CN113991174A - Organic-inorganic composite solid electrolyte membrane and preparation method and application thereof - Google Patents

Organic-inorganic composite solid electrolyte membrane and preparation method and application thereof Download PDF

Info

Publication number
CN113991174A
CN113991174A CN202111239414.6A CN202111239414A CN113991174A CN 113991174 A CN113991174 A CN 113991174A CN 202111239414 A CN202111239414 A CN 202111239414A CN 113991174 A CN113991174 A CN 113991174A
Authority
CN
China
Prior art keywords
solid electrolyte
electrolyte membrane
organic
zif
composite solid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111239414.6A
Other languages
Chinese (zh)
Other versions
CN113991174B (en
Inventor
刘艳侠
杨晓宇
杨宝玉
刘目浩
王爽
李德照
柴丰涛
高文超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhengzhou Institute of Emerging Industrial Technology
Original Assignee
Zhengzhou Institute of Emerging Industrial Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhengzhou Institute of Emerging Industrial Technology filed Critical Zhengzhou Institute of Emerging Industrial Technology
Priority to CN202111239414.6A priority Critical patent/CN113991174B/en
Publication of CN113991174A publication Critical patent/CN113991174A/en
Application granted granted Critical
Publication of CN113991174B publication Critical patent/CN113991174B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

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

Abstract

The invention discloses an organic-inorganic composite solid electrolyte membrane and a preparation method thereof, wherein the solid electrolyte membrane material mainly comprises PEO, LiTFSI and ZiF modified active inorganic filler, and the preparation method comprises the following steps: the ZiF material is synthesized on the surface of the active inorganic filler in situ through in-situ growth reaction, and the modified active inorganic filler powder is obtained through centrifugation, washing and drying; uniformly mixing the modified active inorganic filler powder with PEO and LiTFSI to form composite electrolyte membrane slurry; and pouring the composite electrolyte membrane slurry into a mould by adopting a solution casting method to prepare the organic-inorganic composite solid electrolyte membrane. The ionic conductivity of the prepared electrolyte membrane can reach 7 times of that of a PEO/LiTFSI electrolyte membrane, and the problem of low room-temperature ionic conductivity of the existing PEO-based solid electrolyte is effectively solved. The method has the advantages of simple process, high preparation yield and low cost, and is suitable for large-scale industrial production.

