CN111613833A - Polymer solid electrolyte and preparation method thereof - Google Patents

Polymer solid electrolyte and preparation method thereof Download PDF

Info

Publication number
CN111613833A
CN111613833A CN202010415819.XA CN202010415819A CN111613833A CN 111613833 A CN111613833 A CN 111613833A CN 202010415819 A CN202010415819 A CN 202010415819A CN 111613833 A CN111613833 A CN 111613833A
Authority
CN
China
Prior art keywords
lithium
solid electrolyte
lithium salt
polymer solid
salt
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.)
Pending
Application number
CN202010415819.XA
Other languages
Chinese (zh)
Inventor
陈步天
余意
何凤荣
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.)
Dongguan HEC Tech R&D Co Ltd
Dongguan Dongyang Guangke Research and Development Co Ltd
Original Assignee
Dongguan HEC Tech R&D Co Ltd
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 Dongguan HEC Tech R&D Co Ltd filed Critical Dongguan HEC Tech R&D Co Ltd
Priority to CN202010415819.XA priority Critical patent/CN111613833A/en
Publication of CN111613833A publication Critical patent/CN111613833A/en
Pending legal-status Critical Current

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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M2300/0088—Composites
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

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

Abstract

The invention discloses a polymer solid electrolyte and a preparation method thereof. The polymer solid electrolyte comprises a polymer matrix, lithium salt and an inorganic filler, wherein the polymer matrix is PVDF or a mixture of PVDF and PEO; the lithium salt comprises a lithium salt A, and the lithium salt A is lithium tri-tert-butoxyaluminum hydride (LTTBA) or Lithium Triethylborohydride (LTEB) or a mixture of the lithium salt A and the lithium salt A. The invention also discloses a preparation method of the polymer solid electrolyte. The lithium battery containing the polymer solid electrolyte has excellent cycle performance and rate performance and good interface stability.

