CN117543076A - Oxa-addition polyether ester group all-solid polymer electrolyte and preparation method and application thereof - Google Patents
Oxa-addition polyether ester group all-solid polymer electrolyte and preparation method and application thereof Download PDFInfo
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- CN117543076A CN117543076A CN202410033034.4A CN202410033034A CN117543076A CN 117543076 A CN117543076 A CN 117543076A CN 202410033034 A CN202410033034 A CN 202410033034A CN 117543076 A CN117543076 A CN 117543076A
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 94
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 63
- 229920000570 polyether Polymers 0.000 title claims abstract description 63
- 125000004185 ester group Chemical group 0.000 title claims abstract description 18
- 239000007787 solid Substances 0.000 title claims description 54
- 238000002360 preparation method Methods 0.000 title abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- 150000002148 esters Chemical class 0.000 claims description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- -1 lithium tetrafluoroborate Chemical group 0.000 claims description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims description 23
- 159000000002 lithium salts Chemical class 0.000 claims description 23
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000012528 membrane Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 239000004020 conductor Substances 0.000 claims description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- VOEUMFXKYRCDKK-UHFFFAOYSA-N FS(=N)F.FS(=N)F.[Li] Chemical compound FS(=N)F.FS(=N)F.[Li] VOEUMFXKYRCDKK-UHFFFAOYSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920000379 polypropylene carbonate Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
-
- 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
-
- 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
Abstract
The invention discloses an oxa-addition polyether ester group all-solid-state polymer electrolyte and a preparation method and application thereof, and belongs to the technical field of lithium ion battery electrolytes. The structural formula of the oxa-addition polyether ester group all-solid-state polymer electrolyte isThe block polymer electrolyte has good interface stability and wide electrochemical window>4.5V), high room temperature ionic conductivity>10 ‑5 Scm ‑1 )。
Description
Technical Field
The invention belongs to the technical field of lithium ion battery electrolytes, and particularly relates to an oxa-addition polyether ester-based all-solid-state polymer electrolyte, and a preparation method and application thereof.
Background
Portable energy storage, renewable energy storage, consumer electronics and electric automobileAnd electric aviation, as it is capable of meeting the complex design and energy density requirements of these products. Since the commercialization of lithium ion battery technology in the 90 th century of 20, mobile energy sources have been used based on this technology. However, commercial lithium ion batteries generally use graphite or LiC 6 （372mAh g -1 ) Is a negative electrode material, compared with a lithium metal negative electrode (3840 mAh g) -1 ) Its capacity is only about 10wt.%. Therefore, in order to meet the requirements of the future society on energy storage technology, the development of the lithium metal negative electrode battery has great significance. However, the development of lithium metal batteries faces a number of problems, most notably lithium dendrite growth during charge and discharge of the battery. The non-uniform deposition of lithium dendrites during the charge and discharge cycles of the battery may form lithium dendrites, and its formation may not only lead to capacity fade caused by electrode separation, but also may penetrate the separator to cause short circuit of the battery, causing thermal runaway inside the battery, causing safety problems such as explosion and fire. These problems can be solved by replacing the conventional liquid electrolyte with a solid electrolyte, wherein the solid polymer electrolyte has the advantages of good structural control, high interface compatibility, convenient processing and the like, and is considered as a solid electrolyte material for a lithium metal battery with great prospect. The ionic conductivity at room temperature is very low due to the higher crystallinity of the well-developed conventional solid state electrolytes such as PEO-based solid state electrolytes (10 −8 ~10 −7 S cm −1 ) Can not meet the ionic conductivity requirement of the electrolyte in practical application (at room temperature>10 −4 S cm −1 ) And the reaction time is long, the reaction temperature is high, and further progress is difficult to achieve. Therefore, the development of a polymer electrolyte with high room temperature ionic conductivity, rapid reaction, simple experimental conditions and stable electrochemical performance becomes a hot spot.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an oxa-addition polyether ester group all-solid-state polymer electrolyte, and a preparation method and application thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the technical scheme is as follows: an oxa-addition polyether ester group all-solid polymer electrolyte has a structural formula shown in a formula (I):
(I)
Wherein R is、/>、/>、/>Or->The method comprises the steps of carrying out a first treatment on the surface of the n is any integer between 1 and 500, and m is any integer between 1 and 500.