Description

Organic-inorganic composite solid electrolyte membrane and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to an organic-inorganic composite solid electrolyte membrane and a preparation method and application thereof.
Background
With the rapid development of electric vehicles, lithium metal batteries with high energy density are receiving more and more attention. However, in the conventional liquid electrolyte, the unstable deposition process of lithium metal and the growth of lithium dendrite may cause the short-circuit combustion and even explosion of the battery, which seriously hinders the development of the lithium metal battery. The solid electrolyte with good safety performance and no hidden danger of electrolyte leakage can fundamentally solve the safety problem of the lithium metal battery.
Solid electrolytes, which are the core of all-solid batteries, are the central focus of the entire solid battery development. Currently, solid electrolytes are mainly classified into inorganic solid electrolytes, polymer solid electrolytes, and organic-inorganic composite solid electrolytes. The organic-inorganic composite solid electrolyte has high mechanical strength and high ionic conductivity compared with a polymer solid electrolyte, and has enhanced flexibility and increased interface compatibility compared with an inorganic solid electrolyte, so that the organic-inorganic composite solid electrolyte is one of the most potential solid electrolyte systems. In a common organic polymer electrolyte system, a PEO-based polymer electrolyte has good flexibility and processability, but the high-molecular chains orderly arranged in polyethylene oxide have high crystallinity, so that the migration and transmission of lithium ions in a polymer matrix are seriously hindered, and the practical application of the PEO-based polymer electrolyte is limited.
Researchers slow down the ordered arrangement of the high molecular chain segments by adding the inorganic filler, reduce the crystallinity of the material and further improve the ionic conductivity of the material. Chinese patent CN202011297431.0 discloses a method for preparing a three-dimensional porous lithium lanthanum zirconium oxide and polyethylene oxide composite membrane, which uses a cotton filament sheet as a template to prepare the three-dimensional porous lithium lanthanum zirconium oxide, and forms a composite solid electrolyte membrane with polyethylene oxide. The lithium lanthanum zirconium oxide prepared by the method has a three-dimensional structure, can provide a rapid path for lithium ion movement so as to improve the ionic conductivity, and can improve the flexibility of the solid electrolyte and improve the contact between the solid electrolyte and an electrode after forming a composite electrolyte membrane with polyethylene oxide. Chinese patent CN202110461484.X discloses an ultrathin composite solid electrolyte membrane and a preparation method thereof, wherein oxide solid electrolyte ceramic nanoparticles modified by a binder are added into a polymer matrix, and the obtained thin-film composite solid electrolyte is easy to demould, small in thickness, uniform and compact in components, flat and smooth in surface and small in impedance. The invention obtains better results, but still has the problems of difficult size adjustment, further improvement of cycle stability and the like.
In view of this, the invention is particularly proposed.
Disclosure of Invention
Aiming at the problem of lower ionic conductivity of an organic-inorganic composite solid electrolyte membrane in the prior art, the invention provides a preparation method of the organic-inorganic composite solid electrolyte membrane, which comprises the steps of adding a modified active inorganic filler into a PEO-based polymer electrolyte, destroying the original highly ordered structure of a polymer material, reducing the crystallinity of the polymer material, improving the ionic conductivity of the electrolyte membrane, modifying the surface of the active inorganic filler by using ZiF material, and then having larger specific surface area, enhancing the interfacial compatibility between the inorganic material and the organic material PEO, and effectively reducing the interfacial internal resistance.
The content of the invention is realized by the following technical scheme:
an organic-inorganic composite solid electrolyte membrane is composed of PEO (polyethylene oxide), LiTFSI (lithium bis (trifluoromethanesulfonyl) imide) and ZiF modified active inorganic filler, and a membrane structure with a smooth surface and micropores is formed; the preparation method comprises the following steps:
(1) preparation ZiF of modified active inorganic Filler: adding active inorganic filler powder into a solution containing a surfactant, stirring uniformly, and adding a metal cation soluble compound to obtain a solution A. Then pouring the organic ligand solution (solution B) into the solution A, and stirring the solution A until the solution A is uniform. Then carrying out a series of treatments such as solid-liquid separation, washing, drying and the like to obtain modified active inorganic filler powder;
(2) preparing organic-inorganic composite solid electrolyte membrane slurry: uniformly mixing the modified active inorganic filler serving as a filling material with PEO, LiTFSI and other materials according to a certain mass ratio to form composite electrolyte membrane slurry;
(3) preparing an organic-inorganic composite solid electrolyte membrane: pouring the composite electrolyte membrane slurry into a polytetrafluoroethylene template by adopting a solution casting method, and obtaining the organic-inorganic composite solid electrolyte membrane after the solvent is completely volatilized.
