CN111403804A - Polymer-based composite solid electrolyte film and preparation method thereof - Google Patents
Polymer-based composite solid electrolyte film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polymer-based composite solid electrolyte film using magnetic composite fiber as filler and a preparation method thereof, and the polymer-based composite solid electrolyte film comprises the following components: a magnetic composite fiber; and a polymer matrix in which lithium salt is dissolved, wherein the volume ratio of the magnetic composite fibers is 0.5-2%, the volume ratio of the polymer is 99.5-98%, and the magnetic composite fibers are vertically oriented in the polymer matrix. The method comprises the following steps: 1) preparing the precursor sol into the magnetic composite fiber by an electrostatic spinning method and a calcining process; 2) the polymer matrix dissolved with lithium salt and the magnetic composite fiber are compounded again to form a film, and a magnetic field is introduced for orientation regulation. The process can control the distribution and orientation of the filler in the composite film, thereby improving the mechanical and electrical properties of the composite film by regulating and controlling the distribution structure of the filler and finally improving the room-temperature ionic conductivity of the solid electrolyte film.
Description
Technical Field
The invention belongs to the technical field of solid electrolyte material preparation, and particularly relates to a polymer-based composite solid electrolyte film adopting magnetic composite fibers as a filler and a preparation method thereof.
Background
As an important electrochemical energy storage device, a lithium battery has high energy density, low self-discharge effect and high charging and discharging characteristics, so that the lithium battery is widely applied to portable electronic devices such as mobile phones and notebook computers, and occupies a large share in electric vehicles. In the field of energy storage device materials, with the development of electronic equipment in recent years, widely used energy storage devices are developed towards high energy storage, miniaturization and environmental protection. The electrolyte material of the traditional lithium ion battery consists of an organic solvent dissolved with lithium salt, has the dangers of electrolyte leakage, combustion and even explosion, has high packaging requirements on the battery, and has the problems of easy generation of lithium dendrite, unstable electrolyte, easy decomposition and the like in the using process. On the contrary, the solid electrolyte does not contain liquid components, so that the dangers of electrolyte combustion, explosion and the like can be effectively avoided, and the volume of the whole battery can be compressed to be small due to the fact that the solid electrolyte does not contain liquid components, so that the energy density of the battery is improved; however, the solid electrolyte has poor contact with the electrodes, resulting in large interfacial contact resistance, resulting in low room temperature ionic conductivity. The polymer material is widely applied to solid electrolyte materials due to the advantages of easy processing, good flexibility, light weight, good compatibility with electrodes, capability of being made into large-area films and the like. The polymer material is selected from the group consisting of: light weight, easy processing, low cost, good mechanical property, low glass transition temperature and the like. The polymer solid electrolyte has lower contact resistance between electrodes and better thermodynamic property, but the room-temperature ionic conductivity of the polymer solid electrolyte is lower, and the mechanical property of the polymer solid electrolyte is still to be improved so as to inhibit the problem of lithium dendrite and prevent the occurrence of electrolyte membrane rupture and anode and cathode short circuit caused by collision in the use process of a battery. Research shows that the addition of a certain amount of small-sized inorganic ceramic filler can reduce the crystallinity of the polymer and promote the motion of polymer chain segments, and certain groups of the inorganic ceramic filler possibly have interaction with the polymer matrix and lithium salt, and the interaction is favorable for the dissociation of the lithium salt and the inhibition of the recrystallization kinetic process of the polymer, so that the lithium ion carrier concentration and the motion capability of amorphous chain segments of the polymer are increased, and the room-temperature ionic conductivity is improved.