Description

Polymer solid electrolyte and preparation method thereof
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a polymer solid electrolyte containing novel lithium salt and a preparation method thereof.
Background
The lithium secondary battery has the advantages of no memory effect, high volume specific capacity, high working voltage, wide temperature resistance range, low self-discharge rate, long cycle life and the like, and has good application prospect in new energy fields such as intelligent electronic products, electric automobiles, large-scale energy storage power grids and the like. However, the lithium secondary batteries widely used at present all use liquid organic small-molecule electrolytes, and have potential safety hazards of explosion under abnormal conditions such as overcharge and internal short circuit. In recent years, the safety accidents of the lithium battery frequently burst, which shows that the safety problem of the lithium secondary battery becomes a technical bottleneck restricting the wider and deeper application of the lithium secondary battery. Further development of lithium secondary batteries with higher specific energy and high safety has important significance and value for further development of new energy industries.
The polymer lithium battery using the polymer solid electrolyte to replace the organic micromolecular electrolyte is expected to thoroughly solve the safety concern of the battery while improving the energy density of the lithium battery, so the polymer lithium battery has better development prospect. One of the most common polymer matrices for polymer solid electrolytes today is a polyvinylidene fluoride (PVDF) -based polymer. However, the existing PVDF-based polymer electrolytes still have drawbacks in performance. For example, PVDF has high crystallinity and a high proportion of crystalline regions, which leads to the inability of lithium ions to rapidly transport in the PVDF matrix and poor ionic conductivity; PVDF can react with a lithium metal negative electrode, and by-products generated by the reaction cause the contact between an electrolyte and a lithium metal interface, so that the polarization of the battery is increased, and the interface stability is poor; PVDF reacts in contact with lithium metal, resulting in a lower electrochemical window; the PVDF cannot bear heat generated by thermal runaway, so that the thermal stability of the PVDF is poor and potential safety hazards exist.
Therefore, there is a need for improvement of the existing PVDF-based polymer solid electrolyte.
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the existing PVDF-based polymer solid electrolyte, and therefore, the present invention provides a polymer solid electrolyte containing a novel lithium salt and a method for preparing the same. On one hand, the ionic conductivity, electrochemical window and thermal stability of the PVDF polymer solid electrolyte are improved by adding novel lithium salt; on one hand, the crystallinity of the PVDF polymer solid electrolyte is reduced by adding the inorganic filler, and the ionic conductivity is further improved.
Specifically, the invention adopts the following technical scheme:
in one aspect, the present invention provides a polymer solid electrolyte comprising a polymer matrix, a lithium salt and an inorganic filler, wherein the polymer matrix is PVDF or a mixture of PVDF and PEO; the lithium salt comprises a lithium salt A, and the lithium salt A is lithium tri-tert-butoxyaluminum hydride (LTTBA) or Lithium Triethylborohydride (LTEB) or a mixture of the lithium salt A and the lithium salt A.
The lithium salt A has high thermal decomposition temperature, high ionic conductivity and high electrochemical oxidation voltage, and can effectively improve the thermal stability, ionic conductivity and electrochemical window of PVDF when added into the PVDF polymer solid electrolyte. Meanwhile, the filler is added into the polymer matrix, so that the mechanical property of the PVDF can be improved, and the ionic conductivity, the pressure resistance and the thermal decomposition temperature of the PVDF can be further improved.
In addition, PEO can be added into the polymer matrix to achieve the purpose of improving the interface performance of the polymer solid electrolyte, so that the cycle performance and the rate capability of the PVDF-based polymer solid battery are improved.
According to some embodiments of the present invention, when the polymer matrix is a mixture of PVDF and PEO, the mass ratio of PEO to PVDF is 1:3 to 25, for example: 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, and so forth.
In some embodiments, when the polymer matrix is a mixture of PVDF and PEO, the mass ratio of the PEO to the PVDF is 1: 3-15.
In some embodiments, when the polymer matrix is a mixture of PVDF and PEO, the mass ratio of the PEO to the PVDF is 1: 5-15.
According to some embodiments of the present invention, the mass ratio of the lithium salt to the polymer matrix is 1:1 to 20, for example: 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, and so forth.
In some embodiments, the mass ratio of the lithium salt to the polymer matrix is 1:1 to 15, in some embodiments 1:1 to 12, in some embodiments 1:1 to 5, in some embodiments 1:5 to 20, and in some embodiments 1:12 to 20.
According to some provided embodiments of the invention, the lithium salt a is lithium tri-tert-butoxyaluminum hydride or lithium triethylborohydride.
According to some embodiments of the present invention, the lithium salt a is a mixture of lithium tri-tert-butoxyaluminum hydride and lithium triethylborohydride, which may be mixed in any ratio.
The anion structure in the electrolyte lithium salt is an important factor influencing the lithium salt, and the larger the volume of the lithium salt anion is, the higher the degree of negative charge delocalization is, so that the electrostatic interaction between the lithium salt and the cation can be reduced, the lithium salt is easy to dissociate, and the polymer electrolyte has higher lithium ion conductivity. In addition, during charging and discharging, anions are gathered at an electrode/electrolyte interface to hinder the migration of cations, thereby reducing the energy efficiency and the service life of the battery. The anion with large volume is adopted, and the anion is difficult to migrate in the macromolecule due to the volume factor, so that the cation migration number is increased, and the battery performance is improved. In addition, the large-volume anion also has better electrochemical stability and thermal stability, improves the thermal stability and the electrochemical stability of the lithium salt, and plays an effective plasticizing effect, so that the technical effect of the invention is not necessarily achieved by specially selecting the electrolyte lithium salt containing the lithium salt A and replacing the lithium salt A with other lithium salts of the same type in the technical scheme provided by the invention.
According to some embodiments provided by the present invention, other common lithium salts, namely, lithium salt B in the present invention, may also be added. The addition of the lithium salt B can further improve the conductivity of the polymer solid electrolyte, and the polymer solid electrolyte with better performance can be obtained by combining the lithium salt B with the lithium salt A.