Further, in the step (1), the active inorganic filler may be NASICON type solid electrolyte powder, phosphide type solid electrolyte powder, perovskite type solid electrolyte powder, lithium phosphorus oxynitride solid electrolyte powder (LiPON), and garnet type solid electrolyte powder; preferably, LLZO garnet-type solid electrolyte powder may be selected.
Further, in the step (1), the surfactant may be polyvinylpyrrolidone (PVP), cetyltrimethylammonium bromide (CTAB); preferably, polyvinylpyrrolidone (PVP) may be used as the surfactant.
Further, in the step (1), the solvent used for the solution a and the solution B may be methanol or N, N-Dimethylformamide (DMF), and the amount of the solvent used for the solution a and the solution B is the same. Preferably, methanol is optionally used as solvent.
Further, in the step (1), the metal cation soluble compound may be a compound containing cations such as cobalt, zinc, zirconium, etc.; preferably, one or more of cobalt nitrate, cobalt acetate and cobalt chloride can be selected; the molar ratio of the metal cation compound to the organic ligand is 1:1 to 1:10, and the organic ligand may be dimethylimidazole.
Further, in the step (1), the solution is stirred for 3-24 hours; the solid-liquid separation can adopt the modes of centrifugation, suction filtration and the like; washing for 3-5 times; the drying condition is drying at 60-80 deg.C for 6-24 h. Preferably, centrifugation can be used for solid-liquid separation, and the centrifugation rotation speed is 7000 and 10000 r/min.
Further, in the step (2), the amount ratio of the EO to the LiTFSI substances in the PEO is 5:1-15:1, and the ZiF modified active inorganic filler accounts for 1-50% of the total mass of the PEO and the LiTFSI.
Further, in the step (3), a solution casting method is adopted in a glove box with water and oxygen content less than 0.1ppm, the solution is poured into a polytetrafluoroethylene template, then the polytetrafluoroethylene template is kept stand in the glove box for 48 hours, then the polytetrafluoroethylene template is transferred to a vacuum drying box, the solvent is completely volatilized after drying is carried out for 12 hours at the temperature of 60 ℃, and the organic-inorganic composite solid electrolyte membrane is obtained after membrane uncovering.
The invention also provides a composite electrolyte membrane prepared based on the preparation method of the solid lithium ion composite solid electrolyte and application of the composite electrolyte membrane in a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
1. the modified active inorganic filler in the organic-inorganic composite solid electrolyte membrane provided by the invention has larger specific surface area and adjustable pore size, can limit the movement of larger anions, provides a quick and continuous channel for the transmission of lithium ions, and is beneficial to improving the transference number of the lithium ions. 2. By adding the modified active inorganic filler into the PEO-based polymer electrolyte, the original highly ordered structure of the PEO polymer is destroyed, the crystallinity of the PEO polymer is reduced, and the composite solid electrolyte membrane has higher ionic conductivity; 3. compared with an inorganic solid electrolyte, the composite electrolyte membrane has enhanced flexibility and reduced interface impedance with the anode and cathode pole pieces; 4. because of the modification effect of the ZiF material, the stability of the composite electrolyte membrane is enhanced, and the finally prepared composite solid electrolyte membrane has a wider electrochemical window.
Drawings
FIG. 1 is a transmission scanning electron micrograph of the LLZO @ ZiF-67 material obtained in example 1;
FIG. 2 is a scanning electron micrograph of a composite electrolyte membrane according to example 1;
FIG. 3 is a graph showing AC impedances at different temperatures of the composite electrolyte membrane in example 1;
fig. 4 is a charge-discharge cycle graph of the composite electrolyte membrane in example 1.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
(1) preparation of LLZO @ ZiF-67 powder: adding 0.5g PVP into 50mL of methanol solution, stirring, adding 0.5g LLZO powder, stirring at room temperature for 1 hr, adding 2.3284g (0.008 mol) Co (NO)3)2·6H2O, obtaining a solution A; 2.6272g (0.032 mol) of dimethyl imidazole is added into 50mL of methanol solution and stirred for 3 hours at room temperature to obtain solution B; slowly adding the solution B into the solution A, continuously stirring for 12h at room temperature, then centrifugally separating for 5min at 8000rpm/min, washing the obtained purple precipitate with methanol for three times, transferring the washed purple precipitate into a forced air oven, and drying for 6h at 60 ℃ to finally obtain purple LLZO @ ZiF-67 powder;
(2) preparing 20wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membrane slurry: weighing 0.88g of PEO and 0.3824g of LiTFSI, adding into 22mL of acetonitrile solution, continuously stirring, adding 0.2525g of LLZO @ ZiF-67 (the addition amount of LLZO @ ZiF-67 is 20wt% of the sum of the mass of PEO and LiTFSI) as a filling material, and stirring at room temperature for 12h to form uniform composite electrolyte membrane slurry;
(3) preparation of 20wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membranes: pouring the composite electrolyte membrane slurry into a polytetrafluoroethylene template in a glove box with water and oxygen content less than 0.1ppm by adopting a solution casting method, standing for 48 hours in the glove box, then transferring to a vacuum drying box, drying at 60 ℃ for 12 hours to completely volatilize the solvent, and removing the membrane to obtain the 20wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membrane.
