CN113381065A - Polymer composite solid electrolyte and preparation method and application thereof - Google Patents
Polymer composite solid electrolyte and preparation method and application thereof Download PDFInfo
- Publication number
- CN113381065A CN113381065A CN202110557587.6A CN202110557587A CN113381065A CN 113381065 A CN113381065 A CN 113381065A CN 202110557587 A CN202110557587 A CN 202110557587A CN 113381065 A CN113381065 A CN 113381065A
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- lithium
- polymer composite
- polymer
- composite solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 67
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002608 ionic liquid Substances 0.000 claims abstract description 19
- 239000004593 Epoxy Substances 0.000 claims abstract description 15
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 22
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical group C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 11
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- -1 polyoxyethylene Polymers 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 8
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910013188 LiBOB Inorganic materials 0.000 claims description 3
- 229910010941 LiFSI Inorganic materials 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 claims 1
- 239000003822 epoxy resin Substances 0.000 claims 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims 1
- 229920000647 polyepoxide Polymers 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000010494 dissociation reaction Methods 0.000 abstract description 4
- 230000005593 dissociations Effects 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 239000005518 polymer electrolyte Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 229910000846 In alloy Inorganic materials 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 229910003480 inorganic solid Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 2
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 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
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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 relates to the technical field of lithium ion batteries, in particular to a polymer composite solid electrolyte, and a preparation method and application thereof. The invention improves the mechanical property of the polymer solid electrolyte based on the bicontinuous crosslinking treatment, introduces the ionic liquid and the succinonitrile into a crosslinking system, utilizes the ionic liquid to have higher dissociation tendency to free ions, utilizes the succinonitrile to inhibit the crystallization of the epoxy polymer, improves the solubility of lithium salt, and synergistically improves the ionic conductivity of the polymer solid electrolyte.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a polymer composite solid electrolyte and a preparation method and application thereof.
Background
With the increasing use of electronic devices, people have an increasing interest in energy storage devices, such as lithium ion batteries and supercapacitors. The current demand for emerging electric vehicles, 5G communication technologies and smart grids is rapidly increasing, forcing lithium ion batteries, the primary energy storage technology, to reach limits in terms of power and energy density, and presenting challenges to the development of next-generation high-energy batteries, such as lithium metal solid state batteries. The side reaction of the lithium metal negative electrode with the traditional liquid electrolyte interface and the deterioration evolution of lithium dendrites can generate a large resistance layer on the lithium metal side (solid electrolyte interface), thereby greatly reducing the cycle life and safety of the lithium metal secondary battery.
To cope with these problems, a quasi-solid or all-solid electrolyte may be used as a substitute for a conventional liquid electrolyte. The solid electrolyte can fundamentally solve the problems of the liquid electrolyte, and can be divided into two broad categories, i.e., inorganic electrolytes and polymer electrolytes, generally, inorganic electrolytes are made of a mixture of a multi-component inorganic material and a lithium salt, but the preparation conditions are severe and the cost is high, so that mass production is very difficult, and low ionic conductivity and unstable interface with an electrode are exhibited at room temperature. Therefore, a solid electrolyte based on a polymer film is considered to be an ideal choice for a solid electrolyte due to its excellent safety, compatibility and processability.
Polymer electrolytes are typically prepared by dissolving ionic metal salts of low lattice energy in a polymer matrix by coordination between metal ions and matrix ligands. The main drawback of polymer electrolyte membranes is their low ionic conductivity compared to conventional liquid electrolytes, and there remains a considerable technical challenge to develop solid polymer electrolyte membranes with high ionic conductivity and mechanical strength.
Chinese patent literature discloses "a solid electrolyte and a method for producing the same", and application publication No. CN 112292780a, which improves the ionic conductivity of the electrolyte by adding boron nitride to a solid electrolyte containing polysiloxane. However, boron nitride particles have the disadvantages of easy agglomeration and low interfacial compatibility with polymer electrolytes.
Chinese patent document discloses "a composite solid electrolyte, a method for preparing the same, and an application thereof in a solid secondary battery", wherein the application publication number is CN 112234249a, and the composite solid electrolyte used in the invention is composed of inorganic solid electrolyte particles and a polymer electrolyte coating layer formed on the surface of the inorganic solid electrolyte particles. However, the polymer solid electrolyte is coated on the surface of the inorganic solid electrolyte, and the obtained composite solid electrolyte has poor processability and low compatibility with electrodes, so that certain technical limitations exist.