The second technical scheme is as follows: the preparation method of the oxa-addition polyether ester-based all-solid-state polymer electrolyte comprises the following steps:
adding lithium salt into the conductive material, and performing ultrasonic treatment or stirring until the lithium salt is dissolved to obtain a precursor solution 1;
adding raw materials into the precursor solution 1, and carrying out ultrasonic treatment or stirring until the raw materials are dissolved to obtain a precursor solution 2; wherein the raw material R is ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol or triethylene glycol;
and adding a catalyst into the precursor solution 2, and carrying out ultrasonic treatment or stirring until the catalyst is dissolved, and reacting at room temperature to obtain the oxa-addition polyether ester-based all-solid polymer electrolyte.
When the raw material is ethylene glycol ether, the structural formula of the oxa-addition polyether ester group all-solid polymer electrolyte is as follows:
；
when the raw material is ethylene glycol, the structural formula of the oxa-addition polyether ester-based all-solid-state polymer electrolyte is as follows:
；
when the raw material is 1, 3-propylene glycol, the structural formula of the oxa-addition polyether ester-based all-solid-state polymer electrolyte is as follows:
；
when the raw material is 1, 4-butanediol, the structural formula of the oxa-addition polyether ester group all-solid-state polymer electrolyte is as follows:
；
when the raw material is triethylene glycol, the structural formula of the oxa-addition polyether ester-based all-solid-state polymer electrolyte is as follows:
。
further, the lithium salt is lithium tetrafluoroborate (LiBF 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium bis (oxalato) borate (LiBOB), lithium difluoro (LiDFOB) oxalato borate (LiDFOB), lithium bis (difluoro) sulfonimide (LiLSI), lithium bis (trifluoromethyl) sulfonimide (LiTFSI), lithium perchlorate (LiClO) 4 ) Or lithium hexafluorophosphate (LiPF) 6 ）；
The conductive material is PEGDA (polyethylene glycol dimethacrylate), PTMC (polytrimethylene carbonate), PEG (polyethylene glycol), PEC (chlorinated polyethylene), PDXO (polymer of 3, 4-ethylenedioxythiophene monomer), PEO (polyoxyethylene) or PPC (polypropylene carbonate);
the catalyst is butyl (methyl) acrylate, tetramethyl guanidine, methyl (methyl) acrylate, ethyl (methyl) acrylate, propyl (methyl) acrylate or polyethylene glycol methacrylate.
Further, the molar ratio of the lithium salt to the conductive material to the raw material R to the catalyst is (0.1-1) to (1-5) to 1 to (0.1-1); the reaction time at room temperature is 10min.
The technical scheme is as follows: the oxa-addition polyether ester-based all-solid polymer electrolyte membrane is prepared by using the oxa-addition polyether ester-based all-solid polymer electrolyte.
The technical scheme is as follows: the preparation method of the oxa-addition polyether ester-based all-solid polymer electrolyte membrane comprises the steps of mixing the oxa-addition polyether ester-based all-solid polymer electrolyte with lithium salt, uniformly dripping the obtained precursor solution onto a carrier, and curing for 5-24 hours at 30 ℃ to form a film, thus obtaining the oxa-addition polyether ester-based all-solid polymer electrolyte membrane.
Further, the molar ratio of the oxa-addition polyether ester-based all-solid-state polymer electrolyte to the lithium salt is (1-20) to 1. The carrier may be a nonwoven or glass fiber.
Further, the lithium salt used in preparing the oxa-addition polyether ester-based all-solid polymer electrolyte membrane is different from the lithium salt used in preparing the oxa-addition polyether ester-based all-solid polymer electrolyte membrane, and when the oxa-addition polyether ester-based all-solid polymer electrolyte membrane is prepared, the lithium salt is lithium bis (trifluoromethanesulfonyl) imide, lithium tetrafluoroborate or lithium hexafluorophosphate.
The fifth technical scheme is that: the application of the oxa-addition polyether ester-based all-solid-state polymer electrolyte in a solid-state lithium ion battery.
The sixth technical scheme is as follows: the application of the oxa-addition polyether ester-based all-solid polymer electrolyte membrane in a solid lithium ion battery. The solid lithium ion battery comprises a positive electrode, a negative electrode and an oxa-addition polyether ester-based all-solid polymer electrolyte membrane.
The material of the positive electrode is lithium cobaltate, lithium nickelate or lithium iron phosphate.
The negative electrode is made of metal lithium, metal lithium alloy or graphite.
Compared with the prior art, the invention has the following advantages and technical effects:
1. the polyether ester group all-solid-state polymer electrolyte is prepared through oxa addition reaction.
The polyether ester is fully amorphous and can dissolve Li salt and serve as Li + A transport channel that can increase the ionic conductivity and ionic transport number of the polymer electrolyte at room temperature; the c=c double bond compound can act as a skeleton, improving the mechanical and thermal stability of the block polymer electrolyte. The polymer electrolyte has good interface stability and wide electrochemical window>4.5V), high room temperature ionic conductivity>10 -5 S cm -1 )。
2. The polyether ester group all-solid-state polymer electrolyte has different types of R group structures, and the structure of the whole polymer electrolyte can be changed by adjusting the structure of the R group, so that different mechanical properties and electrochemical properties are obtained to meet different requirements.