The lithium salt B is lithium bistrifluoromethanesulfonate imide (LiTFSI), lithium bistrifluoromethanesulfonate imide (LiFSI), lithium bisoxalato borate (LiBOB) and lithium tetrafluoroborate (LiBF)4) Lithium difluorobis (oxalato) borate (LiODFB), lithium perchlorate (LiClO)4) Lithium hexafluorophosphate (LiPF)6) Tert-butyllithium, bistrimethylsilylaminolithium, bistrifluoromethanesulfonylimide, lithium diisopropylamide, n-butyllithium, sec-butyllithium, tri-sec-butyllithium borohydride, tri-tert-butoxylithium aluminum hydride, lithium methyllithium tert-butoxide, lithium triethylborohydride, bis (tert-butyllithium)At least one of lithium isopropylamide, lithium bistrimethylsilyl, lithium acetoacetate, lithium pentamethylcyclopentadiene, lithium trifluoroethyl trifluorophosphate, 4, 5-dicyano-2-trifluoromethylimidazole (LiTDI), lithium bis (fluoromalonic acid) borate (LiBFMB), 4, 5-dicyano-2-heptafluoropropylimidazole (LiHDI), lithium 4, 5-dicyano-1, 2, 3-triazolate (LiDCTA), lithium fluorosulfonate (n-perfluorobutylsulfonyl) imide (LiNFSI).
In addition to the above-listed lithium salts B, other lithium salts commonly used in the art to achieve comparable technical effects may also be used in the present invention.
According to some embodiments of the present invention, when the lithium salt is a mixture of lithium salt A and lithium salt B, the mass ratio of lithium salt A to lithium salt B is 20-1: 1-10. If the lithium salt B is too much, the mechanical properties of the polymer solid electrolyte are poor and the conductivity is also low; and if the lithium salt B is too little, the conductivity-improving effect of the polymer solid electrolyte is insignificant.
In some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 10-1: 1-10; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 5-1: 1-10; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 5-1: 1-9; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 2-1: 1-10; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 2-1: 1-9.
According to some embodiments of the present invention, when the lithium salt A is lithium triethylborohydride, the mass ratio of the lithium triethylborohydride to the lithium salt B is 20-1: 1-10.
In some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 10-1: 1-10; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 5-1: 1-10; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 5-1: 1-9; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 2-1: 1-10; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 2-1: 1-9.
According to some embodiments of the present invention, when the lithium salt A is lithium tri-tert-butoxyaluminum hydride, the mass ratio of the lithium tri-tert-butoxyaluminum hydride to the lithium salt B is 20-1: 1-10.
In some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 10-1: 1-10; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 5-1: 1-10; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 5-1: 1-9; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 2-1: 1-10; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 2-1: 1-9.
According to some embodiments provided herein, the lithium salt B is lithium bistrifluoromethanesulfonate imide, lithium bistrifluoromethanesulfonate borate, lithium tetrafluoroborate, lithium difluorobis-oxalato borate, lithium perchlorate, lithium hexafluorophosphate, t-butyllithium, lithium bistrimethylsilylamide, lithium bistrifluoromethanesulfonylimide, lithium diisopropylamide, n-butyllithium, sec-butyllithium, lithium tri-sec-butylborohydride, lithium tri-t-butoxyaluminum hydride, lithium tert-butoxymethyllithium, lithium triethylborohydride, lithium diisopropylamide, lithium bistrimethylsilylamide, lithium acetoacetate, lithium pentamethylcyclopentadienyl, lithium trifluoroethyl-trifluorophosphate, 4, 5-dicyano-2-trifluoromethylimidazole, lithium bis (fluoropropanedioate) borate, 4, 5-dicyano-2-heptafluoropropylimidazole, 4, 5-dicyano-1, any one or two of 2, 3-lithium triazolate and lithium fluorosulfonate (n-perfluorobutylsulfonyl) imide.
According to some embodiments of the present invention, the inorganic filler is at least one of alumina, zinc oxide, titanium oxide, silica, molybdenum disulfide, lithium lanthanum zirconium tantalum oxygen, titanium aluminum lithium phosphate, germanium aluminum lithium phosphate, lithium aluminate, germanium lithium sulfur phosphate, lanthanum lithium titanate, montmorillonite, copper oxide, magnesium oxide, lead titanate, and calcium silicate.
In some embodiments, the inorganic filler is any one of alumina, zinc oxide, titanium oxide, silica, molybdenum disulfide, lithium lanthanum zirconium tantalum oxygen, titanium aluminum lithium phosphate, germanium aluminum lithium phosphate, lithium aluminate, sulfur germanium lithium phosphate, lanthanum lithium titanate, montmorillonite, copper oxide, magnesium oxide, lead titanate, and calcium silicate.
In addition to the above-listed inorganic fillers, other inorganic fillers commonly used in the art to achieve comparable technical results can also be used in the present invention.
According to some embodiments of the present invention, the inorganic filler is added in an amount of 5% to 40%, preferably 10% to 20%, of the total mass of the polymer solid electrolyte. If the addition amount of the inorganic filler is too much, the inorganic filler is not well dispersed uniformly, so that the conductivity is greatly reduced; if the amount of the inorganic filler added is too small, the effect of reducing the crystallinity of the polymer cannot be exerted, so that the effect of improving the conductivity of the polymer solid electrolyte is not significant, and the effect of improving the mechanical strength of the polymer is not ideal.
Specifically, the inorganic filler is added in a proportion of the total mass of the polymer solid electrolyte, and the proportion is as follows: 5%, 8%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, etc.
In another aspect, the present invention provides a method for preparing the polymer solid electrolyte, comprising:
stirring and mixing a polymer matrix, lithium salt and an inorganic filler in an organic solvent to obtain slurry;
and casting the slurry in a mold, and drying in vacuum to obtain the polymer solid electrolyte.
According to some embodiments provided herein, the organic solvent is at least one of acetonitrile, N-dimethylpyrrolidone (NMP), Dimethylacetamide (DMAC) and Dimethylformamide (DMF).
In some embodiments, the organic solvent is any one of acetonitrile, N-dimethylpyrrolidone (NMP), Dimethylacetamide (DMAC), and Dimethylformamide (DMF).
The selection of the polymer matrix, the lithium salt and the inorganic filler is the same as that of each component in the polymer electrolyte, and the details are not repeated.
According to some embodiments of the present invention, the temperature of the stirring and mixing is 25 to 80 ℃, for example: 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ and the like; the stirring time is 3-24 h, for example: 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, and so on.
In some embodiments, the temperature of the stirring and mixing is 30-60 ℃, and the stirring time is 6-12 hours. In some embodiments, the temperature of the stirring and mixing is 30-60 ℃, and the stirring time is 12-24 hours; in some embodiments, the temperature of the stirring and mixing is 30-60 ℃, and the stirring time is 16-24 hours.
According to some embodiments of the present invention, the temperature of the vacuum drying is 25 to 60 ℃, for example: 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ and the like; the stirring time is 3-24 h, for example: 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, and so on.