Disclosure of Invention
The invention provides a polymer composite solid electrolyte based on bicontinuous crosslinking, aiming at overcoming the problems in the prior art.
The invention also provides a preparation method of the polymer composite solid electrolyte, which is simple to operate, has no special requirements on equipment and is easy to industrialize.
The invention also provides application of the polymer composite solid electrolyte in preparation of the composite positive plate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polymer composite solid electrolyte is formed by diglycidyl ether A and diglycidyl ether B and an epoxy polymer to form a double-crosslinked structure, and the double-crosslinked structure is filled with an ionic liquid, Succinonitrile (SN) and a lithium salt.
The polymer composite solid electrolyte disclosed by the invention is based on the double cross-linked structure formed by the diglycidyl ether A and the diglycidyl ether B and an epoxy polymer, the mechanical strength of the polymer composite electrolyte is obviously improved by the double cross-linked structure, the ionic liquid is large in ion size and high in dissociation tendency to free ions, the ionic conductivity of the polymer solid electrolyte can be improved, the polymer composite solid electrolyte has excellent interface compatibility with the epoxy polymer and the succinonitrile, and the succinonitrile is uniformly distributed in a matrix and is wrapped in the structure. The succinonitrile SN is a solid organic material, lithium ions are easy to move so as to generate jump conduction, the crystallization of epoxy-based polymers can be inhibited by adding the succinonitrile SN, the solubility of lithium salts is improved, the ionic conductivity of solid electrolytes is improved, and uniform and rapid ion transmission channels are constructed in the high-strength bicontinuous crosslinking PEO-based polymer solid electrolytes.
Preferably, the epoxy-based polymer is selected from one of Polyoxyethylene (PEO), Polyvinylamine (PEI), and polyvinyl formal (PVFM).
Preferably, the diglycidyl ether a is polyethylene glycol diglycidyl ether (PEGDE); the diglycidyl ether B is bisphenol a diglycidyl ether (BADGE).
Preferably, the ionic liquid is 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (EMIMTFSI) or 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF)4)。
Preferably, the lithium salt is selected from lithium bis (trifluoromethanesulfonylimide), LiTFSI, and LiClO4Lithium difluoro (oxalato) borate LIODFB, lithium triflate LiOTF, lithium bis (oxalato) borate LiBOB, lithium bis (fluorosulfonyl) imide LiFSI and lithium 3, 4-difluoromaleimide.
Preferably, the molar ratio of the diglycidyl ether A to the diglycidyl ether B to the ionic liquid to the lithium salt is (1-3): (0.5-4.5): (7-12): (5-8).
Preferably, the molar ratio of the epoxy-based polymer to the succinonitrile is (0.5-1): (3-5).
A preparation method of a polymer composite solid electrolyte comprises the steps of uniformly mixing diglycidyl ether A, diglycidyl ether B, ionic liquid and lithium salt, then adding epoxy polymer and succinonitrile, stirring for cross-linking reaction, and curing to obtain the polymer composite solid electrolyte.
The application of the polymer composite solid electrolyte in preparing the composite positive plate comprises the steps of dripping the polymer composite solid electrolyte before solidification onto the surface of the positive plate, standing, and solidifying at the temperature of 70-100 ℃ to obtain the composite positive plate. Because the reversibility of the crosslinked polymer solid electrolyte is poor, the crosslinked polymer solid electrolyte has low compatibility with the surface of the positive plate, and the interface resistance is increased, the liquid polymer composite solid electrolyte before solidification is required to be dripped on the surface of the positive plate.
Preferably, the preparation method of the positive plate comprises the following steps:
the preparation method comprises the following steps of (1) mixing lanthanum lithium titanate LATP or lanthanum lithium zirconate LLZO, a positive electrode active material, polyvinylidene fluoride PVDF and a conductive agent according to a mass ratio of (0.5-1.0): (1-1.5): (0.05-0.2): (0.05-0.1), adding the mixture into a high-energy vibration ball mill, carrying out ball milling for 30-45 min at normal temperature, transferring the mixed material into a molybdenum-based alloy mold, and pressing the mixed material into a film under the standard atmospheric pressure of 300 plus materials and 400 plus materials to obtain the positive plate.