At present, a great deal of progress has been made in the research work of polymer matrix composite solid electrolyte materials, and the work is mostly from polymer matrix,The inorganic ceramic filler and the interaction of the inorganic ceramic filler and the inorganic ceramic filler are considered to select a polymer matrix with lower glass transition temperature (Tg) and lower crystallinity at room temperature, select a fast ion conductor filler capable of transmitting lithium ions, carry out surface modification by means of atomic deposition (A L D) and the like, design favorable interaction and accelerate lithium ion conduction6.75La3Zr1.75Ta0.25O12) The research finds that L a atom in LL ZTO can be matched with N atom and C ═ O functional group in solvent molecules, such as nitrogen-nitrogen Dimethylformamide (DMF), so that the N atom is in an electron-rich state, the Lewis base property is shown, the dehydrofluorination behavior of a PVDF chain is induced, and the interaction among PVDF, lithium salt and LL ZTO chain segments can be activated by the partially modified PVDF chain segment, so that the ionic conductivity, the mechanical property and the thermal stability of the composite electrolyte are improved3) The effect of the shape of the nanofiller (nanofibers, nanotubes, nanoplatelets) on the performance of polyethylene oxide (PEO) -based electrolytes, studies have found: the BaTiO3 nano filler has better affinity with a PEO matrix due to the organic functional groups on the surface, so that the BaTiO3 nano filler can be uniformly distributed in an electrolyte film; adding BaTiO3When the nano-sheet is used, the main XRD diffraction peak intensity of the polymer matrix PEO is lowest, the DSC melting temperature Tm is lowest, namely BaTiO is added3The influence of the reduction effect of the crystallinity of the polymer matrix of the nanosheet is greatest; investigation of the shift of the C-O-C peak in the Infrared Spectroscopy (FTIR) found BaTiO3the-OH and-OR groups on the surface of the nano filler can be combined with O atoms in a PEO chain segment of a polymer matrix and L i in lithium salt+Interact to weaken L i+The complexation between O atoms promotes L i+Transport along the PEO segment; BaTiO 23The nano filler is subjected to spontaneous polarization and surface charge induction to form an interface, and the formed interface has high dielectric constant and various defects, and is favorable for L i+In which BaTiO is3The nanosheets having the greatest ratioThe surface area is most favorable for the formation of the interface, so that the ionic conductivity is improved most obviously, and BaTiO3The room-temperature ionic conductivity of the nanosheet-PEO-L iTFSI electrolyte reaches 1.8 × 10-5S/cm。
The researchers found that the room temperature ionic conductivity of the electrolyte can be improved by designing the size and shape of the interface between the polymer matrix and the inorganic ceramic filler L iu et al studied the effect of ceramic nanofibers without alignment orientation on the ionic conductivity of the composite polymer electrolyte, found that when the ceramic nanofiber filler in the polymer matrix forms an angle of 0 DEG with the normal direction of the electrode surface, i.e., L i+The shortest rapid conduction path along the fiber-polymer interface is compared to the pure polymer electrolyte without filler (4.31 × 10)-7S/cm), random arrangement of fibrous fillers (7.82 × 10)-6S/cm), the ionic conductivity of the composite polymer electrolyte with good arrangement and shortest rapid conduction path is greatly improved, and the ionic conductivity at room temperature reaches 5.02 × 10-5S/cm, and the corresponding mechanical property and the cycling stability are also improved. Zhang et Al, which studied the effect of continuous vertically aligned nano-scale ceramic-polymer interfaces on the ionic conductivity of composite solid polymer electrolytes, first designed alumina (Al) with different nanotube sizes2O3) Ceramic disk, then laminating polyethylene oxide-lithium bistrifluoromethanesulfonimide (PEO-L iTFSI) solid polymer electrolyte membrane at 65 ℃ under Al2O3Finally, the laminated film and the ceramic disk are put into a 215 ℃ vacuum furnace to ensure that the electrolyte is fully melted and permeated into Al2O3A composite solid polymer electrolyte in the nano-tube with vertical and continuous nano-size interface, and a strong Lewis acid-AlF is deposited on the nano-tube by adopting an atomic deposition technology (A L D)3Further studies have found L i for pure polymer electrolytes (PEO-L iTFSI)+The transmission can be realized only by ether oxygen assisted jumping or polymer chain segment movement, and the composite solid polymer electrolyte (PEO-L iTFSI-Al)2O3) There are two kinds of L i+Conduction pathways, the first being L i induced by ether oxygen or polymer segmental motion+Transport, the second is along the ceramic-polymer interface. Finally, Al of the nano-tube with reasonable smaller size is selected2O3Ceramic chip, and surface modification of nano-tube through A L D, and selecting PEG with smaller molecular weight as polymer matrix to obtain room temperature ionic conductivity of 5.82 × 10-4S/cm of composite solid polymer electrolyte.