The LLZO @ ZiF-67 filler obtained in example 1 was analyzed by transmission scanning electron microscope, and as a result, ZiF-67 was wrapped on the surface of LLZO as shown in FIG. 1, and had a polyhedral structure with a large specific surface area as a whole. When the composite film of example 1 was analyzed by scanning electron microscopy, as shown in FIG. 2, LLZO @ ZiF-67 was uniformly dispersed in the PEO-based polymer solid electrolyte to form a composite film having a smooth overall surface and fine voids. Further testing of the impedance of the composite solid electrolyte membrane of example 1 gave a composite membrane having an ionic conductance of 9.69E-05S cm at room temperature-1The results are shown in FIG. 3. The Li// LFP battery assembled on the organic-inorganic composite solid electrolyte membrane is subjected to charge-discharge cycle test at 60 ℃ according to the current density of 0.1C and the voltage range of 2.5-4.0V, and the result is shown in figure 4, the capacity of the solid battery prepared from the organic-inorganic composite solid electrolyte material is still maintained at about 141mAh/g after 100 cycles, which shows that the impedance inside the battery is better relieved, and the lithium ion transmission inside the battery is more facilitated.
Example 2
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
(1) preparation of LLZO @ ZiF-67 powder: same as in step (1) of example 1;
(2) preparing 10wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membrane slurry: weighing 0.88g of PEO and 0.3824g of LiTFSI, adding into 20mL of acetonitrile solution, continuously stirring, adding 0.1262g of LLZO @ ZiF-67 (the addition amount of LLZO @ ZiF-67 is 10wt% of the sum of the mass of PEO and LiTFSI) as a filling material, and stirring at room temperature for 12h to form uniform composite electrolyte membrane slurry;
(3) preparation of 10wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membranes: pouring the composite electrolyte membrane slurry into a polytetrafluoroethylene template in a glove box with water and oxygen content less than 0.1ppm by adopting a solution casting method, standing for 48 hours in the glove box, then transferring to a vacuum drying box, drying at 60 ℃ for 12 hours to completely volatilize the solvent, and removing the membrane to obtain the 10wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membrane.
Example 3
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
(1) preparation of LLZO @ ZiF-67 powder: same as in step (1) of example 1;
(2) preparing 30wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membrane slurry: weighing 0.88g of PEO and 0.3824g of LiTFSI, adding into 24mL of acetonitrile solution, continuously stirring, adding 0.3787g of LLZO @ ZiF-67 (the addition amount of LLZO @ ZiF-67 is 30wt% of the sum of the mass of PEO and LiTFSI) as a filling material, and stirring at room temperature for 12h to form uniform composite electrolyte membrane slurry;
(3) preparation of 30wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membranes: pouring the composite electrolyte membrane slurry into a polytetrafluoroethylene template in a glove box with water and oxygen content less than 0.1ppm by adopting a solution casting method, standing for 48 hours in the glove box, then transferring to a vacuum drying box, drying at 60 ℃ for 12 hours to completely volatilize the solvent, and stripping the membrane to obtain the 30wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membrane.
Example 4
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
(1) preparation of LLZO @ ZiF-67 powder: same as in step (1) of example 1;
(2) preparing 40wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membrane slurry: weighing 0.88g of PEO and 0.3824g of LiTFSI, adding into 26mL of acetonitrile solution, continuously stirring, adding 0.5049g of LLZO @ ZiF-67 (the addition amount of LLZO @ ZiF-67 is 40wt% of the sum of the mass of PEO and LiTFSI) as a filling material, and stirring at room temperature for 12h to form uniform composite electrolyte membrane slurry;
(3) preparation of 40wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membranes: pouring the composite electrolyte membrane slurry into a polytetrafluoroethylene template in a glove box with water and oxygen content less than 0.1ppm by adopting a solution casting method, standing for 48 hours in the glove box, then transferring to a vacuum drying box, drying at 60 ℃ for 12 hours to completely volatilize the solvent, and stripping the membrane to obtain the 40wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membrane.
Example 5
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
(1) preparation of LLZO @ ZiF-67 powder: same as in step (1) of example 1.
(2) Preparing 50wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membrane slurry: weighing 0.88g of PEO and 0.3824g of LiTFSI, adding into 22mL of acetonitrile solution, continuously stirring, adding 0.6312g of LLZO @ ZiF-67 (the addition amount of LLZO @ ZiF-67 is 50wt% of the sum of the mass of PEO and LiTFSI) as a filling material, and stirring at room temperature for 12h to form uniform composite electrolyte membrane slurry;
(3) preparation of 50wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membranes: pouring the composite electrolyte membrane slurry into a polytetrafluoroethylene template in a glove box with water and oxygen content less than 0.1ppm by adopting a solution casting method, standing for 48 hours in the glove box, then transferring to a vacuum drying box, drying at 60 ℃ for 12 hours to completely volatilize the solvent, and stripping the membrane to obtain the 50wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membrane.
Example 6
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
(1) preparation of LLZO @ ZiF-67 powder: adding 1g of PVP into 50mL of methanol solution, uniformly stirring, then adding 0.5g of LLZO powder, stirring at room temperature for 1 hour, and adding 2.3284g (0.008 mol) of Co (NO3) 2.6H 2O to obtain solution A; 0.6568g (0.008 mol) of dimethyl imidazole is added into 50mL of methanol solution and stirred for 3 hours at room temperature to obtain solution B; slowly adding the solution B into the solution A, continuously stirring for 12h at room temperature, then centrifugally separating for 5min at 8000rpm/min, washing the obtained purple precipitate with methanol for three times, transferring the washed purple precipitate into a forced air oven, and drying for 6h at 60 ℃ to finally obtain purple LLZO @ ZiF-67 powder;