Preferably, the positive active material is selected from one or more of lithium iron phosphate, lithium manganate, lithium cobaltate and layered transition metal oxide.
Preferably, the conductive agent is one selected from carbon black, ketjen black, conductive graphite, carbon nanotubes, and nano conductive fibers.
An application of polymer composite solid electrolyte in lithium ion battery.
Therefore, the invention has the following beneficial effects:
(1) according to the invention, based on the bicontinuous crosslinking treatment, the mechanical property of the polymer solid electrolyte is improved, the ionic liquid and the succinonitrile are introduced into a crosslinking system, the ionic liquid has a higher dissociation tendency to free ions, the succinonitrile is used for inhibiting the crystallization of the epoxy-based polymer, the solubility of lithium salt is improved, and the ionic conductivity of the polymer solid electrolyte is synergistically improved;
(2) the preparation method is simple to operate, has no special requirements on equipment, and is easy to industrialize;
(3) the polymer composite solid electrolyte has higher ionic conductivity and mechanical strength, can be used for preparing a composite positive plate and is applied to a lithium ion battery.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples.
In the present invention, all the equipments and raw materials are commercially available or commonly used in the industry, the reagents used in the present invention are analytical grade, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
(1) Polyethylene glycol diglycidyl ether (PEGDE), bisphenol A diglycidyl ether (BADGE), 1-ethyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide (EMIMTFSI) ionic liquid and lithium bis (trifluoromethylsulfonyl) imide LiTFSI nano-powder are mixed according to a molar ratio of 1.5: 3.0: 8: 6, uniformly mixing, magnetically stirring for 2-6 h at normal temperature, and then adding a mixture with a molar ratio of 1: 3, strongly stirring the Polyoxyethylene (PEO) and the Succinonitrile (SN) for 1 to 3 hours at normal temperature to carry out crosslinking reaction to obtain the polymer composite solid electrolyte;
(2) preparing a positive plate:
the preparation method comprises the following steps of (1) mixing lanthanum lithium titanate (LATP), a positive electrode active material, polyvinylidene fluoride (PVDF) and a conductive agent according to a mass ratio of 0.5: 1: 0.1: 0.08 of the powder is added into a high-energy vibration ball mill, ball milling is carried out for 30-45 min at normal temperature, the mixed material is transferred into a molybdenum-based alloy die, and pressing is carried out to form a film under the standard atmospheric pressure of 300 plus materials and 400, thus obtaining the positive plate;
(3) preparing a composite positive plate:
dripping the mixed solution before curing in the step (1) on the surface of the positive plate obtained in the step (2), standing, and curing at the temperature of 70-100 ℃ to obtain a composite positive plate;
(4) and (3) pressing the composite positive plate prepared in the step (3) on the other side (opposite to the positive side) of the solidified polymer solid electrolyte under 100-200 standard atmospheric pressures by taking a lithium indium alloy plate (the thickness is 50-150 mu m, and the lithium atomic percentage is 40-60%) as a negative electrode in an argon atmosphere, and assembling to obtain the 2035 type button solid battery.
Comparative example 1
Comparative example 1 differs from example 1 in that: 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (EMIMTFSI) ionic liquid and Succinonitrile (SN) are not added, and the rest processes are completely the same.
Comparative example 2
Comparative example 2 differs from example 1 in that: succinonitrile (SN) was not added and the rest of the process was identical.
Comparative example 3
Comparative example 3 differs from example 1 in that: in the step (3), the polymer composite solid electrolyte solidified in the step (1) is directly adopted, and other processes are completely the same.