Disclosure of Invention
The present invention is directed to the above-mentioned prior art, and an object of the present invention is to provide a polymer-based composite solid electrolyte thin film and a method for preparing the same, which can shorten a lithium ion transmission path, achieve rapid transmission of lithium ions, and improve room temperature ionic conductivity of a solid electrolyte.
The technical scheme adopted by the invention for solving the technical problems is as follows: a polymer-based composite solid electrolyte membrane having a composition comprising: a magnetic composite fiber; and a polymer matrix in which lithium salt is dissolved, wherein the volume ratio of the magnetic composite fibers is 0.5-2%, the volume ratio of the polymer is 99.5-98%, and the magnetic composite fibers are vertically oriented in the polymer matrix.
According to the scheme, the magnetic composite fiber is composed of a 1-dimensional fiber substrate and 0-dimensional magnetic oxide particles filled in the fiber, the fiber substrate is made of lanthanum lithium titanate, the 0-dimensional magnetic oxide particles are ferroferric oxide nano particles, and the lithium salt is bis (trifluoromethane) sulfonyl imide lithium.
According to the scheme, the diameter of the magnetic composite fiber is 200 nm-1 μm, the length of the magnetic composite fiber is 1 μm-20 μm, and the diameter of the filled 0-dimensional magnetic oxide particles is 20 nm.
According to the scheme, the polymer matrix is made of one or more materials of polyvinylidene fluoride (PVDF), polyethylene oxide (PEO) and Polyacrylonitrile (PAN).
According to the scheme, the thickness of the composite solid electrolyte membrane is 20-60 mu m.
According to the scheme, the volume ratio of the filled 0-dimensional magnetic oxide particles to the 1-dimensional fiber matrix in the magnetic composite fiber is 1: 2.
The preparation method of the polymer-based composite solid electrolyte film comprises the following steps:
1) preparing the precursor sol into the magnetic composite fiber by an electrostatic spinning method and a calcining process;
2) the polymer matrix dissolved with lithium salt and the magnetic composite fiber are compounded again to form a film, and a magnetic field is introduced for orientation regulation.
According to the scheme, the polymer matrix and the magnetic composite fiber are compounded again to form the membrane, and the membrane is prepared by a solution casting method and a method of introducing an external magnetic field vertical to the upper surface and the lower surface of an electrolyte membrane in the solvent drying process.
According TO the scheme, the precursor sol is prepared by the following method that lithium nitrate and lanthanum nitrate hexahydrate are used as L i and L a sources, the materials are weighed according TO the molar ratio of L i excessive by 10%, the materials are dissolved in DMF and acetic acid, tetrabutyl titanate is added as a Ti source after the materials are completely dissolved, LL TO stock solution is obtained after the materials are completely stirred, then a proper amount of ferroferric oxide nano particles are added, the materials are uniformly stirred, finally polyvinyl pyrrolidone is added, and the spinning precursor sol is obtained after the materials are completely stirred.
In the composite solid polymer electrolyte, the lithium ion transmission path mainly comprises ① passing through a polymer phase, ② passing through a ceramic phase and ③ passing through a polymer/ceramic interface, and because of the excellent electrochemical property of the ceramic phase, lithium ions tend to pass through the ceramic phase and the polymer/ceramic interface, the lithium ion rapid transmission path can be shortened by designing the vertical orientation arrangement of the ceramic filler in a polymer matrix, and the further improvement of the ion conductivity of the composite solid polymer electrolyte is realized.
The invention firstly prepares the magnetic composite fiber, and compounds the processed magnetic composite fiber with the polymer matrix, and the magnetic nano composite fiber is vertically arranged in the polymer matrix under the auxiliary action of an external magnetic field, thereby shortening the transmission path of lithium ions, realizing the rapid transmission of lithium ions, improving the room temperature ionic conductivity of the polymer matrix composite solid electrolyte, and simultaneously, because the ceramic filler is arranged along the outside direction of the electrolyte film surface, the mechanical property of the electrolyte film in the outside direction is further improved, which is beneficial to inhibiting the growth of lithium dendrite in the circulation process of the battery.
