Xie Zhiyu high-tension electrode material to combine can not only constitute the battery with high-energy-density, and also solve electricity
, that is, there is high-tension electrode material and but can not find collocation therewith with high stable voltage window in the one big technical barrier in pond field
Electrolyte, therefore, the present invention disclose polymer dielectric build with high-energy-density battery applications on have it is non-
The prospect of Chang Keguan.
Present invention further teaches a kind of battery, including positive pole, negative pole and the electrolyte between positive pole and negative pole, electricity
Solution matter includes polymer film as described above.
Positive pole include positive electrode active materials, positive electrode active materials participate in electrochemical reaction, including can it is reversible deviate from-be embedded in
Ion or the material of functional group.
Specifically, positive electrode active materials include can it is reversible deviate from-be embedded in lithium ion, sodium ion, zinc ion or magnesium from
The material of son.Wherein, can it is reversible deviate from-material that is embedded in lithium ion included but are not limited to spinel structure or stratiform
The material of structure or olivine structural.
In current Lithium Battery Industry, nearly all positive electrode active materials all can be through modifications such as overdoping, claddings.But mix
Miscellaneous, the means such as coating modification cause the chemical general formula of material to express complicated, such as LiMn2O4Can not represent makes extensively at present
The formula of " LiMn2O4 ", and be construed as widely including by various modified LiMn2O4Positive electrode active materials.Together
Sample, LiFePO4And LiCoO2Also the positive-active being modified by various doping, cladding etc. should be construed broadly to include
Material.
When positive electrode active materials are lithium ion abjection-inlaid scheme, can be from such as LiMn2O4、LiFePO4、
LiCoO2、LiMxPO4、LiMxSiOyCompounds such as a kind of (wherein M are variable valency metal).Additionally, the change of sodium ion can be deviate from-is embedded in
Compound NaVPO4F, can deviate from-be embedded in the compound λ-MnO of zinc ion2, can deviate from-be embedded in the compound Mg M of magnesium ionxOy(its
Middle M is a kind of metal, 0.5<x<3,2<y<6)-the chemical combination of embedded ion or functional group can and with similar functions, be deviate from
Thing can serve as the positive electrode active materials of battery of the present invention.
Positive electrode active materials are corresponding, electrolyte when can deviate from-be embedded in lithium ion, sodium ion, magnesium ion or zinc ion
In salt can be lithium salts, sodium salt, magnesium salts or zinc salt.
Present invention also offers a kind of battery, including positive pole, negative pole and the electrolyte between positive pole and negative pole, just
Best includes participating in less the positive electrode active materials of electrochemical reaction, and positive electrode active materials contain sulfenyl material, and electrolyte is included such as
Upper described polymer film.
Positive electrode active materials contain sulfenyl material, and sulfenyl material accounts for the 70-90% of positive electrode active materials gross weight.Sulfenyl material
Material is selected from elementary sulfur, Li2Sn, containing sulfur compound, organic sulfur compound or carbon-sulfur polymer (C2Sv)mIn at least one, wherein, n
>=1,2.5≤v≤50, m >=2.
Although elemental sulfur has considerable theoretical specific capacity, elemental sulfur is the insulator of electronics and ion at room temperature,
The lithium-sulfur cell of the elemental sulfur positive pole composition of sulfur content 100% is at room temperature that impossible carry out discharge and recharge.Under normal circumstances, will
With sulfenyl material in any suitable manner, such as mixing, ball milling, heat treatment is obtained for carbons conductive material or conducting polymer materials
Sulfur-bearing composite, wherein, carbons conductive material include but are not limited to CNT, carbon black, activated carbon, carbon fiber or
At least one in Graphene, carbon black includes acetylene black, Ketjen black；Conducting polymer materials include but are not limited to polypyrrole
(Ppy), polyacrylonitrile (PAN).
When positive pole is prepared, also need to add conductive agent and binding agent, anode sizing agent is prepared together with positive electrode active materials.