Example 2
(1) Mixing polyethylene glycol diglycidyl ether (PEGDE), bisphenol A diglycidyl ether (BADGE), and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF)4) The ionic liquid and the lithium bis (oxalato) borate LiBOB are mixed according to a molar ratio of 3: 0.5: 7: 5, uniformly mixing, magnetically stirring for 2 hours at normal temperature, and then adding a mixture of the components in a molar ratio of 0.5: 5, strongly stirring the epoxy polymer and the succinonitrile at normal temperature for 3 hours to perform a crosslinking reaction to obtain a polymer composite solid electrolyte;
(2) preparing a positive plate:
the preparation method comprises the following steps of mixing lanthanum lithium titanate LATP or lanthanum lithium zirconate LLZO, a positive electrode active material, polyvinylidene fluoride PVDF and a conductive agent according to the mass ratio of 0.5: 1: 0.1: 0.1, adding the mixture into a high-energy vibration ball mill, carrying out ball milling for 40min at normal temperature, transferring the mixed material into a molybdenum-based alloy die, and pressing the mixed material into a film under 350 standard atmospheric pressures to obtain the positive plate;
(3) preparing a composite positive plate:
dripping the mixed solution before curing in the step (1) on the surface of the positive plate obtained in the step (2), standing, and curing at the temperature of 70-100 ℃ to obtain a composite positive plate;
(3) and (3) pressing the composite positive plate prepared in the step (3) on the other side (opposite to the positive side) of the solidified polymer solid electrolyte under 100-200 standard atmospheric pressures by taking a lithium indium alloy plate (the thickness is 50-150 mu m, and the lithium atomic percentage is 40-60%) as a negative electrode in an argon atmosphere, and assembling to obtain the 2035 type button solid battery.
Example 3
(1) Mixing polyethylene glycol diglycidyl ether (PEGDE), bisphenol A diglycidyl ether (BADGE), and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF)4) The ionic liquid and lithium difluoro (oxalato) borate LIODFB are mixed according to a molar ratio of 1: 4.5: 12: 8, uniformly mixing, magnetically stirring for 6 hours at normal temperature, and then adding a mixture of the components in a molar ratio of 1: 3, strongly stirring the epoxy polymer and the succinonitrile at normal temperature for 1-3 hours to perform a crosslinking reaction to obtain a polymer composite solid electrolyte;
(2) preparing a positive plate:
the preparation method comprises the following steps of (1) mixing lanthanum lithium titanate LATP or lanthanum lithium zirconate LLZO, a positive electrode active material, polyvinylidene fluoride PVDF and a conductive agent according to the mass ratio of 1.0: 1.5: 0.15: 0.05, adding the mixture into a high-energy vibration ball mill, carrying out ball milling for 30min at normal temperature, transferring the mixed material into a molybdenum-based alloy die, and pressing the mixed material into a film under 300 standard atmospheric pressures to obtain the positive plate;
(3) preparing a composite positive plate:
dripping the mixed solution before curing in the step (1) on the surface of the positive plate obtained in the step (2), standing, and curing at the temperature of 70-100 ℃ to obtain a composite positive plate;
(3) and (3) pressing the composite positive plate prepared in the step (3) on the other side (opposite to the positive side) of the solidified polymer solid electrolyte under 100-200 standard atmospheric pressures by taking a lithium indium alloy plate (the thickness is 50-150 mu m, and the lithium atomic percentage is 40-60%) as a negative electrode in an argon atmosphere, and assembling to obtain the 2035 type button solid battery.
Example 4
(1) Polyethylene glycol diglycidyl ether (PEGDE), bisphenol a diglycidyl ether (BADGE), 1-ethyl-3-methylimidazole bis (trifluoromethylsulfonyl) imide (EMIMTFSI) ionic liquid and lithium bis (fluorosulfonimide) LiFSI in a molar ratio of 2: 1.5: 8: 6, uniformly mixing, magnetically stirring for 2 hours at normal temperature, and then adding a mixture of the components in a molar ratio of 0.8: 4, strongly stirring the epoxy polymer and the succinonitrile at normal temperature for 1-3 hours to perform a crosslinking reaction to obtain a polymer composite solid electrolyte;
(2) preparing a positive plate:
the preparation method comprises the following steps of mixing lanthanum lithium titanate LATP or lanthanum lithium zirconate LLZO, a positive electrode active material, polyvinylidene fluoride PVDF and a conductive agent according to the mass ratio of 0.8: 1.2: 0.2: 0.10, adding the mixture into a high-energy vibration ball mill, carrying out ball milling for 33min at normal temperature, transferring the mixed material into a molybdenum-based alloy die, and pressing the mixed material into a film under 400 standard atmospheric pressures to obtain the positive plate;
(3) preparing a composite positive plate:
dripping the mixed solution before curing in the step (1) on the surface of the positive plate obtained in the step (2), standing, and curing at the temperature of 70-100 ℃ to obtain a composite positive plate;
(3) and (3) pressing the composite positive plate prepared in the step (3) on the other side (opposite to the positive side) of the solidified polymer solid electrolyte under 100-200 standard atmospheric pressures by taking a lithium indium alloy plate (the thickness is 50-150 mu m, and the lithium atomic percentage is 40-60%) as a negative electrode in an argon atmosphere, and assembling to obtain the 2035 type button solid battery.
