CN111900463B - Electrolyte material, preparation method thereof, solid electrolyte and battery - Google Patents
Electrolyte material, preparation method thereof, solid electrolyte and battery Download PDFInfo
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- CN111900463B CN111900463B CN201910368877.9A CN201910368877A CN111900463B CN 111900463 B CN111900463 B CN 111900463B CN 201910368877 A CN201910368877 A CN 201910368877A CN 111900463 B CN111900463 B CN 111900463B
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- crown ether
- electrolyte material
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- ion salt
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- 239000002001 electrolyte material Substances 0.000 title claims abstract description 134
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 150000003983 crown ethers Chemical class 0.000 claims abstract description 145
- 229910021645 metal ion Chemical class 0.000 claims abstract description 76
- 239000011159 matrix material Substances 0.000 claims abstract description 69
- 150000003839 salts Chemical class 0.000 claims abstract description 48
- 239000002202 Polyethylene glycol Substances 0.000 claims description 29
- 229920001223 polyethylene glycol Polymers 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 239000012456 homogeneous solution Substances 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 13
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical class [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 11
- -1 aluminum ion salt Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical class [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 9
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical class [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 6
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 16
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 14
- 229910001415 sodium ion Inorganic materials 0.000 description 13
- 229910001629 magnesium chloride Inorganic materials 0.000 description 12
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 12
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 7
- 235000019341 magnesium sulphate Nutrition 0.000 description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 6
- CMWINYFJZCARON-UHFFFAOYSA-N 6-chloro-2-(4-iodophenyl)imidazo[1,2-b]pyridazine Chemical compound C=1N2N=C(Cl)C=CC2=NC=1C1=CC=C(I)C=C1 CMWINYFJZCARON-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 4
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 description 4
- 235000011151 potassium sulphates Nutrition 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- UBAATXSFIFYRLJ-UHFFFAOYSA-N magnesium;cyclohexane Chemical compound [Mg+2].C1CC[CH-]CC1.C1CC[CH-]CC1 UBAATXSFIFYRLJ-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FKOASGGZYSYPBI-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)alumanyl trifluoromethanesulfonate Chemical compound [Al+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F FKOASGGZYSYPBI-UHFFFAOYSA-K 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses an electrolyte material and a preparation method thereof, a solid electrolyte and a battery, and relates to the technical field of batteries, so that the safety performance of the battery is improved on the premise of ensuring the performance of the battery. The electrolyte material comprises a matrix material, and crown ether and a crown ether complex dispersed in the matrix material; the crown ether is used for controlling the crystallinity of the matrix material, and the crown ether complex is formed by coordinating the crown ether and metal ion salt. The solid electrolyte comprises the electrolyte material provided by the technical scheme. The electrolyte material, the preparation method thereof, the solid electrolyte and the battery provided by the invention are used in the ion battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a preparation method of an electrolyte material, the electrolyte material, a solid electrolyte and a battery.
Background
A lithium ion battery is a secondary battery (rechargeable battery) that mainly operates by movement of lithium ions between a positive electrode and a negative electrode. The material has the characteristics of higher energy density, good cycle performance, no memory effect and the like, and becomes the focus of attention of researchers in recent years.
However, the cost of lithium ion batteries has been high due to the lack of lithium resources, and there is a trend toward a new trend. In order to reduce the manufacturing cost of lithium ion batteries, research and development are being carried out on secondary batteries using low-cost elements such as sodium, magnesium, aluminum and the like, and particularly, aluminum ion batteries have the advantages of high storage capacity, high electron gaining and losing number, low cost and the like, and become novel batteries for replacing lithium ion batteries.
Disclosure of Invention
The invention aims to provide an electrolyte material, a preparation method thereof, a solid electrolyte and a battery, so as to improve the safety performance of the battery on the premise of ensuring the performance of the battery.
In order to achieve the above purpose, the invention provides the following technical scheme:
an electrolyte material comprising a matrix material, and a crown ether complex dispersed in the matrix material; the crown ether is used for controlling the crystallinity of the matrix material, and the crown ether complex is formed by coordinating the crown ether and metal ion salt.
Compared with the prior art, the electrolyte material provided by the invention not only comprises a matrix material, but also comprises crown ether complexes and crown ethers dispersed in the matrix material, and the crown ethers contained in the crown ethers and the crown ether complexes have certain coordination, so that metal ions and the matrix material have good compatibility, and the crown ethers contained in the solid electrolyte prepared from the electrolyte material can effectively ensure the stability of the metal ions when no current flows. In addition, the crown ether contained in the electrolyte material and the crown ether contained in the crown ether complex provided by the invention have weaker coordination with metal ions, so that the solid electrolyte prepared from the electrolyte material is easier to separate from the crown ether when current passes through, and the ion transfer is realized by continuously coordinating and separating with other crown ethers.