Conductive agent is used to accelerate the transmission of electronics, while effectively improving migration speed of the lithium ion in positive electrode active materials
Rate.Specifically, conductive agent be selected from conducting polymer, activated carbon, Graphene, carbon black, carbon fiber, metallic fiber, metal dust, with
And one or more in sheet metal.Weight proportion scope of the conductive agent in positive electrode active materials is 5-15%.Specifically,
Conductive agent includes super-P carbon blacks.
Binding agent is selected from polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyimides, polyester, polyethers, fluorination
Polymer, poly- divinyl polyethylene glycol, polyethyleneglycol diacrylate, the one kind in glycol dimethacrylates, or
The mixture and derivative of above-mentioned polymer.Weight proportion scope of the binding agent in positive electrode active materials is 5-15%.Specifically
, binding agent includes Kynoar (PVDF).
Positive pole also includes plus plate current-collecting body, and plus plate current-collecting body is selected from but is not limited only to Copper Foil, copper mesh, aluminium foil, nickel foam or
One kind in stainless (steel) wire.Specifically, plus plate current-collecting body is nickel foam.
Porous polymer film can prevent electrolyte from being revealed in cyclic process, in addition, the polymer that the present invention is provided
Film, can not only absorb substantial amounts of liquid electrolyte, and suppress the dissolving of many lithium sulfides of lithium-sulfur cell intermediate product, improve sulfenyl
The utilization rate of positive electrode, therefore, overcome the major obstacle in lithium-sulfur cell practical development.
Negative pole include negative current collector and negative electrode active material, negative electrode active material be selected from lithium metal, lithium alloy, lithium carbon or
The negative active core-shell material of silica-base material.Lithium alloy includes lithium-aluminium alloy, lithium-magnesium alloy or lithium-tin alloy；Carbon in lithium carbon
The selection of sill is unrestricted, including crystalline carbon, amorphous carbon, or its mixture.Silica-base material is selected from elemental silicon, and silicon is closed
Gold, the silicon of metallic cover, at least one in metal-doped silicon.Silicon alloy includes silicon-carbon alloys, silicon-lithium alloy and silicon-manganese
Alloy.In order to improve the electrical conductivity of material silicon, typically in the Surface coating or the doping metals in silicon of silicon, metal be selected from but not only
It is limited to the copper with good electronic conduction ability, tin, silver etc..
Negative current collector is selected from but is not limited only to Copper Foil, copper mesh, aluminium foil, the one kind in nickel foam or stainless (steel) wire, when negative
When pole active material is lithium metal, lithium metal is also used as negative current collector in itself.
There is the lithium ion of abjection-insertion, selection in order to ensure in charge and discharge process, between the positive pole and negative pole of battery
Sulfenyl material and silica-base material simultaneously without lithium when, to positive pole and/or negative pole pre-embedding lithium processes.Specific pre- embedding lithium mode is not
Limit, including chemically react embedding lithium or the embedding lithium of electrochemical reaction.
As well known to those skilled in the art, during in order to avoid lithium metal as negative pole, negative terminal surface is produced because deposition is uneven
Dendrite, it will usually layer protecting film is formed in negative terminal surface, diaphragm can be the LiPON formed in metallic lithium surface
The interfacial film that compound interface film, or lithium alloy are formed.Therefore, the scope of the invention is also included in negative active core-shell material
Surface forms the negative pole of diaphragm.
The present invention disclose use polymer dielectric battery, because polymer dielectric have excellent mechanical performance,
To heat endurance, ionic nature and the up to voltage stability window of 4.8V are quickly led at room temperature so that the electricity in the present invention
Pond has in terms of capacity and cycle performance and improves a lot, meanwhile, polymer dielectric is semi-solid so that battery
The actual cost of battery can be reduced in composition without using barrier film.
The unit in percent weight in volume in the present invention is well-known to those skilled in the art, such as volume basis
Than the weight for referring to the solute in 100 milliliters of solution.Unless otherwise defined, all specialties and scientific words used in text
It is identical with meaning familiar to one skilled in the art institute.Additionally, any method similar to described content or impartial and material
In all can be applied to the inventive method.Preferable implementation described in text only presents a demonstration with material and is used.