(2) preparing 20wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membrane slurry: same as in step (2) of example 1;
(3) preparation of 20wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membranes: same as in step (3) of example 1.
Example 7
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
(1) preparation of LLZO @ ZiF-67 powder: 2.5g PVP was added to 50mL of methanol solution, 0.5g LLZO powder was added with stirring, stirred at room temperature for 1 hour, and 2.3284g (0.008 mol) Co (NO) was added3)2·6H2O, obtaining a solution A; 6.568g (0.08 mol) of dimethyl imidazole is added into 50mL of methanol solution and stirred for 3h at room temperature to obtain solution B; slowly adding the solution B into the solution A, continuously stirring for 12h at room temperature, then centrifugally separating for 5min at 8000rpm/min, washing the obtained purple precipitate with methanol for three times, transferring the washed purple precipitate into a forced air oven, and drying for 6h at 60 ℃ to finally obtain purple LLZO @ ZiF-67 powder;
(2) preparing 20wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membrane slurry: same as in step (2) of example 1;
(3) preparation of 20wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membranes: same as in step (3) of example 1.
Example 8
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
(1) preparation of LLZO @ ZiF-67 powder: adding 0.5g PVP into 50mL methanol solution, stirring, adding 0.5g LLZO powder, stirring at room temperature for 1 hr, adding 4.6568g (0.016 mol) Co (NO)3)2·6H2O, obtaining a solution A; 5.2546g (0.064 mol) of dimethyl imidazole is added into 50mL of methanol solution and stirred for 3h at room temperature to obtain solution B; slowly adding the solution B into the solution A, continuously stirring for 12h at room temperature, then centrifugally separating for 5min at 8000rpm/min, washing the obtained purple precipitate with methanol for three times, transferring the washed purple precipitate into a forced air oven, and drying for 6h at 60 ℃ to finally obtain purple LLZO @ ZiF-67 powder;
(2) preparing 20wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membrane slurry: same as in step (2) of example 1;
(3) preparation of 20wt% LLZO @ ZiF-67/PEO/LiTFSI composite solid electrolyte membranes: same as in step (3) of example 1.
Example 9
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
(1) preparation of LLZO @ ZiF-8 powder: adding 0.5g PVP into 50mL of methanol solution, stirring, adding 0.5g LLZO powder, stirring at room temperature for 1 hr, adding 2.3780g (0.008 mol) Zn (NO)3)2·6H2O, obtaining a solution A; 2.6272g (0.032 mol) of dimethyl imidazole is added into 50mL of methanol solution and stirred for 3 hours at room temperature to obtain solution B; slowly adding the solution B into the solution A, continuously stirring for 12h at room temperature, then centrifugally separating for 5min at 8000rpm/min, washing the obtained precipitate with methanol for three times, transferring the washed precipitate into a forced air oven, and drying for 6h at 60 ℃ to finally obtain LLZO @ ZiF-8 powder;
(2) preparing 10wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membrane slurry: weighing 0.88g of PEO and 0.3824g of LiTFSI, adding into 20mL of acetonitrile solution, continuously stirring, adding 0.1262g of LLZO @ ZiF-8 (the addition amount of LLZO @ ZiF-8 is 10wt% of the sum of the mass of PEO and LiTFSI) serving as a filling material, and stirring at room temperature for 12h to form uniform composite electrolyte membrane slurry;
(3) preparation of 10wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membranes: pouring the composite electrolyte membrane slurry into a polytetrafluoroethylene template in a glove box with water and oxygen content less than 0.1ppm by adopting a solution casting method, standing for 48 hours in the glove box, then transferring to a vacuum drying box, drying at 60 ℃ for 12 hours to completely volatilize the solvent, and removing the membrane to obtain the 10wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membrane.
Example 10
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
(1) preparation of LLZO @ ZiF-8 powder: same as in step (1) of example 6.
(2) Preparation of 20wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membranes: weighing 0.88g of PEO and 0.3824g of LiTFSI, adding into 22mL of acetonitrile solution, continuously stirring, adding 0.2525g of LLZO @ ZiF-8 (the addition amount of LLZO @ ZiF-8 is 20wt% of the sum of the mass of PEO and LiTFSI) as a filling material, and stirring at room temperature for 12h to form uniform composite electrolyte membrane slurry;
(3) preparation of 20wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membranes: pouring the composite electrolyte membrane slurry into a polytetrafluoroethylene template in a glove box with water and oxygen content less than 0.1ppm by adopting a solution casting method, standing for 48 hours in the glove box, then transferring to a vacuum drying box, drying at 60 ℃ for 12 hours to completely volatilize the solvent, and removing the membrane to obtain the 20wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membrane.
Example 11
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
(1) preparation of LLZO @ ZiF-8 powder: same as in step (1) of example 1;
(2) preparing 30wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membrane slurry: weighing 0.88g of PEO and 0.3824g of LiTFSI, adding into 24mL of acetonitrile solution, continuously stirring, adding 0.3787g of LLZO @ ZiF-8 (the addition amount of LLZO @ ZiF-8 is 30wt% of the sum of the mass of PEO and LiTFSI) serving as a filling material, and stirring at room temperature for 12h to form uniform composite electrolyte membrane slurry;