In addition, the crown ether can control the crystallinity of the matrix material, so that the crown ether can be used as a plasticizer to ensure that the solid electrolyte solidified from the electrolyte material has better elasticity and toughness when the solid electrolyte material is manufactured; moreover, the crown ether is doped in the matrix material, so that the range of an amorphous region of the matrix material is enlarged, and the process of ion conduction is mainly carried out in the amorphous region of the matrix material, therefore, the dynamic diffusion capacity of metal ions in the electrolyte material is greatly increased under the action of current of the solid electrolyte prepared from the electrolyte material provided by the invention.
Therefore, after the metal ions contained in the crown ether complex in the electrolyte material provided by the invention are separated from the crown ether, the metal ions can be quickly conducted through the matrix material, so that the conductivity of the solid electrolyte is effectively improved, and the solid electrolyte prepared from the electrolyte material can be applied to a battery, so that the danger of electrolyte leakage and even explosion can be avoided on the premise of ensuring that the battery has good performance.
The invention also provides a preparation method of the electrolyte material in the technical scheme, which comprises the following steps:
dissolving a matrix material, metal ion salt and crown ether in a solvent to obtain a uniform solution, so that a part of crown ether is coordinated with metal ions contained in the metal ion salt to obtain a crown ether complex, and the other part of crown ether and the crown ether complex are dispersed in the matrix material;
and removing the solvent contained in the uniform solution to obtain the electrolyte material.
Compared with the prior art, the preparation method of the electrolyte material provided by the invention has the same beneficial effects as the electrolyte material in the technical scheme, and the details are not repeated herein.
The invention also provides a solid electrolyte which comprises the electrolyte material or the electrolyte material prepared by the preparation method of the electrolyte material.
Compared with the prior art, the beneficial effects of the solid electrolyte provided by the invention are the same as those of the preparation method of the electrolyte material in the technical scheme, and are not repeated herein.
The invention also provides a battery which comprises the solid electrolyte.
Compared with the prior art, the beneficial effects of the battery provided by the invention are the same as those of the solid electrolyte in the technical scheme, and are not repeated herein.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a flow chart of a process for preparing an electrolyte material according to an embodiment of the present invention;
FIG. 2 is a photograph of a solid electrolyte made of the electrolyte material prepared in the first embodiment of the present invention;
FIG. 3 is a photograph of a solid electrolyte made of the electrolyte material prepared in the second embodiment of the present invention;
FIG. 4 is a photograph of a solid electrolyte made of the electrolyte material prepared in the comparative example;
FIG. 5 is a photograph of a solid electrolyte made of the electrolyte material prepared in comparative example II;
fig. 6 is a rate diagram of a sodium ion battery based on the electrolyte material prepared in comparative example one;
fig. 7 is a rate diagram of a sodium ion battery based on the electrolyte material prepared in example one;
fig. 8 is a graph comparing the cycle performance of sodium ion batteries based on solid electrolytes made of the electrolyte materials prepared in comparative example one and example one.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without any inventive work are within the scope of the present invention.
The electrolyte material provided by the embodiment of the invention comprises a matrix material, and crown ether and a crown ether complex which are dispersed in the matrix material; the crown ether is used for controlling the crystallinity of a matrix material, and the crown ether complex is formed by coordinating the crown ether and metal ion salt. When the electrolyte material is prepared, the matrix material, the crown ether and the metal ion salt can be dissolved in a solvent, so that a part of the crown ether is coordinated with the metal ion salt contained in the metal ion salt to form a crown ether complex, and the other part of the crown ether is used for controlling the crystallinity of the matrix material; meanwhile, the crown ether and the formed crown ether complex can be fully dispersed in the matrix material.
The electrolyte material comprises a matrix material, and also comprises a crown ether complex and a crown ether which are dispersed in the matrix material, wherein the crown ether and the crown ether complex both contain a macrocyclic polyether with a plurality of oxyethylene structural units, and an oxygen atom contained in a cyclic cavity structure can form a coordination bond with a metal ion to generate a metal organic complex, so that when the crown ether and the crown ether complex are dispersed in the matrix material, the metal ion contained in the crown ether complex has good compatibility with the matrix material, and when a solid electrolyte prepared from the electrolyte material does not have current, the crown ether contained in the solid electrolyte can effectively ensure the stability of the metal ion. In addition, the crown ether contained in the electrolyte material and the crown ether complex provided by the embodiment of the invention have weaker coordination with metal ions, so that the solid electrolyte made of the electrolyte material is easier to separate from the crown ether when current passes through, and the ion transfer is realized by continuously coordinating and separating with other crown ethers.