With reference to embodiment, present disclosure is further illustrated.It should be appreciated that implementation of the invention is not limited to
In the following examples, any formal accommodation and/or change made to the present invention fall within the scope of the present invention.
In the present invention, if not refering in particular to, all of part, percentage are unit of weight, and all of equipment and raw material etc. can be from markets
Buy or the industry is conventional.
Embodiment 1
At 70 DEG C, by using azodiisobutyronitrile as the free based method of thermal initiator, by 0.1 mole of methyl
Methyl acrylate (MMA) and 10 mMs of γ-methacryloxypropyl trimethoxy silane (MPTMS) polymerization generation three
The PMMA of methoxy silane substitution.
Under stirring and ultrasound, the PMMA that PVDF-HFP copolymers and trimethoxy silane replace is compared 3 according to weight:1
Mix in acetone, form homogeneous casting solution；Then to being slowly added to methyl tertiary butyl ether(MTBE) in casting solution, and continue stirring mixing
3h, on aluminium sheet, overnight evaporation solvent, obtains polymer film, in order to further at room temperature for the homogeneous phase solution hand teeming for obtaining
The acetone and water of residual are removed, polymer film is vacuum dried 5h at 50 DEG C
Obtained polymer film is immersed in 1M LiPF6EC and DEC mixed solvent in (EC/DEC volume ratio=1:1)
30 minutes, obtain gel polymer electrolyte.
Fig. 1 is PMMA derivatives1H nmr spectrums, in verifying the polymer of synthesis by nuclear magnetic resonance spectroscopy
Contain trimethoxy silane.In Fig. 1, different peak structures has indicated corresponding proton, positioned at the peak of 3.9 and 1.2ppm
OCH is corresponded to respectively2With CH2Si, shows to contain trimethoxy silane in the PMMA derivatives synthesized by free radical polymerisation process.
Fig. 2 and Fig. 3 are respectively thermogravimetric analysis (TGA) and the means of differential scanning calorimetry of the PMMA of trimethoxy silane substitution
(DSC) result curve.The heat endurance of the PMMA that trimethoxy silane replaces can be measured by TGA and DSC and vitrifying turns
Temperature.As can be drawn from Figure 2, the PMMA of trimethoxy silane substitution does not occur significantly when temperature is up to 230 DEG C
Weight loss, shows that the PMMA of the trimethoxy silane substitution when temperature is less than 230 DEG C is highly stable to heat.Can be with from Fig. 3
Draw, about 100 DEG C of the glass transition temperature of the PMMA of trimethoxy silane substitution.
Fig. 4 is SEM (SEM) figure for the polymer film that embodiment 1 is provided.It can be seen that this hair
The polymer film of bright offer has mandruka structure, and aperture very little（Less than 2 microns）, hole is evenly distributed.
The electrochemical stability window of the gel electrolyte that embodiment 1 is provided is detected by Linear Circulation voltammetry.Fig. 5 is
The linear scan cyclic voltammetry curve of lithium metal/gel polymer electrolyte/stainless steel, sweep speed is 5mV/s.In 4.8V
(vs.Li/Li+) place observes that electric current continues to increase, and increases along with voltage, this phenomenon shows electrolyte when less than 4.8V
Electrochemical decomposition will not occur, the polymer film that the present invention is provided has the up to electrochemical stability window of 4.8V.
Fig. 6 is the AC impedance figure of stainless steel/gel polymer electrolyte/stainless steel battery at room temperature, the gel for measuring
The ionic conductivity of polymer dielectric is 4.7 × 10-3S/cm, it is good that ionic conductivity so high shows that polymer film has
Electrolyte absorbent properties.
Comparative example 1
By mechanical agitation and ultrasonication, by Kynoar-hexafluoropropylene copolymer (PVDF-HFP) and poly- first
(PMMA, mean molecule quantity is 350000) to compare 3 according to weight to base methyl acrylate:2 mix in acetone, slow after being well mixed
Deionized water is added, and continues stirring mixing 3h, the homogeneous phase solution hand teeming for obtaining overnight evaporates molten on aluminium sheet, at room temperature
Agent, obtains polymer film, and polymer film then is vacuum dried into 5h at 50 DEG C, to remove the acetone and water of residual, finally obtains
Obtain the polymer film PVDF-HFP/PMMA that thickness is about 80 μm.