The invention has the following effective effects: (1) the preparation process is simpler, and the thickness of the film can be effectively controlled; (2) the general composite solid electrolyte film preparation process can only prepare composite films with randomly dispersed fillers, and the process can control the distribution and orientation of the fillers in the composite films, so that the mechanical and electrical properties of the composite films can be improved by regulating and controlling the distribution structure of the fillers, and the room temperature ionic conductivity of the solid electrolyte films is finally improved.
Drawings
FIG. 1 is a scanning electron microscope picture before calcination of the composite nanofiber prepared by the electrospinning method in example 1;
FIG. 2 is a scanning electron microscope picture and an EDS picture of the composite nanofiber prepared by the electrospinning method in example 1 after calcination;
FIG. 3 is a scanning electron microscope image of the cross section of the solid electrolyte thin film with randomly distributed fibers and vertically oriented fibers prepared by casting after mixing PVDF and composite fibers with different contents in example 2, example 3, example 4 and example 5;
FIG. 4 is an AC impedance spectrum of a composite solid electrolyte having fiber volume fractions of 0 vol%, 0.5 vol%, 1 vol%, and 2 vol% in example 2, example 3, example 4, and example 5, respectively;
fig. 5 is a graph showing changes in room temperature ionic conductivity with respect to the fiber content of the solid electrolyte in which the fiber volume fractions of example 2, example 3, example 4, and example 5 were 0 vol%, 0.5 vol%, 1 vol%, and 2 vol%, respectively, in the random distribution and the vertical orientation distribution of the fibers.
FIG. 6 is a graph showing cell performance at room temperature of solid electrolytes in which the fiber volume fractions are 0 vol%, 0.5 vol%, 1 vol%, and 2 vol%, respectively, in examples 2, 3, 4, and 5, and in which the fibers are randomly distributed and vertically aligned.
Detailed Description
With gamma-Fe2O3The preparation method of the composite fiber and the polymer-based solid electrolyte film comprises the following steps of taking the nano-particles/LL TO nano-composite fiber and PVDF as polymer matrixes and L iTFSI as lithium salt as examples:
(1) preparing precursor sol for composite fiber spinning with gamma-Fe2O3nanoparticle/L i0.33La0.557TiO3Firstly, measuring a certain amount of lithium nitrate and lanthanum nitrate hexahydrate, wherein the mass of lithium is 10 wt% more, the lithium is used for compensating the lithium loss in the subsequent high-temperature sintering process, the remaining L i and L a with the molar ratio of 0.33: 0.557 are dissolved in a certain amount of DMF and acetic acid, adding a certain amount of tetrabutyl titanate after the lithium is completely dissolved, wherein the molar ratio of L a TO Ti is 0.557:1, adding a certain amount of acetylacetone until the solution is uniformly stirred TO obtain LL TO stock solution, then adding an equivalent amount of DMF into a certain amount of the stock solution, and weighing a proper amount of Fe3O4And (3) crushing cells of the nano particles, adding the mixed solution obtained in the previous step, uniformly stirring, finally adding polyvinylpyrrolidone (PVP, M is 1300000), and stirring to a uniform and stable state to form the spinning precursor sol.
(2) And transferring the spinning precursor sol into an injector, performing electrostatic spinning at the voltage of 1kV/cm, and obtaining a precursor of the composite fiber in a roller receiving mode.
(3) And (3) sintering the composite fiber precursor at the temperature rise rate of 5 ℃/min for 2h at 850 ℃ to obtain the composite fiber.
(4) The magnetic composite fiber is treated by means of ultrasonic treatment, drying and the like, added into completely dissolved PVDF and L iTFSI solution, uniformly stirred, prepared into a film with a certain thickness by a solution casting method, and introduced into an external magnetic field with proper magnetic field intensity vertical to the upper surface and the lower surface of an electrolyte film while being dried in vacuum at 80 ℃, so as to finally prepare the solid electrolyte film with the magnetic composite fiber filler in vertical orientation arrangement in a polymer matrix.