In addition, the crown ether can control the crystallinity of the matrix material, so that the crown ether can be used as a plasticizer to ensure that the solid electrolyte solidified from the electrolyte material has better elasticity and toughness when the solid electrolyte material is manufactured; moreover, the crown ether is doped in the matrix material, so that the range of an amorphous region of the matrix material is enlarged, and the process of ion conduction is mainly carried out in the amorphous region of the matrix material, therefore, the dynamic diffusion capacity of metal ions in the electrolyte material is greatly increased under the action of current of the solid electrolyte prepared from the electrolyte material provided by the invention.
Therefore, after metal ions contained in the crown ether complex in the electrolyte material provided by the embodiment of the invention are separated from the crown ether, the metal ions can be quickly conducted through the matrix material, so that the conductivity of the solid electrolyte is effectively improved, and the solid electrolyte prepared by the electrolyte material can be applied to a battery, so that the electrolyte leakage and even explosion danger can be avoided on the premise of ensuring that the battery has good performance.
The crown ether dispersed in the matrix material and the crown ether included in the crown ether complex are compounds having a macrocyclic polyether structure, wherein the cyclic cavity refers to a plurality of oxyethylene structural units, and the cyclic cavity is relatively large, so that the ion transfer process, i.e., the process of coordinating the metal ion with the oxygen atom included in the cyclic cavity by the cyclic cavity and the process of detaching the metal ion from the oxygen atom included in the cyclic cavity by the cyclic cavity, are relatively easy to perform.
It is to be explained that the crown ether included in the above electrolyte material is a generic name of a crown ether substance, but does not contain a crown ether complex formed by the crown ether and a metal ion.
The existing sodium, potassium and aluminum plasma batteries are receiving increasing attention as a low-cost battery. For example: the sodium ion battery includes an anode and a cathode for intercalating/deintercalating sodium ions, a separator for physically preventing internal short circuits, and an organic liquid electrolyte through which sodium ions are transferred, or a solid electrolyte for both functions. The sodium ion battery has the advantages of abundant and easily-obtained raw materials, low cost, wide distribution and the like. In addition, sodium in the battery system can not generate electrochemical alloying reaction with aluminum, so that the sodium ion battery can adopt aluminum foil as a negative current collector, can effectively avoid the problem of current collector oxidation caused by over-discharge, is beneficial to the safety of the battery, and achieves the aim of further reducing the cost of the battery. From many perspectives, sodium ion batteries have great potential for commercialization and sustainable use.
Therefore, it is required to develop a solid organic polymer electrolyte for a sodium, potassium, aluminum plasma battery, which provides a solid ion battery with low cost and high stability, and particularly to develop a method for preparing a solid organic polymer electrolyte to improve the conductivity thereof and improve the overall performance of the battery.
Based on this, the above metal ion salt may include an aluminum ion salt, an alkali metal ion salt, or a magnesium ion salt, but is not limited thereto. The alkali metal ion salt includes an aluminum ion salt, an alkali metal ion salt or a magnesium ion salt, but is not limited thereto.
The metal ion salt is alkali metal ion salt, aluminum ion salt or magnesium ion salt. The aluminum ion salt is formed by mixing one or more of aluminum chloride, aluminum nitrate, aluminum sec-butoxide and aluminum trifluoromethanesulfonate in any proportion; the magnesium ion salt is one or more of magnesium chloride, magnesium nitrate and magnesium sulfate. Alkali metal ion salts include sodium ion salts, lithium ion salts, or potassium ion salts; wherein, the sodium ion salt is one or more of sodium sulfate, sodium chlorate, sodium nitrate or sodium trifluoromethanesulfonate, the lithium ion salt is one or more of lithium sulfate, lithium chloride and lithium trifluoromethanesulfonate, and the potassium ion salt is one or more of potassium sulfate, potassium nitrate and potassium chlorate.
The crown ether is one or more of 15-crown-5, 18-crown-6 and cyclohexane-18-crown-6 mixed at any ratio, but is not limited to the above.
Illustratively, for example: when the crown ether is 18-crown-6, the crown ether complex has the following structural formula:
For example: when M isn+Is Na+The structural formula of the crown ether complex is as follows:
it will be appreciated that the above crown ether complexes include not only crown ethers and metal ions, but also anions which balance the charge of the metal ions.
Such as:
in some embodiments, when the electrolyte material is made into a solid electrolyte, the solid electrolyte is not sensitive to water and oxygen, and the battery assembly can be carried out in the air, so that the investment caused by environmental control is greatly reduced. Further, the matrix material is a film-forming material, so that the electrolyte material is more easily cured. Specifically, the matrix material can be one or more of polyethylene glycol (PEO), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), Polyvinyl Alcohol (PAN), polyvinylpyrrolidone (PVP), and poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) mixed in any proportion, and the listed film-forming materials have good water and oxygen resistance, so that the solid electrolyte prepared from the electrolyte material has better water and oxygen resistance.