In some embodiments, the temperature of the stirring and mixing is 30 to 50 ℃, and the stirring time is 10 to 24 hours. In some embodiments, the temperature of the stirring and mixing is 30-50 ℃, and the stirring time is 12-24 hours; in some embodiments, the temperature of the stirring and mixing is 30-50 ℃, and the stirring time is 16-24 hours.
According to some embodiments of the invention, the mold is a polytetrafluoroethylene mold.
In another aspect, the present invention provides a lithium battery comprising the above-described polymer solid electrolyte material.
The invention has the following technical effects:
(1) in the polymer solid electrolyte provided by the invention, the lithium salt A has high thermal decomposition temperature, high ionic conductivity and high electrochemical oxidation voltage, and can be added into the PVDF polymer solid electrolyte to effectively improve the thermal stability, ionic conductivity and electrochemical window of PVDF. Meanwhile, the inorganic filler is added into the polymer matrix, so that the mechanical property of the PVDF can be improved, and the ionic conductivity, the pressure resistance and the thermal decomposition temperature of the PVDF can be further improved. In addition, the interface performance of the polymer solid electrolyte is improved by adding PEO into the polymer matrix, and the cycle performance and rate capability of the PVDF-based polymer solid battery are improved.
(2) The lithium battery containing the polymer solid electrolyte provided by the invention has the conductivity of 2.4x10-4S cm-1The electrochemical window can reach 4.9V, and the current density is preferably 0.1mA/cm2The catalyst runs for 1180h without short circuit, and has excellent stability and good cycle performance.
Drawings
FIG. 1 shows an impedance diagram of a polymer solid electrolyte prepared in example 1 of the present invention;
FIG. 2 is a graph showing the impedance of a polymer solid electrolyte prepared in example 2 of the present invention;
FIG. 3 is a graph showing the impedance of a polymer solid electrolyte prepared in example 3 of the present invention;
FIG. 4 is a graph showing the impedance of a polymer solid electrolyte prepared in example 4 of the present invention;
FIG. 5 is a graph showing the impedance of a polymer solid electrolyte prepared in example 5 of the present invention;
FIG. 6 is a graph showing the impedance of the polymer solid electrolyte prepared in comparative example 1 of the present invention;
FIG. 7 is a graph showing the impedance of the polymer solid electrolyte prepared in comparative example 2 of the present invention;
FIG. 8 is a graph showing the impedance of a polymer solid electrolyte prepared in comparative example 3 of the present invention;
fig. 9 shows a linear cyclic voltammogram of a polymer solid electrolyte assembled button cell prepared in example 4 of the present invention;
FIG. 10 is a button full cell cycle performance test chart of the polymer solid electrolyte prepared in example 4 of the present invention; and
FIG. 11 is a graph showing the test of the lithium metal interfacial stability of the polymer solid electrolyte prepared in example 4 of the present invention.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety. The term "comprising" or "comprises" is open-ended, i.e. comprising what is specified in the present invention, but not excluding other aspects.
The method for preparing the polymer solid electrolyte will be described in detail below.
According to some embodiments provided herein, the method for preparing the polymer solid electrolyte includes:
stirring and mixing a polymer matrix, lithium salt and an inorganic filler in an organic solvent to obtain slurry;
and casting the slurry in a mold, and drying in vacuum to obtain the polymer solid electrolyte.
According to some embodiments provided herein, the polymer matrix is PVDF or a mixture of PVDF and PEO.
According to some embodiments of the present invention, when the polymer matrix is a mixture of PVDF and PEO, the mass ratio of PEO to PVDF is 1:3 to 25, for example: 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, and so forth.
In some embodiments, when the polymer matrix is a mixture of PVDF and PEO, the mass ratio of the PEO to the PVDF is 1: 3-15.
According to some embodiments of the present invention, the mass ratio of the lithium salt to the polymer matrix is 1:1 to 20, for example: 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, and so forth.
In some embodiments, the mass ratio of the lithium salt to the polymer matrix is 1:1 to 15, in some embodiments 1:1 to 12, in some embodiments 1:1 to 5, in some embodiments 1:5 to 20, and in some embodiments 1:12 to 20.
According to some provided embodiments of the invention, the lithium salt a is lithium tri-tert-butoxyaluminum hydride or lithium triethylborohydride.
According to some embodiments of the present invention, the lithium salt a is a mixture of lithium tri-tert-butoxyaluminum hydride and lithium triethylborohydride, which may be mixed in any ratio.
In the technical scheme provided by the invention, the lithium salt A is replaced by other lithium salts in the field, so that the technical effect of the invention cannot be achieved.
According to some embodiments provided by the present invention, other common lithium salts, namely, lithium salt B in the present invention, may also be added.
The lithium salt B is lithium bistrifluoromethanesulfonate, lithium bisoxalateborate, lithium tetrafluoroborate, lithium difluorobisoxalateborate, lithium perchlorate, lithium hexafluorophosphate, tert-butyllithium, bistrimethylsilyl lithium, bistrifluoromethanesulfonylimide, lithium diisopropylamide, n-butyllithium, sec-butyllithium, lithium tri-sec-butylborohydride, lithium tri-tert-butoxyaluminum hydride, lithium tert-butoxide methyllithium, lithium triethylborohydride, lithium diisopropylamide, bistrimethylsilyl lithium, lithium acetoacetate, lithium pentamethylcyclopentadiene, lithium trifluoroethyl trifluorophosphate, 4, 5-dicyano-2-trifluoromethylimidazole, lithium bis (fluoropropionate) borate, 4, 5-dicyano-2-heptafluoropropylimidazole, 4, 5-dicyano-1, 2, 3-triazolate, lithium tetrafluoroborate, lithium difluoroborate, at least one of lithium fluorosulfonate (n-perfluorobutylsulfonyl) imide. In addition to the above-listed lithium salts B, other lithium salts commonly used in the art to achieve comparable technical effects may also be used in the present invention.
According to some embodiments of the present invention, when the lithium salt is a mixture of lithium salt A and lithium salt B, the mass ratio of lithium salt A to lithium salt B is 20-1: 1-10.
In some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 10-1: 1-10; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 5-1: 1-10; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 5-1: 1-9; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 2-1: 1-10; in some embodiments, the mass ratio of the lithium salt A to the lithium salt B is 2-1: 1-9.