The invention is further illustrated by the following examples:
example 1:
weighing 1.045g of lithium nitrate and 5.47g of lanthanum nitrate hexahydrate, dissolving in 5ml of DMF and 2ml of acetic acid, stirring TO be in a uniform stable state, adding 10.419g of tetrabutyl titanate, continuously stirring TO be in a uniform stable state TO obtain LL TO stock solution, taking out 3ml of the prepared stock solution, adding 0.5g of Fe3O4Crushing nano particles in 3ml DMF at a power of 300W for 8h, adding 3ml LL TO stock solution taken out in the previous step, stirring for 30min uniformly, adding 0.5g PVP, stirring for 3h TO form stable sol, transferring the sol into a syringe for electrostatic spinning, performing electrostatic spinning under an electric field of 1kV/cm, changing the sol every 30min, and obtaining the shape of the electrostatic spun fiber by a roller collection mode, wherein the diameter of the fiber before calcination is about 1 mu m, and Fe is shown in a Scanning Electron Microscope (SEM) picture 13O4The nano particles are uniformly attached to the surface of the fiber; and then calcining the fiber at 800 ℃ for 2h at the heating rate of 5 ℃/min to obtain the final magnetic composite fiber. The morphology of the obtained magnetic composite fiber is as shown in a Scanning Electron Microscope (SEM) 2, the diameter of the calcined fiber is reduced to about 200nm, and the uniform distribution of magnetic particles on the surface of the fiber can be seen in an EDS energy spectrum.
Comparative example 2:
weighing 1g PVDF powder, 0.33g L iTFSI in a glove box, dissolving in 10ml DMF solvent, stirring thoroughly for 24h, solution-casting, drying at 80 deg.C for 24hObtaining PVDF/L iTFSI solid polymer electrolyte film, as shown in a in FIG. 30、a1It can be seen that the cross-section of the pure PVDF/L iTFSI solid polymer electrolyte membrane is denser, with no significant voids being generated, which facilitates the transport of lithium ions.
Example 3:
taking 0.05g of the magnetic composite fiber in the embodiment 1 to be placed in 50ml of ethanol, carrying out ultrasonic treatment for 2min under 40W power, then carrying out centrifugation and drying treatment to obtain a short magnetic composite fiber with the size of 1-20 mu m, measuring 3ml of DMF solvent, adding 0.014g of the composite fiber, carrying out ultrasonic treatment for 2min under 40W, then adding the short magnetic composite fiber into sol dissolved with PVDF and L iTFSI which are uniformly stirred in advance, stirring for 5h to a uniform and stable state, then carrying out tape casting on the mixed solution, drying for 24h at 80 ℃, carrying out normal drying on one part, introducing a parallel magnetic field with appropriate magnetic field intensity along the upper surface and the lower surface of an electrolyte film while drying the other part, and obtaining the composite solid electrolyte film with the volume fraction of 0.5 vol% and the random distribution orientation of the fiber and the vertical orientation arrangement of the fiber, as shown in b in figure 30、b1It can be seen that the fibrous filler in the composite electrolyte thin film oriented by the magnetic field apparently shows a vertical orientation alignment tendency (graph b)0Shown), the fiber filler obviously shows random distribution and has a tendency of parallel distribution along the surface in the composite electrolyte film which is not regulated by the magnetic field. (FIG. b)1Shown in
Example 4:
taking 0.05g of the composite fiber in the embodiment 1 into 50ml of ethanol, performing ultrasonic treatment for 2min under 40W power, obtaining short magnetic composite fiber with the size of 1-20 mu m through centrifugation and drying treatment, measuring 3ml of DMF solvent, adding 0.028g of the composite fiber, performing ultrasonic treatment for 2min under 40W, adding the short magnetic composite fiber into sol dissolved with PVDF and L iTFSI which are uniformly stirred in advance, stirring for 5h to be in a uniform and stable state, casting the mixed solution, drying for 24h at 80 ℃, normally drying one part, introducing a parallel magnetic field with proper magnetic field intensity along the upper surface and the lower surface of an electrolyte film into the other part while drying, and obtaining the composite solid electrolyte film with the volume fraction of 1 vol%, wherein the fibers are randomly distributed and oriented and the fibers are vertically oriented and arranged, as shown in c in figure 30、c1It can be seen that the fibrous filler in the composite electrolyte thin film oriented by the magnetic field apparently shows a vertical orientation alignment tendency (graph c)0Shown), the fiber filler obviously shows random distribution and has a tendency of parallel distribution along the surface in the composite electrolyte film which is not regulated by the magnetic field. (FIG. c)1Shown) at the same time, due to the increase of the content of the fibrous filler, the filler begins to agglomerate in the polymer matrix, which is not beneficial to the transmission of lithium ions.