In some embodiments, if the metal ion salt is less, the conductivity of the solid electrolyte made of the electrolyte material will be lower; therefore, the mass of the metal ion salt is 5-30% of that of the matrix material, and the solid electrolyte made of the electrolyte material has high conductivity and meets the requirement of the battery on the electrolyte.
In some embodiments, when the content of the crown ether is higher, the strength of the electrolyte thin film is reduced, and when the content of the crown ether is lower, the control of the crystallinity of the matrix material by the crown ether is not obvious, and the crystallinity of the solid electrolyte made of the corresponding electrolyte material is not good, so that the total molar amount of the crown ether contained in the crown ether and the crown ether complex is 1.1 to 3 times of the molar amount of the metal ion salt, so that the metal ion can rapidly migrate in the solid electrolyte made of the electrolyte material while the solid electrolyte has lower crystallinity. Meanwhile, when the crystallinity of the solid electrolyte is reduced, the solid electrolyte has good toughness and mechanical strength, so that the environmental adaptability of the solid electrolyte is better.
As shown in fig. 1, an embodiment of the present invention further provides a method for preparing the above electrolyte material, where the method for preparing the electrolyte material includes:
step S100: dissolving a matrix material, metal ion salt and crown ether in a solvent to obtain a uniform solution, coordinating a part of crown ether with metal ions contained in the metal ion salt to obtain a crown ether complex, and dispersing the other part of crown ether and crown ether complex in the matrix material.
Step S200: and removing the solvent contained in the uniform solution to obtain the electrolyte material.
Compared with the prior art, the beneficial effects of the electrolyte material provided by the embodiment of the invention are the same as those of the electrolyte material, and are not described herein again. In addition, the matrix material, the metal ion salt and the crown ether are dissolved in the solvent, so that under the action of the matrix material, the contact probability of metal ions contained in the metal ion salt and the crown ether is reduced, thereby ensuring that a part of the crown ether can be doped in the matrix material to control the crystallinity of the matrix material, and the other part of the crown ether is coordinated with the metal ions contained in the metal ion salt to form a crown ether complex which is doped in the matrix material. Therefore, in the preparation method of the electrolyte material provided by the embodiment of the invention, the doping of the crown ether and the crown ether complex in the matrix material and the formation of the crown ether complex are both carried out in the same system; therefore, the preparation method of the electrolyte material provided by the embodiment of the invention can effectively ensure that the prepared electrolyte material contains both crown ether and a crown ether complex.
In addition, even in the case where the amount of the metal ion salt added is constant, the crown ether added is not sufficient to coordinate with the metal ions contained in the metal ion salt, and in the method for producing an electrolyte material according to an embodiment of the present invention, the crown ether added does not coordinate with all the metal ions contained in the metal ion salt in the presence of the matrix material; in other words, even if the crown ether is added in an insufficient amount to coordinate with the metal ion contained in the metal ion salt, the produced electrolyte material still contains the crown ether and the crown ether ligand.
It is to be understood that the specific kinds of the matrix material, crown ether, and metal ion salt used in the above method for producing an electrolyte material can be referred to above.
In some embodiments, the solvent is one or more selected from acetone, butyl ester, glycerol, pyridine, tetrahydrofuran, acetonitrile, N-methylpyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide.
In some embodiments, the mass of the metal ion salt is 5% to 30% of the mass of the matrix material; the molar amount of crown ether dissolved in the solvent is 1.1 to 3 times the molar amount of the metal ion salt.
In some embodiments, in view of the solubility of the matrix material, the metal ion salt, and the crown ether in the solvent, for which the dissolving of the matrix material, the metal ion salt, and the crown ether in the solvent described above, obtaining a uniform solution comprises:
dissolving the matrix material, the metal ion salt and the crown ether in a solvent at 20-80 ℃, wherein the total mass of the matrix material, the metal ion salt and the crown ether dissolved in each milliliter of the solvent is 500-1000 mg, so that the matrix material, the metal ion salt and the crown ether can be sufficiently dissolved in the solvent.
Moreover, the formed uniform solution has moderate viscosity, and the material cannot be doped unevenly because the dissolved matrix material, the metal ion salt and the crown ether are excessive and excessively viscous; and the problem that the film forming property of the electrolyte material is poor due to long time for removing the solvent caused by too little dissolved matrix material, metal ion salt and crown ether and too low viscosity is solved.
In some embodiments, the removing the solvent contained in the homogeneous solution to obtain the electrolyte material comprises: and (3) evaporating the solvent contained in the uniform solution at 40-110 ℃ to obtain the electrolyte material. When the solvent contained in the homogeneous solution is distilled off at 40 ℃ to 110 ℃, the solvent can be gradually distilled off from the homogeneous solution, and the coordination bond of the crown ether complex can be ensured not to be influenced.