Polymer film is immersed into liquid electrolyte, double fluoroform sulphonyl of the liquid electrolyte comprising 1.0M in glove box
The tetraethyleneglycol dimethyl ether solution (Aldrich, purity 99%) of imine lithium (LiTFSI), obtains gel polymer electrolyte.Liquid
Electrolyte absorption rate passes through formula (W2-W1)×100/W1Calculate and, wherein, W1And W2Respectively before and after absorption liquid electrolyte
Polymer film weight.
Fig. 7 is the SEM figures of the PVDF-HFP/PMMA polymer films that comparative example 1 is provided.It can be seen that PVDF-
HFP/PMMA polymer films are similarly loose structure, and the diameter in hole is from 0.1 to 10 microns.After being immersed in liquid electrolyte, gather
Content liquid in compound film is 72wt%.
Fig. 8 is the TGA curves of PVDF-HFP/PMMA polymer films that are dry and absorbing liquid electrolyte.From figure
It can be seen that：The PVDF-HFP/PMMA polymer films for absorbing liquid electrolyte do not occur substantially when temperature is more than 110 DEG C
Weight loss.
Fig. 9 is that the ionic conductance of the PVDF-HFP/PMMA polymer films for absorbing liquid electrolyte is bent with the relation of temperature
Line.The ionic conductivity of the gel polymer electrolyte that comparative example 1 is provided is 3.37mS/cm at room temperature, compared with embodiment 1,
The ionic conductivity of the gel electrolyte containing PVDF-HFP/PMMA polymer films is less than and contains PVDF-HFP/PMMA derivatives
The gel electrolyte of polymer film, i.e., the ionic conductance of the gel electrolyte containing PVDF-HFP/PMMA derivative polymer films
Rate is substantially improved.
The electrochemical stability window of the gel electrolyte that comparative example 1 is provided is detected by Linear Circulation voltammetry.Figure 10
It is the linear scan cyclic voltammetry curve of lithium metal/gel electrolyte/stainless steel, sweep speed is 0.1mV/s.Potential is to anode
During scanning, observe that electric current flies up in 4.5V or so, this phenomenon can be attributed in inert electrode interface electrolyte hair
Solution estranged, this phenomenon shows that electrolyte will not occur electrochemical decomposition when less than 4.5V.Compared with embodiment 1, comparative example 1
The voltage stability window of the gel polymer electrolyte of offer is less than the gel polymer electrolyte that embodiment 1 is provided, explanation
PMMA is carried out into function dough, introducing trimethoxy silane can make the voltage stabilization of gel polymer electrolyte of final acquisition
Window increases.
Embodiment 2
The chemical property of PVDF-HFP/PMMA derivative gel polymer dielectrics is studied in assembled battery.
By positive electrode active materials LiCoO2, binding agent PVDF and conductive agent super-P carbon blacks compare 85 according to weight:10:5
Anode sizing agent is mixed to prepare in NMP, anode sizing agent is coated in positive pole is obtained on graphite foil collector；Negative pole is lithium metal；Will
Polymer film PVDF-HFP/PMMA derivatives are immersed in 1MLiPF6EC and DEC mixed solvent in (EC/DEC=1:1V)30
Minute, obtain gel polymer electrolyte.
By the battery in embodiment 2 with 0.2C constant current charge-discharges, Figure 11 is the pass of the charge/discharge capacity with voltage of battery
It is curve, Figure 12 is the relation curve of discharge capacity of the cell and coulombic efficiency to cycle-index.It can be seen that battery is first
Discharge capacity can still reach 130mAh/g after secondary discharge capacity is 140mAh/g, and battery charging and discharging circulates 100 times.
Embodiment 3
In embodiment 3, positive electrode active materials select sulfenyl composite, specifically, comparing 4 according to weight:1 mixing elemental sulfur
With polyacrylonitrile (PAN), and 3 hours prepared S/PAN composites are heat-treated at 300 DEG C under argon gas protection in the tube furnace.Electricity
Remaining composition of pond and preparation method are with embodiment 2.