Example 5:
taking 0.05g of the composite fiber in the embodiment 1 into 50ml of ethanol, performing ultrasonic treatment for 2min under 40W power, obtaining short magnetic composite fiber with the size of 1-20 mu m through centrifugation and drying treatment, measuring 3ml of DMF solvent, adding 0.056g of the composite fiber, performing ultrasonic treatment for 2min under 40W, adding the short magnetic composite fiber into sol dissolved with PVDF and L iTFSI which are uniformly stirred in advance, stirring for 5h to be in a uniform and stable state, casting the mixed solution, drying for 24h at 80 ℃, normally drying one part, introducing a parallel magnetic field with proper magnetic field intensity along the upper surface and the lower surface of an electrolyte film into the other part while drying, and obtaining the composite solid electrolyte film with the volume fraction of 2 vol%, wherein the fibers are randomly distributed and oriented and the fibers are vertically oriented, and the composite solid electrolyte film is characterized in that the fibers are vertically oriented and arranged, as shown in d in figure 30、 d1It can be seen that the fibrous filler in the composite electrolyte thin film subjected to magnetic field orientation clearly exhibits a tendency of homeotropic alignment (graph d)0Shown), the fiber filler obviously shows random distribution and has a tendency of parallel distribution along the surface in the composite electrolyte film which is not regulated by the magnetic field. (FIG. d)1Shown) and, due to the further increase of the content of the fibrous filler, the agglomeration phenomenon of the filler in the polymer matrix is severe, and the cross section of the electrolyte membrane begins to appear obvious holes.
Example 6:
a L iCoO solid state electrolyte membrane was assembled in a glove box from the pure PVDF/L iTFSI solid state polymer electrolyte membrane of example 2 and the composite solid state electrolyte membrane of example 4 in which the fibers having a filler content of 1 vol% were randomly distributed and oriented and the fibers were arranged in a vertical orientation2A solid state electrolyte membrane | L i cell, cycled 30 cycles at 0.1C rate,comparing the cycling performance of the three cells, as shown in FIG. 6, it can be seen that the cycling performance of the pure PVDF/L iTFSI solid polymer electrolyte cell is poor due to the low room temperature ionic conductivity, and the capacity after 30 cycles is determined by the first cycle of 119.8mAh g-1Attenuation was 38.0mAh g-1(see FIG. 6 a); the 1 vol% fiber randomly distributed and oriented composite solid electrolyte battery has obviously improved battery cycle performance due to the improvement of room temperature ionic conductivity, and the capacity after 30 circles is 113.9mAhg of the first circle-1Attenuation is 111.4mAh g-1However, the battery cycle is not stable due TO the redox reaction between LL TO and L i metal in the composite fiber (as shown in figure 6b), the cycle performance of the battery is obviously improved due TO the further improvement of room-temperature ionic conductivity of the composite solid electrolyte battery with 1 vol% of fiber out-of-plane distribution orientation, and the capacity after 30 circles is increased from 117.0mAh g of the first circle-1It became 119.5mAh g-1And because the contact area between the composite fiber and L i metal is smaller when the fiber is vertically oriented along the electrolyte membrane, a great deal of reaction between the fiber filler and L i metal is avoided, and the cycle performance of the battery is more stable and excellent (as shown in figure 6c)
Fig. 4 is an ac impedance spectrum of the electrolyte thin films prepared in examples 2, 3, 4, and 5, the bulk impedance of the electrolyte film can be obtained according to the ac impedance spectrum, and then the peak ion conductivity of each electrolyte thin film is calculated according to an ion conductivity calculation formula as shown in fig. 5, it can be found that, after the ceramic filler is added, the ion conductivity of the composite solid dielectric thin film is higher than that of a pure polymer electrolyte thin film, and in all components, the ion conductivity of the composite solid electrolyte thin film in which the fibers are vertically oriented and arranged is further improved, and is higher than that of a composite solid electrolyte thin film in which the fibers of the same component are randomly distributed.