The embodiment of the invention also provides a solid electrolyte which comprises the electrolyte material or the electrolyte material prepared by the preparation method of the electrolyte material.
Compared with the prior art, the beneficial effects of the solid electrolyte provided by the embodiment of the invention are the same as those of the electrolyte material or the preparation method of the electrolyte material, and are not repeated herein.
The embodiment of the invention also provides a battery which comprises the solid electrolyte.
Compared with the prior art, the beneficial effects of the battery provided by the embodiment of the invention are the same as the beneficial effects of the electrolyte material or the preparation method of the electrolyte material provided by the embodiment, and the details are not repeated herein.
The battery may be an alkali metal battery, an aluminum ion battery, or a magnesium ion battery, and the details are not repeated here.
The following is a detailed description of the method for producing the electrolyte material provided in the examples of the present invention, and the following description is given for illustrative purposes only and is not intended to be limiting.
Example one
The preparation method of the electrolyte material provided by the embodiment comprises the following steps:
step S100: dissolving polyethylene glycol, sodium chlorate and 18-crown ether-6 in tetrahydrofuran at 20 ℃ to obtain a uniform solution, so that a part of 18-crown ether-6 is coordinated with sodium ions contained in the sodium chlorate to obtain a crown ether complex, and the other part of 18-crown ether-6 and the crown ether complex are dispersed in the polyethylene glycol; the mass of the sodium chlorate is 15% of the mass of the polyethylene glycol; the molar amount of 18-crown-6 is 2 times that of sodium chlorate; the total mass of polyethylene glycol, sodium chlorate and 18-crown-6 dissolved in tetrahydrofuran was 500mg per ml.
Step S200: tetrahydrofuran contained in the homogeneous solution was distilled off at 67 ℃ to obtain an electrolyte material.
It is understood that the sodium chlorate used in the first example can be replaced by lithium ion salts or potassium ion salts. The potassium ion salt is potassium sulfate, potassium nitrate or potassium chlorate, and the lithium ion salt is lithium sulfate, lithium chloride or lithium trifluoromethanesulfonate.
Example two
The preparation method of the electrolyte material provided by the embodiment comprises the following steps:
step S100: dissolving polyethylene glycol, sodium trifluoromethanesulfonate and 18-crown ether-6 in N, N-dimethylacetamide at 56 ℃ to obtain a uniform solution, so that a part of 18-crown ether-6 is coordinated with sodium ions contained in the sodium trifluoromethanesulfonate to obtain a crown ether complex, and the other part of 18-crown ether-6 and the crown ether complex are dispersed in the polyethylene glycol; the mass of the sodium trifluoromethanesulfonate is 30% of that of the polyethylene glycol; the molar weight of the 18-crown-6 is 1.1 times of that of the sodium trifluoromethanesulfonate; the total mass of polyethylene glycol, sodium triflate and 18-crown-6 dissolved in N, N-dimethylacetamide per ml was 1000 mg.
Step S200: the N, N-dimethylacetamide contained in the homogeneous solution was distilled off at 110 ℃ to obtain an electrolyte material.
It will be appreciated that the sodium trifluoromethanesulfonate used in the second example above may be replaced by a lithium ion salt or a potassium ion salt. The potassium ion salt is potassium sulfate, potassium nitrate or potassium chlorate, and the lithium ion salt is lithium sulfate, lithium chloride or lithium trifluoromethanesulfonate.
EXAMPLE III
The preparation method of the electrolyte material provided by the embodiment comprises the following steps:
step S100: dissolving polyvinylidene fluoride, sodium sulfate, sodium trifluoromethanesulfonate and 15-crown ether-5 in N, N-dimethylformamide at 40 ℃ to obtain a uniform solution, so that a part of 15-crown ether-5 is coordinated with sodium ions contained in the sodium trifluoromethanesulfonate and the sodium sulfate to obtain a crown ether complex, and the other part of 15-crown ether-5 and the crown ether complex are dispersed in the polyvinylidene fluoride; the total mass of the sodium sulfate and the sodium trifluoromethanesulfonate is 25% of the mass of the polyvinylidene fluoride; the molar quantity of the 15-crown-5 is 2.5 times of the total molar quantity of the sodium trifluoromethanesulfonate and the sodium sulfate; the total mass of polyvinylidene fluoride, sodium trifluoromethanesulfonate, sodium sulfate and 15-crown-5 dissolved in each milliliter of N, N-dimethylformamide is 800mg, and the mass ratio of the sodium sulfate to the sodium trifluoromethanesulfonate is 1: 2.
Step S200: the N, N-dimethylformamide contained in the homogeneous solution was distilled off at 100 ℃ to obtain an electrolyte material.