Figure 13 is the battery of offer in embodiment 3 with 0.2C discharge and recharges, the relation song between cell voltage and discharge capacity
Line, the series platform observed in voltage curve correspond to the different vulcanization intermediate product produced in cell process.It is based on
The content of sulphur in positive active material, battery initial discharge capacity is 1400mAh/g, circulates the discharge capacity after 2 times and 100 times
Respectively 1070 and 930mAh/g.
Comparative example 2
In comparative example 2, polymer film PVDF-HFP is immersed in 1M LiPF6EC and DEC mixed solvent in (EC/
DEC volume ratio=1:1) 30 minutes, gel polymer electrolyte is obtained.Remaining composition of battery and preparation method are with embodiment 3.
Figure 14 is the discharge capacity of the cell that embodiment 3 is provided and coulombic efficiency to cycle-index relation curve and comparative example
The discharge capacity of 2 batteries for providing is to cycle-index relation curve.It can be seen that battery is relative to right in embodiment 3
Battery has initial discharge capacity and more preferable capability retention higher in ratio 2.The efficiency of battery about 100% in embodiment 3
Show that it has circulation reappearance well.This result shows the battery containing polymer film PVDF-HFP/PMMA derivatives
Cycle performance and capacity compared to the battery containing polymer film PVDF-HFP are all significantly improved.
Comparative example 3
In comparative example 3, electrolyte is the 1M LiPF of liquid6EC and DEC mixed solution (EC/DEC volume ratio=1:
1).Remaining composition of battery and preparation method are with embodiment 3.
Figure 15 is the relation curve of charge/discharge capacity and coulombic efficiency to cycle-index of battery in comparative example 3.From figure
It can be seen that, although the discharge capacity first of battery in comparative example 3（1600mAh/g）Put first higher than battery in embodiment 3
Capacitance（1400mAh/g）, but its cycle performance is much poorer than battery in embodiment 3, and the capacity of battery is only after circulation 100 times
It is 200mAh/g, only the 15% of initial capacity, mainly due to polysulfide, the quick electrochemistry in liquid electrolyte is molten for this
Solution.This result shows the gel polymer electrolyte battery containing polymer film PVDF-HFP/PMMA derivatives compared to not
The cycle performance and capacity of the liquid state electrolyte battery containing polymer film are all significantly improved.
Figure 16 be embodiment 3, comparative example 2 and in comparative example 3 battery AC impedance figure.As illustrated, electricity in embodiment 3
The ohmage in pond is smaller than the ohmage of battery in comparative example 2, although showing that polymer film PVDF-HFP/PMMA derivatives have
Smaller hole, but its pore size distribution is evenly, and the connectedness in hole is more preferably so more beneficial for the migration of lithium ion.
Comparative example 4
Assembling button cell studies the chemical property of PVDF-HFP/PMMA gel polymer electrolytes.
Battery anode active material is sulfenyl composite S/KB, specifically, by elemental sulfur（S）It is dissolved in tetrahydrofuran
In, then it is added thereto to superconductive carbon black（KB）, the weight ratio of wherein S and KB is 2:1；Then it is said mixture ball milling 2 is small
When, rotating speed is 400rpm, then mixture is dried into 6 hours to remove solvent at 60 DEG C of vacuum drying chamber；Then protected in argon gas
Said mixture is heat-treated in the tube furnace of shield, is first heated 5 hours at 150 DEG C, S is adsorbed to the hole of KB
In, it is further continued for being warming up to 300 DEG C, it is heat-treated 3 hours, S of the absorption on KB surfaces is volatilized, finally give S/KB composites.