3. The polyether ester group all-solid-state polymer electrolyte has simple preparation process and can be quantitatively produced.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application, illustrate and explain the application and are not to be construed as limiting the application. In the drawings:
FIG. 1 is a flow chart of the chemical reaction of the present invention.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The present invention employs such oxanucleophilic addition reactions for the synthesis of oxapolyether ester-based polymer electrolytes. The synthesis of oxygen is a method commonly used in organic synthesis, which can build up an oxygen-containing heterocyclic structure by introducing oxygen atoms. The oxa reaction can construct a plurality of sites of oxygen atoms for complexing lithium ions in the structure, and the rate of lithium ion transmission is increased so as to greatly improve the electrochemical performance of the lithium ion.
The "room temperature" as used herein is calculated as 25.+ -. 2 ℃ unless otherwise indicated.
The raw materials used in the following examples of the present invention are all commercially available.
The anode and cathode materials in the assembled battery are not the research focus of the invention, and can be realized only by selecting conventional materials in the field, and the subsequent description is omitted.
The following examples serve as further illustrations of the technical solutions of the invention.
Example 1
When the raw material is ethylene glycol ether, the structural formula of the oxa-addition polyether ester group all-solid polymer electrolyte is as follows:
wherein n=2 and m=1.
Preparation of oxa-addition polyether ester-based all-solid-state polymer electrolyte:
lithium salt lithium bis (trifluoromethylsulfonyl) imide (1.04 g,0.45 mmol) was added to a beaker with a magnet, and the conductive material PEGDA (4 g,10mmol, used PEGDA molecular weight 400 g/mol) was dissolved in the beaker with stirring for 5 min; then adding ethylene glycol ether (0.176 g,20 mmol), stirring for 5min for dissolution; finally, adding catalyst tetramethylguanidine (0.115 g,1 mmol) into a beaker, stirring for 5min for dissolution, and then reacting for 10min at room temperature to obtain the oxa-addition polyether ester group all-solid polymer electrolyte.
Preparation of oxa-addition polyether ester-based all-solid polymer electrolyte membrane:
and mixing the prepared 300 mu L of oxa-addition polyether ester-based all-solid polymer electrolyte and lithium salt (LiTFSI) according to the mol ratio of 5:1, uniformly dripping the obtained precursor solution onto a glass fiber carrier, and curing for 12 hours at 30 ℃ to form a film to obtain the oxa-addition polyether ester-based all-solid polymer electrolyte membrane.
Assembling a battery:
the polyether ester based all solid polymer electrolyte is clamped by two stainless steel sheets, a 2032 button cell is assembled, the ion conductivity at room temperature is measured, L is the thickness of the polymer electrolyte according to the formula sigma=L/SR, S is the area of the stainless steel sheets, R is the measured impedance value, and the test result is shown in Table 1.
The polyether ester based all-solid-state polymer electrolyte is clamped by a stainless steel sheet and a lithium sheet to form a 2032 button cell, and the block polymer all-solid-state lithium ion battery comprises the following structures: positive electrode shell-spring sheet-stainless steel gasket-positive electrode material-polymer electrolyte-negative electrode material-negative electrode shell. Electrochemical stability window (initiation voltage 2.4V, most preferably) was measured by linear voltammetric scanningHigh potential 5.5V, scanning speed 1mVs -1 ）。
Example 2
The difference is that in the preparation process of the oxa-addition polyether ester-based all-solid polymer electrolyte, the conductive material is PEG, and the dosage is 4g and 10mmol.
Example 3
The difference is that in the preparation process of the oxa addition polyether ester group all-solid polymer electrolyte, the conductive material is PDXO, and the dosage is 5g and 11mmol.
TABLE 1 Properties of oxa-addition polyetherester-based all-solid Polymer electrolytes obtained in examples 1 to 3
As can be seen from Table 1, in the oxapolyether ester-based all-solid polymer electrolyte, as the content of EO chain increases, the room temperature ion conductivity of the electrolyte also increases, indicating that EO segments and ester groups in the polyether ester-based all-solid polymer electrolyte are favorable for Li + Transmitted, and the like.
Example 4
The difference is that in the preparation process of the oxa addition polyether ester group all-solid polymer electrolyte, the catalyst is polyethylene glycol methacrylate.