It is understood that the sodium sulfate and the sodium trifluoromethanesulfonate used in the third embodiment can be replaced by any two lithium ion salts or any two potassium ion salts. For example: the potassium ion salt is any two of potassium sulfate, potassium nitrate and potassium chlorate, and the lithium ion salt is any two of lithium sulfate, lithium chloride and lithium trifluoromethanesulfonate.
Example four
The preparation method of the electrolyte material provided by the embodiment comprises the following steps:
step S100: dissolving polymethyl methacrylate, polyvinyl alcohol, magnesium nitrate and cyclohexane-18-crown-6 in pyridine at 56 ℃ to obtain a uniform solution, so that a part of cyclohexane-18-crown-6 is coordinated with magnesium ions contained in the magnesium nitrate to obtain a crown ether complex, and the other part of cyclohexane-18-crown-6 and the crown ether complex are dispersed in the polymethyl methacrylate and the polyvinyl alcohol; the mass of the magnesium nitrate is 10% of the total mass of the polymethyl methacrylate and the polyvinyl alcohol; the molar weight of the cyclohexane-18-crown-6 is 1.5 times that of the magnesium nitrate; the total mass of the polymethyl methacrylate and the polyvinyl alcohol, the magnesium nitrate and the cyclohexane-18-crown-6 dissolved in each milliliter of pyridine is 600mg, and the mass ratio of the polymethyl methacrylate to the polyvinyl alcohol is 1: 1.
Step S200: pyridine contained in the homogeneous solution is distilled off at 80 ℃ to obtain an electrolyte material.
EXAMPLE five
The preparation method of the electrolyte material provided by the embodiment comprises the following steps:
step S100: dissolving polyvinylpyrrolidone, magnesium chloride and cyclohexane-18-crown-6 in glycerol at 20 ℃ to obtain a uniform solution, so that a part of cyclohexane-18-crown-6 is coordinated with magnesium ions contained in the magnesium chloride to obtain a crown ether complex, and the other part of cyclohexane-18-crown-6 and the crown ether complex are dispersed in the polyvinylpyrrolidone; the mass of the magnesium chloride is 5% of that of the polyvinylpyrrolidone; the molar amount of cyclohexane-18-crown-6 is 1.5 times that of magnesium chloride; the total mass of polyvinylpyrrolidone, magnesium chloride and cyclohexane-18-crown-6 dissolved in glycerol per ml was 700 mg.
Step S200: the glycerin contained in the homogeneous solution was distilled off at 40 ℃ to obtain an electrolyte material.
EXAMPLE six
The preparation method of the electrolyte material provided by the embodiment comprises the following steps:
step S100: dissolving poly (vinylidene fluoride-co-hexafluoropropylene), magnesium sulfate, magnesium chloride and 15-crown-5 in butyl ester at 20 ℃ to obtain a uniform solution, so that a part of 15-crown-5 is coordinated with magnesium ions contained in the magnesium sulfate and the magnesium chloride to obtain a crown ether complex, and the other part of 15-crown-5 and the crown ether complex are dispersed in the poly (vinylidene fluoride-co-hexafluoropropylene); the total mass of the magnesium chloride and the magnesium sulfate is 15% of the mass of the poly (vinylidene fluoride-co-hexafluoropropylene); the molar amount of 15-crown-5 is 2.3 times the total molar amount of magnesium chloride and magnesium sulfate; the total mass of poly (vinylidene fluoride-co-hexafluoropropylene), magnesium sulfate, magnesium chloride and 15-crown-5 dissolved in each ml of butyl ester was 500mg, and the mass ratio of magnesium sulfate to magnesium chloride was 3: 1.
Step S200: the butyl ester contained in the homogeneous solution was distilled off at 60 ℃ to obtain an electrolyte material.
EXAMPLE six
The preparation method of the electrolyte material provided by the embodiment comprises the following steps:
step S100: dissolving polyethylene glycol, aluminum chloride and 15-crown ether-5 in N-methyl pyrrolidone at 38 ℃ to obtain a uniform solution, so that a part of 15-crown ether-5 is coordinated with aluminum ions contained in the aluminum chloride to obtain a crown ether complex, and the other part of 15-crown ether-5 and the crown ether complex are dispersed in the polyethylene glycol; the mass of the aluminum chloride is 15 percent of that of the polyethylene glycol; the molar weight of the 15-crown-5 is 1.8 times that of the aluminum chloride; the total mass of polyethylene glycol, aluminum chloride and 15-crown-5 dissolved in each ml of N-methylpyrrolidone was 650 mg.
Step S200: and (3) evaporating nitrogen-methyl pyrrolidone contained in the uniform solution at 90 ℃ to obtain the electrolyte material.