Specifically, when the lithium salt is a mixture of a lithium salt a and a lithium salt B, the mass ratio of the lithium salt a to the lithium salt B may be: 20:1, 20:2, 20:3, 20:4, 20:5, 20:6, 20:7, 20:8, 20:9, 20:10, 19:1, 19:2, 19:3, 19:4, 19:5, 19:6, 19:7, 19:8, 19:9, 19:10, 18:1, 18:2, 18:3, 18:4, 18:5, 18:6, 18:7, 18:8, 18:9, 18:10, 17:1, 17:2, 17:3, 17:4, 17:5, 17:6, 17:7, 17:8, 17:9, 17:10, 16:1, 16:3, 16:5, 16:6, 16:7, 16:9, 16:10, 15:1, 15:2, 15:4, 15:6, 15:7, 15:8, 15:9, 15: 14, 14: 14, 14:7, 14: 14, 14:8, 14, 13:1, 13:2, 13:3, 13:4, 13:5, 13:6, 13:7, 13:8, 13:9, 13:10, 12:1, 12:5, 12:7, 12:9, 12:10, 11:1, 11:2, 11:3, 11:4, 11:5, 11:6, 11:7, 11:8, 11:9, 11:10, 10:1, 10:2, 10:3, 10:4, 10:5, 10:6, 10:7, 10:9, 9:1, 9:2, 9:4, 9:5, 9:6, 9:7, 9:8, 9:10, 8:1, 8:2, 8:3, 8:4, 8:5, 8:7, 8:9, 8:10, 7:1, 7:2, 7:3, 7:4, 7:5, 7:6, 7: 5:6, 7:5, 7:5, 8:5, 7:5, 7:5, 8, 5:6, 5:7, 5:8, 5:9, 5:10, 4:1, 4:3, 4:5, 4:6, 4:7, 4:9, 3:1, 3:2, 3:4, 3:5, 3:6, 3:7, 3:8, 3:9, 3:10, 2:1, 2:3, 2:4, 2:5, 2:6, 2:7, 2:8, 2:9, 2:10, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1: 10.
According to some embodiments of the present invention, when the lithium salt A is lithium triethylborohydride, the mass ratio of the lithium triethylborohydride to the lithium salt B is 20-1: 1-10.
In some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 10-1: 1-10; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 5-1: 1-10; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 5-1: 1-9; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 2-1: 1-10; in some embodiments, the mass ratio of lithium triethylborohydride to lithium salt B is 2-1: 1-9.
Specifically, when the lithium salt a is lithium triethylborohydride, the mass ratio of the lithium triethylborohydride to the lithium salt B may be: 20:1, 20:2, 20:3, 20:4, 20:5, 20:6, 20:7, 20:8, 20:9, 20:10, 19:1, 19:2, 19:3, 19:4, 19:5, 19:6, 19:7, 19:8, 19:9, 19:10, 18:1, 18:2, 18:3, 18:4, 18:5, 18:6, 18:7, 18:8, 18:9, 18:10, 17:1, 17:2, 17:3, 17:4, 17:5, 17:6, 17:7, 17:8, 17:9, 17:10, 16:1, 16:3, 16:5, 16:6, 16:7, 16:9, 16:10, 15:1, 15:2, 15:4, 15:6, 15:7, 15:8, 15:9, 15: 14, 14: 14, 14:7, 14: 14, 14:8, 14, 13:1, 13:2, 13:3, 13:4, 13:5, 13:6, 13:7, 13:8, 13:9, 13:10, 12:1, 12:5, 12:7, 12:9, 12:10, 11:1, 11:2, 11:3, 11:4, 11:5, 11:6, 11:7, 11:8, 11:9, 11:10, 10:1, 10:2, 10:3, 10:4, 10:5, 10:6, 10:7, 10:9, 9:1, 9:2, 9:4, 9:5, 9:6, 9:7, 9:8, 9:10, 8:1, 8:2, 8:3, 8:4, 8:5, 8:7, 8:9, 8:10, 7:1, 7:2, 7:3, 7:4, 7:5, 7:6, 7: 5:6, 7:5, 7:5, 8:5, 7:5, 7:5, 8, 5:6, 5:7, 5:8, 5:9, 5:10, 4:1, 4:3, 4:5, 4:6, 4:7, 4:9, 3:1, 3:2, 3:4, 3:5, 3:6, 3:7, 3:8, 3:9, 3:10, 2:1, 2:3, 2:4, 2:5, 2:6, 2:7, 2:8, 2:9, 2:10, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1: 10.
According to some embodiments of the present invention, when the lithium salt A is lithium tri-tert-butoxyaluminum hydride, the mass ratio of the lithium tri-tert-butoxyaluminum hydride to the lithium salt B is 20-1: 1-10.
In some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 10-1: 1-10; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 5-1: 1-10; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 5-1: 1-9; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 3-1: 1-10; in some embodiments, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B is 3 to 1:1 to 9.
Specifically, when the lithium salt a is lithium tri-tert-butoxyaluminum hydride, the mass ratio of lithium tri-tert-butoxyaluminum hydride to lithium salt B may be exemplified by: 20:1, 20:2, 20:3, 20:4, 20:5, 20:6, 20:7, 20:8, 20:9, 20:10, 19:1, 19:2, 19:3, 19:4, 19:5, 19:6, 19:7, 19:8, 19:9, 19:10, 18:1, 18:2, 18:3, 18:4, 18:5, 18:6, 18:7, 18:8, 18:9, 18:10, 17:1, 17:2, 17:3, 17:4, 17:5, 17:6, 17:7, 17:8, 17:9, 17:10, 16:1, 16:3, 16:5, 16:6, 16:7, 16:9, 16:10, 15:1, 15:2, 15:4, 15:6, 15:7, 15:8, 15:9, 15: 14, 14: 14, 14:7, 14: 14, 14:8, 14, 13:1, 13:2, 13:3, 13:4, 13:5, 13:6, 13:7, 13:8, 13:9, 13:10, 12:1, 12:5, 12:7, 12:9, 12:10, 11:1, 11:2, 11:3, 11:4, 11:5, 11:6, 11:7, 11:8, 11:9, 11:10, 10:1, 10:2, 10:3, 10:4, 10:5, 10:6, 10:7, 10:9, 9:1, 9:2, 9:4, 9:5, 9:6, 9:7, 9:8, 9:10, 8:1, 8:2, 8:3, 8:4, 8:5, 8:7, 8:9, 8:10, 7:1, 7:2, 7:3, 7:4, 7:5, 7:6, 7: 5:6, 7:5, 7:5, 8:5, 7:5, 7:5, 8, 5:6, 5:7, 5:8, 5:9, 5:10, 4:1, 4:3, 4:5, 4:6, 4:7, 4:9, 3:1, 3:2, 3:4, 3:5, 3:6, 3:7, 3:8, 3:9, 3:10, 2:1, 2:3, 2:4, 2:5, 2:6, 2:7, 2:8, 2:9, 2:10, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1: 10.
According to some embodiments provided herein, the lithium salt B is lithium bistrifluoromethanesulfonate imide, lithium bistrifluoromethanesulfonate borate, lithium tetrafluoroborate, lithium difluorobis-oxalato borate, lithium perchlorate, lithium hexafluorophosphate, t-butyllithium, lithium bistrimethylsilylamide, lithium bistrifluoromethanesulfonylimide, lithium diisopropylamide, n-butyllithium, sec-butyllithium, lithium tri-sec-butylborohydride, lithium tri-t-butoxyaluminum hydride, lithium tert-butoxymethyllithium, lithium triethylborohydride, lithium diisopropylamide, lithium bistrimethylsilylamide, lithium acetoacetate, lithium pentamethylcyclopentadienyl, lithium trifluoroethyl-trifluorophosphate, 4, 5-dicyano-2-trifluoromethylimidazole, lithium bis (fluoropropanedioate) borate, 4, 5-dicyano-2-heptafluoropropylimidazole, 4, 5-dicyano-1, any one or two of 2, 3-lithium triazolate and lithium fluorosulfonate (n-perfluorobutylsulfonyl) imide.
According to some embodiments of the present invention, the inorganic filler is at least one of alumina, zinc oxide, titanium oxide, silica, molybdenum disulfide, lithium lanthanum zirconium tantalum oxygen, titanium aluminum lithium phosphate, germanium aluminum lithium phosphate, lithium aluminate, germanium lithium sulfur phosphate, lanthanum lithium titanate, montmorillonite, copper oxide, magnesium oxide, lead titanate, and calcium silicate.
In some embodiments, the inorganic filler is any one of alumina, zinc oxide, titanium oxide, silica, molybdenum disulfide, lithium lanthanum zirconium tantalum oxygen, titanium aluminum lithium phosphate, germanium aluminum lithium phosphate, lithium aluminate, sulfur germanium lithium phosphate, lanthanum lithium titanate, montmorillonite, copper oxide, magnesium oxide, lead titanate, and calcium silicate.
In addition to the above-listed inorganic fillers, other inorganic fillers commonly used in the art to achieve comparable technical results can also be used in the present invention.
According to some embodiments of the present invention, the inorganic filler is added in an amount of 5% to 40%, preferably 5% to 30%, more preferably 8% to 30%, and particularly preferably 10% to 20% of the total mass of the polymer solid electrolyte.
Specifically, the inorganic filler is added in a proportion of the total mass of the polymer solid electrolyte, and the proportion is as follows: 5%, 8%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, etc.
According to some embodiments provided herein, the organic solvent is at least one of acetonitrile, N-dimethylpyrrolidone (NMP), Dimethylacetamide (DMAC) and Dimethylformamide (DMF).
In some embodiments, the organic solvent is any one of acetonitrile, N-dimethylpyrrolidone (NMP), Dimethylacetamide (DMAC), and Dimethylformamide (DMF).
According to some embodiments of the present invention, the temperature of the stirring and mixing is 25 to 80 ℃, for example: 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ and the like; the stirring time is 3-24 h, for example: 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, and so on.
In some embodiments, the temperature of the stirring and mixing is 30-60 ℃, and the stirring time is 6-12 hours. In some embodiments, the temperature of the stirring and mixing is 30-60 ℃, and the stirring time is 12-24 hours; in some embodiments, the temperature of the stirring and mixing is 30-60 ℃, and the stirring time is 16-24 hours.
According to some embodiments of the present invention, the temperature of the vacuum drying is 25 to 60 ℃, for example: 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ and the like; the stirring time is 3-24 h, for example: 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, and so on.