(3) preparation of 30wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membranes: pouring the composite electrolyte membrane slurry into a polytetrafluoroethylene template in a glove box with water and oxygen content less than 0.1ppm by adopting a solution casting method, standing for 48 hours in the glove box, then transferring to a vacuum drying box, drying at 60 ℃ for 12 hours to completely volatilize the solvent, and stripping the membrane to obtain the 30wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membrane.
Example 12
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
(1) preparation of LLZO @ ZiF-8 powder: same as in step (1) of example 1;
(2) preparing 40wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membrane slurry: weighing 0.88g of PEO and 0.3824g of LiTFSI, adding into 26mL of acetonitrile solution, continuously stirring, adding 0.5049g of LLZO @ ZiF-8 (the addition amount of LLZO @ ZiF-8 is 40wt% of the sum of the mass of PEO and LiTFSI) as a filling material, and stirring at room temperature for 12h to form uniform composite electrolyte membrane slurry;
(3) preparation of 40wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membranes: pouring the composite electrolyte membrane slurry into a polytetrafluoroethylene template in a glove box with water and oxygen content less than 0.1ppm by adopting a solution casting method, standing for 48 hours in the glove box, then transferring to a vacuum drying box, drying at 60 ℃ for 12 hours to completely volatilize the solvent, and removing the membrane to obtain the 40wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membrane.
Example 13
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
(1) preparation of LLZO @ ZiF-8 powder: same as in step (1) of example 1;
(2) preparing 50wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membrane slurry: weighing 0.88g of PEO and 0.3824g of LiTFSI, adding into 22mL of acetonitrile solution, continuously stirring, adding 0.6312g of LLZO @ ZiF-8 (the addition amount of LLZO @ ZiF-8 is 50wt% of the sum of the mass of PEO and LiTFSI) serving as a filling material, and stirring at room temperature for 12h to form uniform composite electrolyte membrane slurry;
(3) preparation of 50wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membranes: pouring the composite electrolyte membrane slurry into a polytetrafluoroethylene template in a glove box with water and oxygen content less than 0.1ppm by adopting a solution casting method, standing for 48 hours in the glove box, then transferring to a vacuum drying box, drying at 60 ℃ for 12 hours to completely volatilize the solvent, and removing the membrane to obtain the 50wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membrane.
Example 14
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
(1) preparation of LLZO @ ZiF-8 powder: 1g PVP was added to 50mL of methanol solution, 0.5g LLZO powder was added after stirring, stirred at room temperature for 1 hour, and 2.3780g (0.008 mol) Zn (NO) was added3)2·6H2O, obtaining a solution A; 0.6568g (0.008 mol) of dimethyl imidazole is added into 50mL of methanol solution and stirred for 3 hours at room temperature to obtain solution B; slowly adding solution B into solution A, stirring at room temperature for 12 hr, and centrifuging at 8000rpm/min for 5minWashing the obtained precipitate with methanol for three times, transferring the washed precipitate into a forced air oven, and drying at 60 ℃ for 6h to finally obtain LLZO @ ZiF-8 powder;
(2) preparing 10wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membrane slurry: same as in step (2) of example 8;
(3) preparation of 10wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membranes: same as in step (3) of example 8.
Example 15
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
(1) preparation of LLZO @ ZiF-8 powder: 2.5g PVP was added to 50mL of methanol solution, 0.5g LLZO powder was added with stirring, stirred at room temperature for 1 hour, and 2.3780g (0.008 mol) Zn (NO) was added3)2·6H2O, obtaining a solution A; 6.568g (0.08 mol) of dimethyl imidazole is added into 50mL of methanol solution and stirred for 3h at room temperature to obtain solution B; slowly adding the solution B into the solution A, continuously stirring for 12h at room temperature, then centrifugally separating for 5min at 8000rpm/min, washing the obtained precipitate with methanol for three times, transferring the washed precipitate into a forced air oven, and drying for 6h at 60 ℃ to finally obtain LLZO @ ZiF-8 powder;
(2) preparing 10wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membrane slurry: same as in step (2) of example 8;
(3) preparation of 10wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membranes: same as in step (3) of example 8.
Example 16
A method for preparing an organic-inorganic composite solid electrolyte membrane, comprising the steps of:
((1) preparation of LLZO @ ZiF-8 powder 0.5g PVP was added to 50mL of methanol solution, stirred well, 0.5g LLZO powder was added, stirred at room temperature for 1 hour, 4.7598g (0.016 mol) Zn (NO) was added3)2·6H2O, obtaining a solution A; 5.2546g (0.064 mol) of dimethyl imidazole is added into 50mL of methanol solution and stirred for 3h at room temperature to obtain solution B; slowly adding solution B into solution A, stirring at room temperature for 12 hr, centrifuging at 8000rpm/min for 5min, and collecting precipitateWashing with alcohol for three times, transferring the washed precipitate into a forced air oven, and drying at 60 ℃ for 6h to finally obtain LLZO @ ZiF-8 powder;
(2) preparing 10wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membrane slurry: same as in step (2) of example 8;
(3) preparation of 10wt% LLZO @ ZiF-8/PEO/LiTFSI composite solid electrolyte membranes: same as in step (3) of example 8.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (10)