EXAMPLE seven
Step S100: dissolving polyethylene glycol, aluminum trifluoromethanesulfonate and 15-crown ether-5 in acetonitrile at 38 ℃ to obtain a uniform solution, so that a part of 15-crown ether-5 is coordinated with aluminum ions contained in the aluminum trifluoromethanesulfonate to obtain a crown ether complex, and the other part of 15-crown ether-5 and the crown ether complex are dispersed in the polyethylene glycol; the mass of the aluminum trifluoromethanesulfonate is 8% of the mass of the polyethylene glycol; the molar weight of the 15-crown-5 is 2.5 times that of the aluminum chloride; the total mass of polyethylene glycol, aluminum triflate and 15-crown-5 dissolved in acetonitrile per ml was 780 mg.
Step S200: acetonitrile contained in the homogeneous solution was distilled off at 45 ℃ to obtain an electrolyte material.
Example eight
Step S100: dissolving polyethylene glycol, aluminum nitrate, aluminum sec-butoxide and 15-crown ether-5 in acetone at 25 ℃ to obtain a uniform solution, so that a part of 15-crown ether-5 is coordinated with aluminum ions contained in the aluminum nitrate and the aluminum sec-butoxide to obtain a crown ether complex, and the other part of 15-crown ether-5 and the crown ether complex are dispersed in the polyethylene glycol; the total mass of the aluminum nitrate and the aluminum sec-butoxide accounts for 8 percent of the mass of the polyethylene glycol; the molar amount of 15-crown-5 is 3 times the total molar amount of aluminum nitrate and aluminum sec-butoxide; the total mass of polyethylene glycol, aluminum trifluoromethanesulfonate and 15-crown-5 dissolved in acetone per ml was 950mg, and the mass ratio of aluminum nitrate to aluminum sec-butoxide was 2: 3.
Step S200: the acetone contained in the homogeneous solution was distilled off at 30 ℃ to obtain an electrolyte material.
Comparative example 1
The preparation method of the electrolyte material provided by the embodiment comprises the following steps:
step S100: dissolving polyethylene glycol and sodium chlorate in tetrahydrofuran at 20 ℃ to obtain a uniform solution, wherein the mass of the sodium chlorate is 15% of the mass of the polyethylene glycol; the total mass of polyethylene glycol and sodium chlorate dissolved in tetrahydrofuran was 500mg per ml.
Step S200: tetrahydrofuran contained in the homogeneous solution was distilled off at 67 ℃ to obtain an electrolyte material.
FIG. 2 is an electron microscope image of a solid electrolyte made of the electrolyte material prepared in the first example; fig. 4 shows an electron microscope image of a solid electrolyte made of the electrolyte material prepared in comparative example one. As can be seen from a comparison of fig. 2 and 4, the doping uniformity of the electrolyte material prepared in example one is better than that of the electrolyte material prepared in comparative example one.
Comparative example No. two
The preparation method of the electrolyte material provided by the embodiment comprises the following steps:
step S100: dissolving polyethylene glycol and sodium trifluoromethanesulfonate in N, N-dimethylacetamide at 56 deg.C to obtain a uniform solution; the mass of the sodium trifluoromethanesulfonate is 30% of that of the polyethylene glycol; the total mass of polyethylene glycol and sodium trifluoromethanesulfonate dissolved in each ml of N, N-dimethylacetamide was 1000 mg.
Step S200: the N, N-dimethylacetamide contained in the homogeneous solution was distilled off at 110 ℃ to obtain an electrolyte material.
FIG. 3 is an electron microscope image of a solid electrolyte made of the electrolyte material prepared in example two; fig. 5 shows an electron microscope image of a solid electrolyte made of the electrolyte material prepared in comparative example two. Comparing fig. 3 and 5, it can be seen that the doping uniformity of the electrolyte material prepared in example two is better than that of the electrolyte material prepared in comparative example two. Table 1 shows the conductivity of the solid electrolyte made of the electrolyte material.
TABLE 1 conductivity of solid electrolyte made of electrolyte material
| Sample(s) | conductivity/S/cm |
| Example one | 2×10-3 |
| Example two | 0.6×10-3 |
| Example four | 1.8×10-3 |
| EXAMPLE six | 2.7×10-3 |
| Comparative example 1 | 5.3×10-4 |
| Comparative example No. two | 7.9×10-4 |
As can be seen from table 1: in the electrolyte material provided by the embodiment of the invention, crown ether with weak coordination and large supporting holes is selected as a channel for metal ion migration, so that the stability of metal ions and the compatibility of the metal ions and a matrix material can be effectively improved, and the crystallinity of the matrix can be effectively reduced by taking the crown ether as a plasticizer, so that the dynamic diffusion capacity of the metal ions is greatly improved, and the conductivity of a solid electrolyte prepared from the electrolyte material can reach 10-3S/cm, therefore, the electrolytic material prepared by the embodiment of the invention can meet the requirement of a solid electrolyte, so that the solid electrolyteWhen the electrolyte is applied to the battery, the stable performance of the battery is ensured.