Mechanical property characterization:
in order to test the mechanical strength and ionic conductivity of the polymer solid electrolyte membrane, the mixed solution is directly coated on a glass plate, and then the glass plate is transferred to a vacuum oven with the temperature of 70-100 ℃ for solidification, so that the polymer solid electrolyte membrane is obtained.
According to GB1040-92 plastic tensile property test method, performing tensile force test under the condition of 10mm/min, wherein the test temperatures are respectively 30 ℃ and 60 ℃, each sample is repeatedly tested for 5 times, and the average value of the three middle values is taken; testing the AC internal resistance of the pressed solid electrolyte at 30 ℃ by adopting a double-probe method, wherein the frequency range is 1-106HZ and alternating current impedance directly reflect the lithium ion transmission resistivity, and in order to reduce measurement errors, gold is sprayed on the bottom and the top of a sample before testing.
(II) battery performance characterization:
the 2035 button solid-state battery obtained in each of examples 1 to 3 and 1 to 5 was subjected to charge/discharge cycles at a rate of 0.1C at a temperature of 30 ℃ in a voltage range of 2.8 to 4.2V, and the test was stopped when the battery short-circuited at the time of termination of the life (at a voltage drop rate exceeding 5 mV/S).
TABLE 1 mechanical Property test results of the Polymer composite solid electrolyte films of examples 1 to 5 and comparative examples 1 to 3
TABLE 2 results of cell performance test for examples 1-5 and comparative examples 1-3
As can be seen from table 1: the method provided by the invention can obviously improve the mechanical strength and electrochemical performance of the PEO-based polymer solid electrolyte, and the bicontinuous crosslinking treatment can effectively improve the mechanical strength of an electrolyte membrane and inhibit the crystallinity of PEO; the added ionic liquid has excellent compatibility with a PEO matrix, enhances the dissociation tendency of lithium ions, improves the distribution uniformity of the high-conductivity SN filler, obviously improves the ionic conductivity of the electrolyte and has no obvious negative effect on the mechanical strength; the uncured solid electrolyte is adopted, so that the compatibility with the interface of the pole piece is enhanced, the internal resistance of interface ion transmission is further reduced, and the cycle life of the solid battery is greatly prolonged.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. The polymer composite solid electrolyte is characterized in that diglycidyl ether A and diglycidyl ether B and an epoxy polymer form a double-crosslinking structure, and the double-crosslinking structure is filled with an ionic liquid, succinonitrile and a lithium salt.
2. The polymer composite solid electrolyte according to claim 1, wherein the epoxy-based polymer is one selected from the group consisting of polyoxyethylene, polyvinylamine, and polyvinyl formal.
3. The polymer composite solid electrolyte according to claim 1, wherein the diglycidyl ether a is one of polyethylene glycol diglycidyl ether or other epoxy resins containing a diethylene ether chain; the diglycidyl ether B is bisphenol A diglycidyl ether or one of other bisphenol A epoxy resins.
4. The polymer composite solid electrolyte as claimed in claim 1, wherein the ionic liquid is 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide (EMIMTFSI) or 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF)4）。
5. The polymer composite solid electrolyte according to claim 1, wherein the lithium salt is selected from the group consisting of lithium bis (trifluoromethanesulfonylimide), LiTFSI, and lithium perchlorate, LiClO4Lithium difluoro (oxalato) borate LIODFB, lithium triflate LiOTF, lithium bis (oxalato) borate LiBOB, lithium bis (fluorosulfonyl) imide LiFSI and lithium 3, 4-difluoromaleimide.
6. The polymer composite solid electrolyte according to claim 1,
the molar ratio of the diglycidyl ether A to the diglycidyl ether B to the ionic liquid to the lithium salt is (1-3): (0.5-4.5): (7-12): (5-8);
the molar ratio of the epoxy group polymer to the succinonitrile is (0.5-1): (3-5).