1. An organic-inorganic composite solid electrolyte membrane characterized in that: the organic-inorganic composite solid electrolyte membrane is a membrane structure with a smooth surface and micropores, and consists of PEO, LiTFSI and ZiF modified active inorganic fillers.
2. The method of producing an organic-inorganic composite solid electrolyte membrane according to claim 1, characterized by comprising the steps of:
(1) preparation ZiF of modified active inorganic Filler: adding active inorganic filler powder into a solution containing a surfactant, stirring uniformly, and adding a metal cation soluble compound to obtain a solution A; pouring the organic ligand solution into the solution A, stirring the solution A uniformly, and then carrying out solid-liquid separation, washing and drying to obtain ZiF modified active inorganic filler;
(2) preparing organic-inorganic composite solid electrolyte membrane slurry: ZiF modified active inorganic filler is used as a filling material and is uniformly mixed with PEO and LiTFSI according to a certain mass ratio to form composite electrolyte membrane slurry;
(3) preparing an organic-inorganic composite solid electrolyte membrane: pouring the composite electrolyte membrane slurry into a polytetrafluoroethylene template by adopting a solution casting method, and obtaining the organic-inorganic composite solid electrolyte membrane after the solvent is completely volatilized.
3. The method for producing an organic-inorganic composite solid electrolyte membrane according to claim 2, characterized in that: in the step (1), the active inorganic filler is NASICON type solid electrolyte powder, phosphide solid electrolyte powder, perovskite type solid electrolyte powder, lithium phosphorus oxygen nitrogen solid electrolyte powder or garnet type solid electrolyte powder.
4. The method for producing an organic-inorganic composite solid electrolyte membrane according to claim 2, characterized in that: the surfactant in the step (1) adopts polyvinylpyrrolidone and hexadecyl trimethyl ammonium bromide; the solvent used by the solution containing the surfactant and the organic ligand solution is methanol or N, N-dimethylformamide, and the amount of the solvent used by the solution containing the surfactant and the organic ligand solution is the same.
5. The method for producing an organic-inorganic composite solid electrolyte membrane according to claim 2, characterized in that: in the step (1), the soluble compound of the metal cation is a compound containing cobalt, zinc or zirconium cation; the organic ligand is dimethyl imidazole.
6. The method for producing an organic-inorganic composite solid electrolyte membrane according to claim 2, characterized in that: the mass ratio of the active inorganic filler powder to the surfactant in the step (1) is 1:1-1: 5; the molar ratio of the metal cation compound to the organic ligand is 1:1-1: 10; the mass ratio of the metal cation compound to the active inorganic filler powder is 4:1-10: 1.
7. The method for producing an organic-inorganic composite solid electrolyte membrane according to claim 2, characterized in that: in the step (1), solid-liquid separation adopts centrifugation or suction filtration; washing with solvent for 3-5 times; the drying condition is drying at 60-80 deg.C for 6-24 h.
8. The method for producing an organic-inorganic composite solid electrolyte membrane according to claim 2, characterized in that: in the step (2), the mass ratio of EO to LiTFSI in the PEO is 5:1-15:1, and the ZiF modified active inorganic filler accounts for 1-50% of the total mass of the PEO and the LiTFSI.
9. The method for producing an organic-inorganic composite solid electrolyte membrane according to claim 2, characterized in that: in the step (3), a solution casting method is adopted in a glove box with water and oxygen content less than 0.1ppm, the solution is poured into a polytetrafluoroethylene template, then the polytetrafluoroethylene template is kept stand in the glove box for 48 hours, then the polytetrafluoroethylene template is transferred to a vacuum drying box, the solvent is completely volatilized after drying is carried out for 12 hours at the temperature of 60 ℃, and the organic-inorganic composite solid electrolyte membrane is obtained after membrane uncovering.
10. Use of the organic-inorganic composite solid electrolyte membrane according to claim 1 in a lithium ion battery.
CN202111239414.6A 2021-10-25 2021-10-25 Organic-inorganic composite solid electrolyte membrane and preparation method and application thereof Active CN113991174B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111239414.6A CN113991174B (en) 2021-10-25 2021-10-25 Organic-inorganic composite solid electrolyte membrane and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111239414.6A CN113991174B (en) 2021-10-25 2021-10-25 Organic-inorganic composite solid electrolyte membrane and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113991174A true CN113991174A (en) 2022-01-28
CN113991174B CN113991174B (en) 2023-06-23