Specifically positive pole preparation process is：S/KB, conductive agent acetylene black, binding agent PVDF are compared 8 according to weight:1:1 mixing,
(anode sizing agent for obtaining is laid in a diameter of 1cm circular shaped foams for NMP, purity >=99.5%) to be dispersed in N- methyl-pyrrolidons
On nickel collector, then dried 12 hours in vacuum drying oven at 60 DEG C.In order that having between positive active material and collector
Good contact, by positive pole roll-in under roll squeezer.By accurate weighing, compacting and control make the weight of the positive pole of preparation and
Thickness is about the same；Negative pole contains lithium metal；Electrolyte is gel polymer electrolyte, specifically, by polymer film PVDF-
HFP/PMMA immerses liquid electrolyte, double trifluoromethanesulfonimide lithiums of the liquid electrolyte comprising 1.0M in glove box
(LiTFSI) tetraethyleneglycol dimethyl ether solution.
Figure 17 is the battery constant current charging-discharging curve that comparative example 4 is provided, it can be seen that battery discharge capacity first
Reach 753.8mAh/g, the discharge capacity after circulating battery 30 times is 600mAh/g.The battery provided in embodiment 3 holds in electric discharge
The battery provided in comparative example 4 will be better than in amount and cycle performance, this result shows to contain polymer film PVDF-HFP/
The performance of the battery of PMMA derivatives will be substantially better than the battery containing polymer film PVDF-HFP/PMMA.
Comparative example 5
In comparative example 5, electrolyte is liquid electrolyte, double trifluoromethanesulfonimide lithiums of the liquid electrolyte comprising 1.0M
(LiTFSI) tetraethyleneglycol dimethyl ether solution.Barrier film is capillary polypropylene, and remaining battery composition is identical with comparative example 4.
Constant current test is carried out to the battery for assembling by multi-channel battery test instrument, voltage range is 1-3V (Li+/ Li),
Current density is 100mA/g, and the weight based on positive pole S calculates the electric current and specific capacity for applying.
Figure 18 is the relation curve of the capability retention with cycle-index of the battery that comparative example 4 and comparative example 5 are provided.Contrast
Capacity is kept relative to initial capacity more than 80% after circulating battery 40 times in example 4, in comparative example 5 discharge capacity of battery with
Cycle-index increases sharp-decay.
Figure 19 is the relation curve of the coulombic efficiency with cycle-index of the battery that comparative example 4 and comparative example 5 are provided.Comparative example
Coulombic efficiency of the battery after charge and discharge cycles 40 times is about 85% in 4, and battery is after charge and discharge cycles 40 times in comparative example 5
Coulombic efficiency is about 72%.
Comparative example 5 is compared with embodiment 2,3, illustrating the polymer film of present invention offer can effectively suppress to contain sulphur
Shuttle effect in the battery of base anode material, the polymer film being located in battery between positive pole and negative pole is anti-as physical barriers
Only soluble many lithium sulfide migrations, there is provided the utilization rate of sulphur.Therefore, the invertibity of positive pole reaction is improved, coulombic efficiency is produced
Active influence.
Although inventor has done elaboration in greater detail and has enumerated to technical scheme, it will be appreciated that for
For those skilled in the art, above-described embodiment is modified and/or flexible or be obvious using equivalent alternative solution
, can not all depart from the essence of spirit of the present invention, the term occurred in the present invention be used for the elaboration of technical solution of the present invention and
Understand, can not be construed as limiting the invention.
Claims (11)
1. a kind of polymer film, the copolymer at least including Kynoar and hexafluoropropene, it is characterised in that：The polymer
Film also includes polymethyl methacrylate derivative, and the polymethyl methacrylate derivative replaces including trimethoxy silane
Polymethyl methacrylate, the polymethyl methacrylate derivative account for the polymer film specific gravity range be 5-
25%.
2. polymer film according to claim 1, it is characterised in that：The polymer film has porous spongy structure,
The aperture size of the polymer film is micron order or submicron order.
3. polymer film according to claim 1, it is characterised in that：The porosity ranges of the polymer film are 20-
90%.