7. A method for preparing the polymer composite solid electrolyte according to any one of claims 1 to 6, wherein the polymer composite solid electrolyte is obtained by uniformly mixing diglycidyl ether A, diglycidyl ether B, ionic liquid and lithium salt, adding epoxy polymer and succinonitrile, stirring for crosslinking reaction, and curing.
8. The application of the polymer composite solid electrolyte as claimed in any one of claims 1 to 6 in the preparation of a composite positive plate, wherein the polymer composite solid electrolyte before curing is dripped on the surface of the positive plate, and after standing, the polymer composite solid electrolyte is cured at the temperature of 70-100 ℃ to obtain the composite positive plate.
9. The application of claim 8, wherein the preparation method of the positive plate comprises the following steps:
the preparation method comprises the following steps of (1) mixing lanthanum lithium titanate LATP or lanthanum lithium zirconate LLZO, a positive electrode active material, polyvinylidene fluoride PVDF and a conductive agent according to a mass ratio of (0.5-1.0): (1-1.5): (0.05-0.2): (0.05-0.1) adding the mixture into a high-energy vibration ball mill, carrying out ball milling for 30-45 min at normal temperature, transferring the mixed material into a molybdenum-based alloy mold, and pressing the mixed material into a film under the standard atmospheric pressure of 300 plus materials and 400 plus materials to obtain the positive plate;
the positive active material is selected from one or more of lithium iron phosphate, lithium manganate, lithium cobaltate and layered transition metal oxide;
the conductive agent is selected from one of carbon black, ketjen black, conductive graphite, carbon nanotubes and nano conductive fibers.
10. Use of the polymer composite solid electrolyte according to any one of claims 1 to 6 in a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110557587.6A CN113381065A (en) | 2021-05-21 | 2021-05-21 | Polymer composite solid electrolyte and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110557587.6A CN113381065A (en) | 2021-05-21 | 2021-05-21 | Polymer composite solid electrolyte and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113381065A true CN113381065A (en) | 2021-09-10 |
Family
ID=77571552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110557587.6A Pending CN113381065A (en) | 2021-05-21 | 2021-05-21 | Polymer composite solid electrolyte and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113381065A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115133111A (en) * | 2022-08-31 | 2022-09-30 | 清陶(昆山)能源发展股份有限公司 | Composite electrolyte, preparation method thereof and lithium ion battery |
| CN115304038A (en) * | 2022-07-25 | 2022-11-08 | 佳化化学科技发展（上海）有限公司 | Preparation method of lithium bis (fluorosulfonate) imide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105914405A (en) * | 2016-04-21 | 2016-08-31 | 中国科学院青岛生物能源与过程研究所 | Preparation method of all-solid polymer electrolyte through in-situ ring opening polymerization of epoxy compound, and application of the all-solid polymer electrolyte in all-solid lithium battery |
| CN108365262A (en) * | 2018-02-08 | 2018-08-03 | 广东猛狮新能源科技股份有限公司 | A kind of 3D networks hybrid inorganic-organic all solid state electrolyte and a kind of lithium secondary battery |
| CN111430688A (en) * | 2020-03-18 | 2020-07-17 | 蜂巢能源科技有限公司 | Solid-state battery and preparation method and application thereof |
| CN112490433A (en) * | 2020-11-05 | 2021-03-12 | 中国电子科技集团公司第十八研究所 | Solid-state battery and method for improving rate capability and safety of solid-state battery |
| CN112500673A (en) * | 2020-11-26 | 2021-03-16 | 山东大学 | Polymer solid electrolyte containing lithium-philic metal ions, preparation method and application thereof |
-
2021
- 2021-05-21 CN CN202110557587.6A patent/CN113381065A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105914405A (en) * | 2016-04-21 | 2016-08-31 | 中国科学院青岛生物能源与过程研究所 | Preparation method of all-solid polymer electrolyte through in-situ ring opening polymerization of epoxy compound, and application of the all-solid polymer electrolyte in all-solid lithium battery |
| CN108365262A (en) * | 2018-02-08 | 2018-08-03 | 广东猛狮新能源科技股份有限公司 | A kind of 3D networks hybrid inorganic-organic all solid state electrolyte and a kind of lithium secondary battery |