Family

ID=79740861

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111239414.6A Active CN113991174B (en) 2021-10-25 2021-10-25 Organic-inorganic composite solid electrolyte membrane and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113991174B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023244745A1 (en) * 2022-06-15 2023-12-21 Giner, Inc. Solid-state electrolyte battery including plastic crystal electrolyte interlayer

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014156434A (en) * 2013-02-18 2014-08-28 Kansai Univ Functional metal-organic framework material containing novel composite particles
CN104492491A (en) * 2014-12-12 2015-04-08 大连理工大学 ZIF-8 film coated millimeter-level large-sphere Pd/Al2O3 eggshell type catalyst and preparation method thereof
CN109776423A (en) * 2019-03-20 2019-05-21 厦门大学 A kind of double imidazole ring functional ion liquids and preparation method thereof and electrolyte and lithium secondary battery
CN112786881A (en) * 2019-11-07 2021-05-11 北京新能源汽车股份有限公司 Solid-state lithium battery and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014156434A (en) * 2013-02-18 2014-08-28 Kansai Univ Functional metal-organic framework material containing novel composite particles
CN104492491A (en) * 2014-12-12 2015-04-08 大连理工大学 ZIF-8 film coated millimeter-level large-sphere Pd/Al2O3 eggshell type catalyst and preparation method thereof
CN109776423A (en) * 2019-03-20 2019-05-21 厦门大学 A kind of double imidazole ring functional ion liquids and preparation method thereof and electrolyte and lithium secondary battery
CN112786881A (en) * 2019-11-07 2021-05-11 北京新能源汽车股份有限公司 Solid-state lithium battery and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ZHENGZHANG ETAL: "MOF-derived multifunctional filler reinforced polymer electrolyte for solid-state lithium batteries", 《JOURNAL OF ENERGY CHEMISTRY》 *
ZHENGZHANG ETAL: "MOF-derived multifunctional filler reinforced polymer electrolyte for solid-state lithium batteries", 《JOURNAL OF ENERGY CHEMISTRY》, vol. 60, 29 January 2021 (2021-01-29), pages 259 - 271, XP086547852, DOI: 10.1016/j.jechem.2021.01.013 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023244745A1 (en) * 2022-06-15 2023-12-21 Giner, Inc. Solid-state electrolyte battery including plastic crystal electrolyte interlayer

Also Published As

Publication number Publication date
CN113991174B (en) 2023-06-23

Similar Documents

Publication Publication Date Title
CN109004173B (en) Lithium-sulfur battery positive electrode and manufacturing method thereof
CN112397772B (en) Solid electrolyte and preparation method and application thereof
CN111180791A (en) Preparation method of metal organic framework/ionic liquid based composite solid electrolyte
CN111048829A (en) Solid lithium ion composite electrolyte membrane and preparation method thereof
US20230098496A1 (en) All solid-state electrolyte composite based on functionalized metal-organic framework materials for lithium secondary battery and method for manufacturing the same
CN113054249A (en) Preparation method and application of MOF material PVDF-HFP gel electrolyte
CN116130748A (en) Composite solid electrolyte membrane and preparation method thereof
Ai et al. A chitosan/poly (ethylene oxide)‐based hybrid polymer composite electrolyte suitable for solid‐state lithium metal batteries
CN115064764A (en) Ceramic filler modified high-conductivity wide-voltage-window composite electrolyte material, and preparation method and application thereof
CN114388745B (en) High-performance lithium ion battery self-supporting polymer thick pole piece and preparation method thereof
Li et al. Composite solid electrolyte with Li+ conducting 3D porous garnet-type framework for all-solid-state lithium batteries
CN113991174B (en) Organic-inorganic composite solid electrolyte membrane and preparation method and application thereof
CN115020802A (en) In-situ ultraviolet light curing nanofiber composite solid electrolyte and preparation method and application thereof
CN114497707A (en) High-performance low-cost composite solid electrolyte and preparation method and application thereof
CN114373985A (en) Cellulose membrane reinforced polymer solid electrolyte membrane and preparation method and application thereof
CN110061294A (en) Preparation method of rigid-flexible parallel-type composite all-solid-state polymer electrolyte
CN109888183B (en) Preparation method and application of organic-inorganic hybrid film
CN116487682A (en) Flame-retardant organic-inorganic composite solid electrolyte, and preparation method and application thereof
CN114243098A (en) Composite solid electrolyte and preparation method and application thereof
CN114361577A (en) Pure cubic phase nano lithium gallium lanthanum zirconium oxygen powder and preparation method and application thereof
CN114256561A (en) Composite diaphragm for lithium metal battery and preparation method thereof
Yuan et al. Study of poly (organic palygorskite-methyl methacrylate)/poly (vinylidene fluoride-co-hexafluoropropylene) blended gel polymer electrolyte for lithium-ion batteries
CN114006028B (en) Modified inorganic fast ion conductor and preparation method and application thereof
CN113964378B (en) Composite solid electrolyte and manufacturing method thereof
CN117691199B (en) Glass fiber-based composite material and preparation method and application thereof

Legal Events

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