In some embodiments, the temperature of the stirring and mixing is 30 to 50 ℃, and the stirring time is 10 to 24 hours. In some embodiments, the temperature of the stirring and mixing is 30-50 ℃, and the stirring time is 12-24 hours; in some embodiments, the temperature of the stirring and mixing is 30-50 ℃, and the stirring time is 16-24 hours.
According to some embodiments of the invention, the mold is a polytetrafluoroethylene mold.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples were carried out under the conditions described in the specification, under the conventional conditions or under the conditions recommended by the manufacturer, unless otherwise specified. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
3(5PVDF-PEO) - (LTTBA-3LiTFSI) -0.1ZnO polymer solid electrolyte is prepared, wherein the ratio of matrix (PVDF-PEO) to lithium salt (LTTBA-3LiTFSI) is 3:1, the ratio of ZnO to the total mass of the polymer solid electrolyte (matrix + lithium salt + ZnO) is 0.1:1, the mass ratio of PVDF to PEO is 5:1, and the mass ratio of LTTBA to LiTFSI is 1: 3.
Weighing 1g of LTTBA, 3g of LiTFSI, 10g of PVDF, 2g of PEO and 1.78g of ZnO in 150ml of MAC solvent, stirring for 6h at 30 ℃ to obtain a polymeric solid electrolyte slurry, then casting the slurry in a polytetrafluoroethylene mold, self-leveling, transferring into a vacuum drying oven, and carrying out vacuum drying for 24h at 30 ℃ to obtain the 3(5PVDF-PEO) - (LTTBA-3LiTFSI) -0.1ZnO polymeric solid electrolyte.
The obtained polymer solid electrolyte was cut into a circular sheet having a diameter of 15mm and a thickness of about 170 μm, and subjected to an AC impedance test, as shown in FIG. 1, to obtain an impedance value of about 260. omega. and a conductivity of 3.8X10 as calculated from the graph-5S/cm。
Example 2
5(9PVDF-PEO)-(LTTBA-LiClO4) -0.15 preparation of LAGP Polymer solid electrolyte, in which matrix (PVDF-PEO) is mixed with lithium salt (LTTBA-LiClO)4) The ratio of LAGP to the total mass of the polymer solid electrolyte (matrix + lithium salt + ZnO) was 5:1, the ratio of PVDF to PEO was 9:1, and the ratio of LTTBA to LiClO was 0.1:14The mass ratio of (A) to (B) is 1: 1.
Weighing 1g of LTTBA and 1g of LiClO49g PVDF, 1g PEO and 2.12g LAGP in 170mL acetonitrile solvent, stirred at 30 ℃ for 12h to obtain a polymeric solid electrolyte slurry, and then the slurry was cast on polytetrafluoroethyleneSelf-leveling in an ethylene mould, transferring into a drying oven, and blowing and drying for 18h at 30 ℃ by nitrogen to obtain 5(9PVDF-PEO) - (LTTBA-LiClO)4) -0.15LAGP polymer solid electrolyte.
The obtained polymer solid electrolyte was cut into a circular sheet having a diameter of 15mm and a thickness of about 136 μm, and subjected to an AC impedance test, as shown in FIG. 2, from which it was calculated that the impedance value was about 55. omega. and the conductivity was 1.4X10-4S/cm。
Example 3
12(15PVDF-PEO)-(LTEB-9LiBOB)-0.2SiO2Preparation of a Polymer solid electrolyte in which the matrix (PVDF-PEO) and lithium salt ((LTEB-9LiBOB) ratio was 12:1, SiO2The ratio of the total mass of the polymer solid electrolyte (matrix + lithium salt + ZnO) to the total mass of the polymer solid electrolyte is 0.2:1, the mass ratio of PVDF to PEO is 5:1, and the mass ratio of LTEB to LiBOB is 1: 9.
0.1g of LTEB, 0.9g of LiBOB, 11.25g of PVDF, 0.75g of PEO and 3.25g of SiO were weighed out2Stirring in 120ml NMP solvent at 50 deg.C for 8h to obtain solid electrolyte slurry, casting the slurry in polytetrafluoroethylene mould, self-leveling, transferring into vacuum drying oven, and vacuum drying at 50 deg.C for 16h to obtain 12(15PVDF-PEO) - (LTEB-9LiBOB) -0.20SiO2A polymer solid electrolyte.
The obtained polymer solid electrolyte was cut into a circular sheet having a diameter of 15mm and a thickness of about 180 μm, and subjected to an AC impedance test, as shown in FIG. 3, from which it was calculated that the impedance value was about 320. omega. and the conductivity was 3.2X10-5S/cm。
Example 4
4(3PVDF-PEO)-(2LTEB-3LiClO4) -0.1 preparation of LLZTO Polymer solid electrolyte, in which matrix (PVDF-PEO) is mixed with lithium salt (2LTEB-3 LiClO)4) The ratio is 4:1, the ratio of LLZTO to the total mass of the polymer solid electrolyte (matrix + lithium salt + ZnO) is 0.1:1, the mass ratio of PVDF to PEO is 3:1, and LTEB and LiClO4The mass ratio of (A) to (B) is 2: 3.
0.4g of LTEB and 0.6g of LiClO were weighed out43g PVDF, 1g PEO and 0.56g LLZTO in 80ml DMF solvent, stirring at 45 deg.C for 12h to obtain polymeric solidCasting the slurry in a polytetrafluoroethylene mould, automatically leveling, transferring into a vacuum drying oven, and vacuum drying at 45 ℃ for 18h to obtain 4(3PVDF-PEO) - (2LTEB-3Li ClO4) -0.1LLZTO polymer solid electrolyte.
The obtained polymer solid electrolyte was cut into a circular sheet having a diameter of 15mm and a thickness of about 190 μm, and subjected to an AC impedance test, as shown in FIG. 4, from which it was calculated that the impedance value was about 45. omega. and the conductivity was 2.4X10-4S/cm。
Example 5
4(3PVDF-PEO) -LTEB-0.1LLZTO polymer solid electrolyte is prepared, wherein the ratio of matrix (PVDF-PEO) to lithium salt (LTEB) is 4:1, the ratio of LLZTO to the total mass of the polymer solid electrolyte (matrix + lithium salt + ZnO) is 0.1:1, and the mass ratio of PVDF to PEO is 3: 1.
Weighing 1.0g of LTEB, 3g of PVDF, 1g of PEO and 0.56g of LLZTO in 100ml of mixed solution of DMMF, stirring for 12h at 45 ℃ to obtain slurry of the polymerized solid electrolyte, casting the slurry in a polytetrafluoroethylene mold, self-leveling, transferring into a vacuum drying oven, and vacuum-drying for 18h at 45 ℃ to obtain 4(3PVDF-PEO) -LTEB-0.1LLZTO polymer solid electrolyte.
The obtained polymer solid electrolyte was cut into a circular piece having a diameter of 15mm and a thickness of about 218 μm, and subjected to an AC impedance test, as shown in FIG. 5, from which it was calculated that the impedance value was about 1122. omega. and the conductivity was 1.1X10-5S/cm。
Comparative example 1
4(3PVDF-PEO)-LiClO4-0.1 preparation of LLZTO Polymer solid electrolyte, wherein matrix (PVDF-PEO) and lithium salt (LiClO)4) The ratio is 4:1, the ratio of LLZTO to the total mass of the polymer solid electrolyte (matrix + lithium salt + ZnO) is 0.1:1, and the mass ratio of PVDF to PEO is 3: 1.
1.0g LiClO was weighed43g of PVDF, 1g of PEO and 0.56g of LLZTO are put in a 100ml of mixed solution of DMMF and stirred for 12 hours at the temperature of 45 ℃ to obtain slurry of the polymerized solid electrolyte, then the slurry is cast in a polytetrafluoroethylene mould to be self-leveled and is transferred into a vacuum drying oven to be dried for 18 hours in vacuum at the temperature of 45 ℃,4(3PVDF-PEO) -LiClO is obtained4-0.1LLZTO polymer solid electrolyte.
The obtained polymer solid electrolyte was cut into a circular sheet having a diameter of 15mm and a thickness of about 154 μm, and subjected to an AC impedance test, as shown in FIG. 6, from which it was calculated that the impedance value was about 58. omega. and the conductivity was 1.5X10-4S/cm。
Comparative example 2
5(9PVDF-PEO)-(LAH-LiClO4) -0.15 preparation of LAGP Polymer solid electrolyte, in which matrix (PVDF-PEO) is mixed with lithium salt (LAH-LiClO)4) The ratio of LAGP to the total mass of the polymer solid electrolyte (matrix + lithium salt + ZnO) was 5:1, the ratio of PVDF to PEO was 9:1, and the ratio of LAH to LiClO was 0.1:14The mass ratio of (A) to (B) is 1: 1.