Example 5
The difference from example 1 is that in the preparation of the oxa-addition polyether ester-based all-solid polymer electrolyte, the catalyst is ethyl (meth) acrylate.
Example 6
The difference from example 1 is that in the preparation of the oxa-addition polyether ester-based all-solid polymer electrolyte, the catalyst is butyl (meth) acrylate.
By analyzing the polymer electrolytes obtained in examples 4 to 6, it was found that the polyether ester-based all solid polymer electrolytes were successfully prepared by adding all of the above three catalysts, and the ionic conductivity at room temperature was 1.23X 10 in this order -4 S cm -1 、1.18×10 -4 S cm -1 、1.16×10 -4 S cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The electrochemical stability window was 5.10V, 5.08V, 5.12V in this order.
Overall, it was found that the change of the catalyst did not have a great influence on the system.
Example 7
As in example 1, the difference is that in the preparation of the oxa-addition polyether ester-based all-solid polymer electrolyte, the lithium salt is lithium hexafluorophosphate (LiPF 6 )。
Example 8
As in example 1, the difference is that in the preparation of the oxa-addition polyether ester-based all-solid polymer electrolyte, the lithium salt is lithium tetrafluoroborate (LiBF 4 )。
By analyzing the polymer electrolytes obtained in examples 7 to 8, it was found that the polyether ester based all solid polymer electrolytes were also successfully prepared by adding the above two lithium salts, and the ionic conductivity at room temperature was 2.30X10 in order -4 S cm -1 、2.52×10 -4 S cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The electrochemical stability window was 4.72V, 4.82V in order.
Example 9
The difference from example 1 is that n=17, m=12, the specific method is: lithium salt (1.04 g,0.45 mmol) was added to a beaker with a magnet, and the conductive material PEGDA (4 g,10 mmol/(4000 g/mol; brand microphone)) was dissolved in the beaker with stirring for 5 min; then adding ethylene glycol ether (0.176 g,20 mmol), stirring for 5min for dissolution; finally, adding catalyst tetramethylguanidine (0.115 g,1 mmol) into a beaker, stirring for 5min for dissolution, and then reacting for 10min at room temperature to obtain the oxa-addition polyether ester group all-solid polymer electrolyte precursor solution. And (3) sucking 300 mu L of the prepared oxa-addition polyether ester-based all-solid polymer electrolyte precursor solution by a pipetting gun, uniformly dripping the oxa-addition polyether ester-based all-solid polymer electrolyte precursor solution onto a glass fiber carrier, and curing the oxa-addition polyether ester-based all-solid polymer electrolyte precursor solution at 30 ℃ for 12 hours to form a film, thus obtaining the oxa-addition polyether ester-based all-solid polymer electrolyte membrane.
The polymer electrolyte prepared in this example was analyzed to have an ion conductivity of 3.3X10 at room temperature -4 S cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The electrochemical stability window was 5.20V.
Example 10
The difference from example 1 is that the starting material is ethylene glycol.
The polymer electrolyte prepared in this example was analyzed to have an ion conductivity of 1.65X10 at room temperature -5 S cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The electrochemical stability window was 4.5V.
Example 11
The difference from example 1 is that the starting material is 1, 3-propanediol.
The polymer electrolyte prepared in this example was analyzed to have an ion conductivity of 1.72X10 at room temperature -5 S cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The electrochemical stability window was 4.70V.
Example 12
The same as in example 1 was followed except that 1, 4-butanediol was used as the starting material.
The polymer electrolyte prepared in this example was analyzed to have an ion conductivity of 1.63X10 at room temperature -5 S cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The electrochemical stability window was 4.62V.
Example 13
The difference from example 1 is that the starting material is triethylene glycol.
The polymer electrolyte prepared in this example was analyzed to have an ion conductivity of 1.32X10 at room temperature -4 S cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The electrochemical stability window was 4.8V.
Example 14
The difference from example 1 is that LiTFSI lithium salt is added in an amount of 0.52g.
Example 15
The difference from example 1 is that LiTFSI lithium salt is added in an amount of 1.56g.
The polymer electrolytes prepared in example 1, example 14 and example 15 were tested for electrochemical basic properties, and the results are shown in table 2.
TABLE 2 Properties of oxa-addition polyetherester-based all-solid Polymer electrolytes obtained in examples 1, 14 and 15
Wherein the test criteria are:
ion conductivity is typically tested by electrochemical impedance spectroscopy (electrochemical impedance spectroscopy EIS). The electrochemical impedance spectrum method is an electric measurement method which takes sine wave potential with small amplitude as disturbance signal. Because the system is disturbed by the small-amplitude electric signal, on one hand, the system can be prevented from generating large color sounds, and on the other hand, the disturbance and the response of the system are approximately in a linear relation, so that the mathematical processing of the measurement result is simplified. The impedance of the polymer electrolyte is obtained by EIS test, and then the impedance is calculated according to the following formula
Ion conductivity of the polymer electrolyte was calculated:
σ = L / RS
wherein: sigma-ion conductivity (S/cm), L-electrolyte thickness cm), R-electrolyte impedance (omega), S-electrolyte area (cm).