4. a kind of preparation method of polymer film, it is characterised in that：The preparation method comprises the following steps：
The copolymer of Kynoar and hexafluoropropene and polymethyl methacrylate derivative are dissolved in a solvent, machinery is stirred
Ultrasonically treated, the homogeneous casting solution of formation is carried out after mixing；
To non-solvent, mechanical agitation is added in casting solution until obtaining homogeneous phase solution, homogeneous phase solution of casting treats solvent and non-solvent
After evaporation, polymer film is obtained；
Polymer film is dried treatment；
The polymethyl methacrylate derivative includes the polymethyl methacrylate of trimethoxy silane substitution, the poly- first
The specific gravity range that base methyl acrylate derivate accounts for the polymer film is 5-25%.
5. preparation method according to claim 4, it is characterised in that：Prepare the polymethyl methacrylate derivative bag
Include following steps：
At 50-70 DEG C of temperature range, by free based method, using azodiisobutyronitrile as thermal initiator, by methyl-prop
E pioic acid methyl ester and γ-methacryloxypropyl trimethoxy silane polymerization generation polymethyl methacrylate derivative.
6. preparation method according to claim 4, it is characterised in that：The solvent includes acetone.
7. preparation method according to claim 4, it is characterised in that：The non-solvent includes water, ethanol or methyl- tert fourth
One kind in base ether.
8. preparation method according to claim 4, it is characterised in that：The dried process is to carry out under vacuum,
The temperature range of the dried process is 50-80 DEG C, and the time range of dried process is 5-12h.
9. a kind of electrolyte, it is characterised in that：The electrolyte is included such as polymer any one of in claim 1-3
Film.
10. a kind of battery, including positive pole, negative pole and the electrolyte between positive pole and negative pole, it is characterised in that：The electricity
Solution matter is included such as polymer film any one of in claim 1-3.
A kind of 11. batteries, including positive pole, negative pole and the electrolyte between positive pole and negative pole, it is characterised in that：It is described just
Best includes participating in less the positive electrode active materials of electrochemical reaction, and the positive electrode active materials contain sulfenyl material, the electrolysis
Matter is included such as polymer film any one of in claim 1-3.
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| CN104088155B (en) * | 2014-06-25 | 2016-05-04 | 江苏华东锂电技术研究院有限公司 | Composite diaphragm and preparation method thereof, and lithium ion battery |
| CN105713198B (en) * | 2016-05-04 | 2018-09-28 | 华东理工常熟研究院有限公司 | Polyimides, lithium ion battery and its preparation method and application |
| CN105870493A (en) * | 2016-05-12 | 2016-08-17 | 深圳市沃特玛电池有限公司 | Lithium-sulfur battery, lithium-sulfur battery intermediate and preparation method thereof |
| CN107474270B (en) * | 2016-06-07 | 2021-01-12 | 上海恩捷新材料科技有限公司 | Preparation method of polymer electrolyte membrane |
| CN107492681A (en) * | 2017-08-09 | 2017-12-19 | 上海纳晓能源科技有限公司 | Solid electrolyte film and preparation method thereof |
| CN107959049B (en) * | 2017-11-23 | 2021-01-29 | 南开大学 | Preparation method of gel electrolyte, gel electrolyte and lithium ion battery |
| JP6959885B2 (en) * | 2018-03-14 | 2021-11-05 | 株式会社クレハ | Polymer gel electrolyte and non-aqueous electrolyte rechargeable batteries for non-aqueous electrolyte rechargeable batteries |
| CN108550908A (en) * | 2018-06-08 | 2018-09-18 | 东莞市杉杉电池材料有限公司 | A kind of lithium ion battery polymer electrolyte film and preparation method thereof |
| CN109616697A (en) * | 2018-11-01 | 2019-04-12 | 深圳清华大学研究院 | Magnesium ion battery polymer dielectric film and preparation method thereof |
| CN110483924B (en) * | 2019-08-21 | 2021-06-15 | 陕西科技大学 | Super-hydrophobic self-cleaning radiation cooling film and preparation method thereof |
| CN110943258A (en) * | 2019-12-16 | 2020-03-31 | 电子科技大学 | PVDF-HFP composite lignocellulose gel polymer electrolyte membrane and preparation method thereof |
| CN111342123B (en) * | 2020-03-09 | 2023-06-13 | 中国科学院青岛生物能源与过程研究所 | Selectively-infiltrated polymer electrolyte, and preparation and application thereof |
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