1g of Lithium Aluminum Hydride (LAH) and 1g of LiClO were weighed49g of PVDF, 1g of PEO and 2.12g of LAGP were stirred in 170mL of acetonitrile solvent at 30 ℃ for 12 hours to obtain a slurry of the polymeric solid electrolyte, and then the slurry was cast in a polytetrafluoroethylene mold and self-leveled, transferred into a drying oven, and dried at 30 ℃ for 18 hours under nitrogen purge to obtain 5(9PVDF-PEO) - (LAH-LiClO4) -0.15LAGP polymeric solid electrolyte.
The obtained polymer solid electrolyte was cut into a circular sheet having a diameter of 15mm and a thickness of about 220 μm, and subjected to an AC impedance test, as shown in FIG. 7, from which it was calculated that the impedance value was about 277. omega, and the conductivity was 4.5X10- 5S/cm。
Comparative example 3
4(3PVDF-PEO)-(2LBH-3LiClO4) -0.1 preparation of LLZTO Polymer solid electrolyte, in which matrix (PVDF-PEO) is mixed with lithium salt (2LBH-3 LiClO)4) The ratio of LLZTO to the total mass of the polymer solid electrolyte (matrix + lithium salt + ZnO) was 0.1:1, the mass ratio of PVDF to PEO was 3:1, LBH to LiClO4The mass ratio of (A) to (B) is 2: 3.
0.4g of Lithium Borohydride (LBH) and 0.6g of LiClO were weighed out43g PVDF, 1g PEO and 0.56g LLZTO in 80ml DMF solvent, stirring at 45 deg.C for 12h to obtain solid electrolyte slurry, and casting the slurry in polytetrafluoroethylene moldLeveling, transferring into a vacuum drying oven, and vacuum drying at 45 deg.C for 18h to obtain 4(3PVDF-PEO) - (2LBH-3LiClO4) -0.1LLZTO polymer solid electrolyte.
The obtained polymer solid electrolyte was cut into a circular piece having a diameter of 15mm and a thickness of about 179 μm, and subjected to an AC impedance test, as shown in FIG. 8, from which it was calculated that the impedance value was about 135. omega. and the conductivity was 7.5X10-5S/cm。
Lithium battery performance test
The polymer solid electrolyte membrane obtained in example 4 was cut into disks with a diameter of 15mm, and assembled into different button cells, and subjected to a linear cyclic voltammetry test, a full cell cyclic performance test, and a lithium intercalation-deintercalation test, with the results shown in fig. 9 to 11.
As can be seen from FIG. 9, 4(3PVDF-PEO) - (2LTEB-3 LiClO) was prepared by casting4) The electrochemical window of-0.1 LLZTO polymer solid electrolyte can reach 4.9V, which shows that the solid electrolyte has good high-voltage resistance.
As can be seen in FIG. 10, the assembled Li/4(3PVDF-PEO) - (2LTEB-3 LiClO)4)-0.1LLZTO/LiFePO4The button type full cell is subjected to cycle test at 45 ℃ and 0.4C, the first effect can reach 92.5 percent, the first loop capacity is 144mAh/g, the capacity retention rate is 99 percent, and the result shows that 4(3PVDF-PEO) - (2LTEB-3 LiClO)4) The-0.1 LLZTO polymer solid electrolyte has good cycle performance and rate capability.
As can be seen from FIG. 11, 4(3PVDF-PEO) - (2LTEB-3 LiClO)4) -0.1LLZTO polymer solid electrolyte has good lithium intercalation-deintercalation capability at a current density of 0.1mA/cm-2Can stably operate for 1180h without short circuit at the current density of (2) and shows that 4(3PVDF-PEO) - (2LTEB-3 LiClO)4) The-0.1 LLZTO polymer solid electrolyte has good interface stability to the lithium metal cathode.
In the description herein, references to the description of the terms "some embodiments," "other embodiments," "an embodiment," "an example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention and examples have been shown and described above, it is understood that the above embodiments, examples are illustrative and not to be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments, examples by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A polymer solid electrolyte, which is characterized by comprising a polymer matrix, lithium salt and inorganic filler, wherein the polymer matrix is PVDF or a mixture of PVDF and PEO; the lithium salt comprises a lithium salt A, and the lithium salt A is lithium tri-tert-butoxyaluminum hydride or lithium triethylborohydride or a mixture of the lithium tri-tert-butoxyaluminum hydride and the lithium triethylborohydride.
2. The polymer solid electrolyte according to claim 1, wherein when the polymer matrix is a mixture of PVDF and PEO, the mass ratio of PEO to PVDF is 1: 3-25, preferably 1: 3-15.
3. The polymer solid electrolyte according to claim 1, wherein the lithium salt further comprises a lithium salt B, and the lithium salt B is lithium bistrifluoromethanesulfonate imide, lithium bistrifluorosulfonate imide, lithium bisoxalato borate, lithium tetrafluoroborate, lithium difluorobisoxalato borate, lithium perchlorate, lithium hexafluorophosphate, t-butyllithium, lithium bistrimethylsilylamide, lithium bistrifluoromethanesulfonylimide, lithium diisopropylamide, n-butyllithium, sec-butyllithium, lithium tri-sec-butylborohydride, lithium tri-t-butoxyaluminum hydride, lithium tert-butoxymethyllithium, lithium triethylborohydride, lithium diisopropylamide, lithium bistrimethylsilylamide, lithium acetoacetate, lithium pentamethylcyclopentadienyl, lithium trifluoroethyl trifluorophosphate, 4, 5-dicyano-2-trifluoromethylimidazole, lithium bis (fluoropropanoate) borate, 4, 5-dicyano-2-heptafluoropropylimidazole, lithium bis (fluoropropanoate), lithium salt B, lithium salt, 4, 5-dicyano-1, 2, 3-triazolate lithium, and lithium fluorosulfonate (n-perfluorobutylsulfonyl) imide.
4. The polymer solid electrolyte according to claim 3, wherein when the lithium salt is a mixture of lithium salt A and lithium salt B, the mass ratio of lithium salt A to lithium salt B is 20-1: 1-10, preferably 10-1: 1-10, and more preferably 5-1: 1-10.
5. The polymer solid electrolyte according to claim 1, wherein the mass ratio of the lithium salt to the polymer matrix is 1:1 to 20.
6. The polymer solid electrolyte according to claim 1, wherein the inorganic filler is at least one of alumina, zinc oxide, titanium oxide, silica, molybdenum disulfide, lithium lanthanum zirconium tantalum oxygen, lithium titanium aluminum phosphate, lithium germanium aluminum phosphate, lithium aluminate, lithium germanium sulfide, lithium lanthanum titanate, montmorillonite, copper oxide, magnesium oxide, lead titanate, and calcium silicate.
7. The polymer solid electrolyte according to claim 1, wherein the inorganic filler is added in an amount of 5 to 40%, preferably 10 to 20% of the total mass of the polymer solid electrolyte.
8. The method for producing a polymer solid electrolyte according to any one of claims 1 to 7, comprising:
stirring and mixing a polymer matrix, lithium salt and an inorganic filler in an organic solvent to obtain slurry;
and casting the slurry in a mold, and drying in vacuum to obtain the polymer solid electrolyte.
9. The method of claim 1, wherein the organic solvent is at least one of acetonitrile, N-dimethylpyrrolidone, dimethylacetamide, and dimethylformamide.
10. A lithium battery comprising the polymer solid electrolyte according to any one of claims 1 to 7.
CN202010415819.XA 2020-05-16 2020-05-16 Polymer solid electrolyte and preparation method thereof Pending CN111613833A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010415819.XA CN111613833A (en) 2020-05-16 2020-05-16 Polymer solid electrolyte and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010415819.XA CN111613833A (en) 2020-05-16 2020-05-16 Polymer solid electrolyte and preparation method thereof