The electrochemical stability window is the voltage range over which the polymer electrolyte can operate stably. The operating voltage range of lithium batteries is typically 3-4.5V (vs. Li/Li), which requires that the polymer electrolyte be able to ensure proper and stable operation of the battery within the electrochemical stability window. The electrochemical stability window of the polymer electrolyte is tested by using an electrochemical workstation to conduct linear sweep voltammetry test by sandwiching the polymer electrolyte between a lithium sheet and a steel sheet until the temperature reaches or is used, typically a metal sheet is used as a negative electrode, a reference electrode and a stainless steel sheet. The test range is generally 0-6V, the voltage sweeping speed is set to be 2.5-6V, and the three-electrode system is tested.
In conclusion, the room temperature ionic conductivity of the polymer electrolyte is 1.63 multiplied by 10 -5 -3.28×10 -4 S cm -1 The electrochemical stability window is 4.5-5.2V.
The foregoing is merely a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present application should be covered in the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. An oxa-addition polyether ester group all-solid polymer electrolyte is characterized in that the structural formula is shown as the formula (I):
(I)
Wherein R is、/>、/>、/>Or->The method comprises the steps of carrying out a first treatment on the surface of the n is any integer between 1 and 500, and m is any integer between 1 and 500.
2. A method for preparing the oxa-addition polyether ester-based all-solid-state polymer electrolyte according to claim 1, comprising the steps of:
adding lithium salt into the conductive material, and performing ultrasonic treatment or stirring until the lithium salt is dissolved to obtain a precursor solution 1;
adding raw materials into the precursor solution 1, and carrying out ultrasonic treatment or stirring until the raw materials are dissolved to obtain a precursor solution 2; wherein the raw materials are ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol or triethylene glycol;
and adding a catalyst into the precursor solution 2, and carrying out ultrasonic treatment or stirring until the catalyst is dissolved, and reacting at room temperature to obtain the oxa-addition polyether ester-based all-solid polymer electrolyte.
3. The method for preparing an oxa-addition polyether ester-based all-solid-state polymer electrolyte according to claim 2, wherein,
the lithium salt is lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium bisdifluorosulfimide, lithium bistrifluoromethylsulfonimide, lithium perchlorate or lithium hexafluorophosphate;
the conductive material is PEGDA, PTMC, PEG, PEC, PDXO, PEO or PPC;
the catalyst is butyl (methyl) acrylate, tetramethyl guanidine, methyl (methyl) acrylate, ethyl (methyl) acrylate, propyl (methyl) acrylate or polyethylene glycol methacrylate.
4. The method for preparing the oxa-polyether-ester-based all-solid-state polymer electrolyte according to claim 2, wherein the molar ratio of the lithium salt to the conductive material to the raw material to the catalyst is (0.1-1) to (1-5) to 1 to (0.1-1).
5. An oxa-polyether-ester-based all-solid polymer electrolyte membrane prepared by using the oxa-polyether-ester-based all-solid polymer electrolyte according to claim 1.
6. The method for preparing an oxa-addition polyether ester-based all-solid polymer electrolyte membrane according to claim 5, wherein the oxa-addition polyether ester-based all-solid polymer electrolyte is mixed with lithium salt, the obtained precursor solution is uniformly dripped on a carrier, and the obtained precursor solution is solidified to form a membrane, so that the oxa-addition polyether ester-based all-solid polymer electrolyte membrane is obtained.
7. The method for producing an oxa-polyether-ester-based all-solid polymer electrolyte membrane according to claim 6, wherein the molar ratio of the oxa-polyether-ester-based all-solid polymer electrolyte to the lithium salt is (1-20): 1.
8. The method for producing an oxa-addition polyether ester-based all-solid polymer electrolyte membrane according to claim 6, wherein the lithium salt is lithium bistrifluoromethane sulfonimide, lithium tetrafluoroborate or lithium hexafluorophosphate.
9. Use of the oxa-addition polyether ester-based all-solid-state polymer electrolyte according to claim 1 in solid-state lithium ion batteries.
10. Use of the oxa-addition polyether ester-based all-solid polymer electrolyte membrane according to claim 5 in solid lithium ion batteries.
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