| CN111430688A (en) * | 2020-03-18 | 2020-07-17 | 蜂巢能源科技有限公司 | Solid-state battery and preparation method and application thereof |
| CN112490433A (en) * | 2020-11-05 | 2021-03-12 | 中国电子科技集团公司第十八研究所 | Solid-state battery and method for improving rate capability and safety of solid-state battery |
| CN112500673A (en) * | 2020-11-26 | 2021-03-16 | 山东大学 | Polymer solid electrolyte containing lithium-philic metal ions, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘宏民 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115304038A (en) * | 2022-07-25 | 2022-11-08 | 佳化化学科技发展（上海）有限公司 | Preparation method of lithium bis (fluorosulfonate) imide |
| CN115304038B (en) * | 2022-07-25 | 2024-03-08 | 佳化化学科技发展（上海）有限公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN115133111A (en) * | 2022-08-31 | 2022-09-30 | 清陶(昆山)能源发展股份有限公司 | Composite electrolyte, preparation method thereof and lithium ion battery |
| CN115133111B (en) * | 2022-08-31 | 2022-12-16 | 清陶(昆山)能源发展股份有限公司 | Composite electrolyte, preparation method thereof and lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102639836B1 (en) | Mixed solid-liquid electrolyte lithium storage battery | |
| CN108963327B (en) | Inorganic filler composite PEO solid electrolyte material, preparation method and all-solid-state battery | |
| CN111834662B (en) | Interface functional layer, preparation method thereof and lithium ion battery | |
| CN111900456B (en) | Composite positive pole piece, preparation method thereof and all-solid-state lithium ion battery | |
| CN102610862A (en) | Preparation method for lithium battery taking polypyrrole-coated magnesium borate as anode material | |
| CN112133961B (en) | Gel electrolyte precursor and application thereof | |
| CN110444731B (en) | Method for modifying cathode interface of all-solid-state lithium battery | |
| CN113381065A (en) | Polymer composite solid electrolyte and preparation method and application thereof | |
| CN110931852A (en) | Composite solid electrolyte, method for preparing same, and lithium secondary solid battery comprising same | |
| CN111725561A (en) | Solid electrolyte, preparation method thereof and all-solid-state battery | |
| CN110911741B (en) | Carbon oxide sphere doped solid polymer electrolyte membrane and preparation method and application thereof | |
| CN113036268A (en) | Lithium metal structure battery with structure energy storage function | |
| CN111799502B (en) | Garnet type solid composite electrolyte, preparation method and application | |
| CN111916815B (en) | Lithium metal battery | |
| CN114937813A (en) | Lithium ion battery and electronic device | |
| JP2022170697A (en) | Lithium ion secondary battery negative electrode, method for manufacturing lithium ion secondary battery negative electrode, and lithium ion secondary battery | |
| CN111816842B (en) | Lithium electrode containing passivation protective film, preparation method thereof and lithium ion battery | |
| CN112803061A (en) | All-solid-state lithium battery and preparation method and application thereof | |
| CN110676515B (en) | Preparation method of low-temperature high-energy-density lithium ion battery | |
| CN109301318B (en) | Polymer electrolyte, preparation method thereof and all-solid-state lithium ion battery prepared from polymer electrolyte | |
| CN115911263A (en) | Lithium metal composite pole piece and preparation method and application thereof | |
| CN113451643B (en) | In-situ preparation method and application of amide-based composite solid electrolyte | |
| CN112701347B (en) | Electrochemical device and electronic equipment | |
| Zhang et al. | Ion-compensation regime between electrolyte and cathode to prepare advanced lithium metal batteries | |
| CN113363573B (en) | Preparation method of solid electrolyte, solid electrolyte and all-solid-state battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20211110 Address after: 311215 No. 855, Jianshe Second Road, economic and Technological Development Zone, Xiaoshan District, Hangzhou City, Zhejiang Province Applicant after: Wanxiang A123 Co.,Ltd. Address before: 311215 No. 855, Jianshe Second Road, Xiaoshan Economic and Technological Development Zone, Xiaoshan District, Hangzhou City, Zhejiang Province Applicant before: Wanxiang A123 Co.,Ltd. Applicant before: WANXIANG GROUP Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210910 |
|
| RJ01 | Rejection of invention patent application after publication |