Publications (1)

Publication Number Publication Date
CN111613833A true CN111613833A (en) 2020-09-01

Family

ID=72203404

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010415819.XA Pending CN111613833A (en) 2020-05-16 2020-05-16 Polymer solid electrolyte and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111613833A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112266313A (en) * 2020-10-09 2021-01-26 西安近代化学研究所 alpha-AlH3-PVDF double-shell structure compound, preparation method and application
CN112290083A (en) * 2020-10-29 2021-01-29 西安越遴新材料研究院有限公司 High-safety composite solid electrolyte and preparation method thereof
CN113097562A (en) * 2021-04-13 2021-07-09 无锡新锂辰能源科技有限公司 Lithium borohydride-garnet type oxide composite solid electrolyte material and preparation method and application thereof
CN113206292A (en) * 2021-04-25 2021-08-03 华南理工大学 Polymer-based composite solid electrolyte and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120251871A1 (en) * 2011-03-29 2012-10-04 Tohoku University All-solid-state battery
CN105098234A (en) * 2015-09-22 2015-11-25 中国科学院物理研究所 Solid electrolyte material, and electrolyte layer and lithium ion battery comprising solid electrolyte material
US20170018768A1 (en) * 2015-07-13 2017-01-19 Sila Nanotechnologies Inc. Stable lithium fluoride-based cathodes for metal and metal-ion batteries
CN107834104A (en) * 2017-12-12 2018-03-23 清陶（昆山）能源发展有限公司 A kind of composite solid electrolyte and preparation method thereof and the application in solid lithium battery
CN108963327A (en) * 2017-05-18 2018-12-07 珠海市赛纬电子材料股份有限公司 A kind of compound PEO solid electrolyte material of inorganic filler and preparation method and all-solid-state battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120251871A1 (en) * 2011-03-29 2012-10-04 Tohoku University All-solid-state battery
US20170018768A1 (en) * 2015-07-13 2017-01-19 Sila Nanotechnologies Inc. Stable lithium fluoride-based cathodes for metal and metal-ion batteries
CN105098234A (en) * 2015-09-22 2015-11-25 中国科学院物理研究所 Solid electrolyte material, and electrolyte layer and lithium ion battery comprising solid electrolyte material
CN108963327A (en) * 2017-05-18 2018-12-07 珠海市赛纬电子材料股份有限公司 A kind of compound PEO solid electrolyte material of inorganic filler and preparation method and all-solid-state battery
CN107834104A (en) * 2017-12-12 2018-03-23 清陶（昆山）能源发展有限公司 A kind of composite solid electrolyte and preparation method thereof and the application in solid lithium battery

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112266313A (en) * 2020-10-09 2021-01-26 西安近代化学研究所 alpha-AlH3-PVDF double-shell structure compound, preparation method and application
CN112266313B (en) * 2020-10-09 2022-03-15 西安近代化学研究所 alpha-AlH3-PVDF double-shell structure compound, preparation method and application
CN112290083A (en) * 2020-10-29 2021-01-29 西安越遴新材料研究院有限公司 High-safety composite solid electrolyte and preparation method thereof
CN113097562A (en) * 2021-04-13 2021-07-09 无锡新锂辰能源科技有限公司 Lithium borohydride-garnet type oxide composite solid electrolyte material and preparation method and application thereof
CN113097562B (en) * 2021-04-13 2024-04-05 无锡新锂耀辉能源科技有限公司 Lithium borohydride-garnet type oxide composite solid electrolyte material and preparation method and application thereof
CN113206292A (en) * 2021-04-25 2021-08-03 华南理工大学 Polymer-based composite solid electrolyte and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN111613833A (en) Polymer solid electrolyte and preparation method thereof
KR100982325B1 (en) Rechargeable lithium battery
CN100546077C (en) Composite positive pole, battery-super electric capacity energy storage means and preparation method
KR101718061B1 (en) Organic electrolytic solution and and Lithium battery comprising the solution
KR101615413B1 (en) Anode active material for lithium secondary battery, preparation method of thereof, and lithium secondary battery comprising the same
CN108767263B (en) Preparation method and application of modified metal lithium negative electrode copper foil current collector
KR20110136740A (en) Electrolyte for electrochemical device, the preparation method thereof and electrochemical device comprising the same
CN115799601A (en) Lithium ion battery
KR20150005492A (en) Electrolyte for electrochemical device and the electrochemical device thereof
CN111048831B (en) Electrolyte for secondary battery and lithium secondary battery comprising same
WO2021189161A1 (en) All solid-state electrolyte composite based on functionalized metal-organic framework materials for li thoum secondary battery and method for manufacturing the same
KR102211367B1 (en) Organic electrolyte and lithium battery employing said electrolyte
KR20140139906A (en) Additive for electrolyte of lithium battery, organic electrolytic solution comprising the same and Lithium battery using the solution
KR20190136382A (en) Lithium secondary battery
KR101142533B1 (en) Metal based Zn Negative Active Material and Lithium Secondary Battery Comprising thereof
WO2019142744A1 (en) Non-aqueous electrolyte secondary battery
CN114864916A (en) Niobium pentoxide coated graphite composite negative electrode material and preparation method thereof
KR101044577B1 (en) Lithium Secondary Battery
KR100698372B1 (en) Manufacturing Mathod of Negative Active Material For Lithium Secondary Battery And Lithium Secondary Battery Comprising The Same
CN108987803B (en) Lithium metal negative electrode film-forming electrolyte for lithium-sulfur battery and additive thereof
CN114204118A (en) PVDF (polyvinylidene fluoride) -based composite solid electrolyte and preparation method thereof
KR20140081466A (en) Negative active material for rechargeable lithium battery, method of preparing the same, and negative electrode and rechargeable lithium battery including the same
KR101853149B1 (en) Anode active material for lithium secondary battery having core-shell structure, lithium secondary battery comprising the material, and method of preparing the material
KR20160105348A (en) Positive electrode active material, and positive electrode and lithium secondary battery comprising the same
CN111342133A (en) Novel non-aqueous electrolyte for lithium ion battery and lithium ion battery

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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200901