In addition, in the electrolyte material provided by the embodiment of the invention, coordination between metal ions and crown ether is weak coordination, and a part of crown ether is doped in the matrix material as a plasticizer, so that the migration speed of the metal ions in the matrix material is accelerated, and the rate capability and the cycling stability of a battery can be effectively improved when the solid electrolyte prepared from the electrolyte material is applied to the battery.
Fig. 6 shows a rate chart of a battery based on the electrolyte material prepared in comparative example one, and fig. 7 shows a rate chart of a battery based on the electrolyte material prepared in example one. Comparing fig. 6 and fig. 7, it can be found that: compared with the battery made of the electrolyte material prepared in the first comparative example, when the solid electrolyte made of the electrolyte material prepared in the embodiment of the invention is applied to the battery, the rate performance of the battery is better, and the charging and discharging efficiency of the battery is higher under the condition of the same rate.
Fig. 8 shows a cycle performance chart of batteries based on the electrolyte materials prepared in comparative example one and example one. As can be seen from fig. 8: compared with the battery made of the electrolyte material prepared in the first comparative example, when the solid electrolyte made of the electrolyte material prepared by the electrolyte preparation method provided by the embodiment of the invention is applied to the battery, the cycling stability of the battery is better.
In the foregoing description of embodiments, the particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (14)
1. An electrolyte material, comprising a matrix material, and a crown ether complex dispersed in the matrix material; the crown ether is used for controlling the crystallinity of the matrix material, and the crown ether complex is formed by coordinating crown ether and metal ion salt;
wherein the total molar amount of the crown ether and the crown ether complex is 2-3 times of the molar amount of the metal ion salt.
2. The electrolyte material of claim 1, wherein the metal ion salt comprises an aluminum ion salt, an alkali metal ion salt, or a magnesium ion salt.
3. The electrolyte material of claim 2, wherein the alkali metal salt is a lithium ion salt, a sodium ion salt, or a potassium ion salt.
4. The electrolyte material of claim 1, wherein the crown ether is one or more of 15-crown-5, 18-crown-6, and cyclohexane-18-crown-6 mixed at any ratio.
5. The electrolyte material of claim 1, wherein the matrix material is a film-forming material.
6. The electrolyte material as claimed in claim 5, wherein the matrix material is one or more of polyethylene glycol, polyvinylidene fluoride, polymethyl methacrylate, polyvinyl alcohol, polyvinyl pyrrolidone, and poly (vinylidene fluoride-co-hexafluoropropylene) mixed at any ratio.
7. The electrolyte material of claim 1, wherein the mass of the metal ion salt is 5-30% of the mass of the matrix material.
8. A method for producing the electrolyte material according to any one of claims 1 to 7, characterized by comprising:
dissolving a matrix material, metal ion salt and crown ether in a solvent to obtain a uniform solution, so that a part of crown ether is coordinated with metal ions contained in the metal ion salt to obtain a crown ether complex, and the other part of crown ether and the crown ether complex are dispersed in the matrix material;
and removing the solvent contained in the uniform solution to obtain the electrolyte material.
9. The method of producing an electrolyte material according to claim 8, characterized in that the molar amount of the crown ether dissolved in a solvent is 2 times to 3 times the molar amount of the metal ion salt.
10. The method of preparing an electrolyte material according to claim 8, wherein dissolving the matrix material, the metal ion salt, and the crown ether in a solvent to obtain a homogeneous solution comprises:
dissolving the matrix material, the metal ion salt and the crown ether in a solvent at the temperature of 20-80 ℃, wherein the total mass of the dissolved metal ion salt, the crown ether and the matrix material in each milliliter of the solvent is 500-1000 mg.
11. The method for producing an electrolyte material according to claim 8, wherein the removing the solvent contained in the homogeneous solution to obtain the electrolyte material comprises:
and (3) evaporating the solvent contained in the uniform solution at 40-110 ℃ to obtain the electrolyte material.
12. The method of claim 8, wherein the solvent is one or more selected from acetone, butyl ester, glycerol, pyridine, tetrahydrofuran, acetonitrile, N-methylpyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide.
13. A solid electrolyte comprising the electrolyte material according to any one of claims 1 to 7 or the electrolyte material produced by the method for producing an electrolyte material according to any one of claims 8 to 12.
14. A battery comprising the solid electrolyte according to claim 13.
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| CN1051569A (en) * | 1989-11-07 | 1991-05-22 | 广州市华远电热电器厂 | High-molecular composite solid electrolyte and method for making |
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