Claims (9)
1. A polymer-based composite solid electrolyte membrane having a composition comprising: a magnetic composite fiber; and a polymer matrix in which lithium salt is dissolved, wherein the volume ratio of the magnetic composite fibers is 0.5-2%, the volume ratio of the polymer is 99.5-98%, and the magnetic composite fibers are vertically oriented in the polymer matrix.
2. The polymer-based composite solid electrolyte membrane according to claim 1, wherein the magnetic composite fiber is composed of a 1-dimensional fiber matrix and 0-dimensional magnetic oxide particles filled in the fiber, the fiber matrix is made of lanthanum lithium titanate, the 0-dimensional magnetic oxide particles are ferroferric oxide nanoparticles, and the lithium salt is lithium bistrifluoromethanesulfonylimide.
3. The polymer-based composite solid electrolyte membrane according to claim 2, characterized in that the magnetic composite fiber has a diameter of 200nm to 1 μm and a length of 1 μm to 20 μm, and the filled 0-dimensional magnetic oxide particle has a diameter of 20 nm.
4. The polymer-based composite solid electrolyte membrane according to claim 1, wherein the polymer matrix is made of one or more materials selected from polyvinylidene fluoride, polyethylene oxide, and polyacrylonitrile.
5. The polymer-matrix composite solid electrolyte membrane according to claim 1, characterized in that the thickness of said composite solid electrolyte membrane is 20 μm to 60 μm.
6. The polymer-based composite solid electrolyte membrane according to claim 2, characterized in that the magnetic composite fiber has a volume ratio of filled 0-dimensional magnetic oxide particles to 1-dimensional fiber matrix of 1: 2.
7. The method for producing a polymer-based composite solid electrolyte membrane according to claim 1, comprising the steps of:
1) preparing the precursor sol into the magnetic composite fiber by an electrostatic spinning method and a calcining process;
2) the polymer matrix dissolved with lithium salt and the magnetic composite fiber are compounded again to form a film, and a magnetic field is introduced for orientation regulation.
8. The method for producing a polymer-based composite solid electrolyte membrane according to claim 7, wherein the polymer matrix and the magnetic composite fiber are again compounded to form a membrane by a solution casting method and an external magnetic field is introduced perpendicularly to the upper and lower surfaces of the electrolyte membrane during solvent drying.
9. The preparation method of the polymer-based composite solid electrolyte film according TO claim 7 or 8, characterized in that the precursor sol is prepared by taking lithium nitrate and lanthanum nitrate hexahydrate as L i and L a sources, weighing according TO the molar ratio of L i excessive by 10%, dissolving in DMF and acetic acid, adding tetrabutyl titanate as a Ti source after complete dissolution, stirring completely TO obtain LL TO stock solution, then adding a proper amount of ferroferric oxide nanoparticles, stirring uniformly, finally adding polyvinylpyrrolidone, and stirring completely TO obtain spinning precursor sol.
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| CN111816916A (en) * | 2020-07-22 | 2020-10-23 | 珠海冠宇电池股份有限公司 | Composite solid electrolyte membrane, preparation method thereof and lithium ion battery |
| CN113140786A (en) * | 2021-03-15 | 2021-07-20 | 佛山仙湖实验室 | Solid electrolyte and preparation method and application thereof |
| CN113594539A (en) * | 2021-06-22 | 2021-11-02 | 上海电气集团股份有限公司 | Composite electrolyte with gradient structure, solid-state battery and preparation method and application of composite electrolyte |
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