CN114530629B - Preparation and application of solid electrolyte and additive thereof - Google Patents
Preparation and application of solid electrolyte and additive thereof Download PDFInfo
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- CN114530629B CN114530629B CN202210086542.XA CN202210086542A CN114530629B CN 114530629 B CN114530629 B CN 114530629B CN 202210086542 A CN202210086542 A CN 202210086542A CN 114530629 B CN114530629 B CN 114530629B
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 105
- 239000000654 additive Substances 0.000 title claims abstract description 60
- 230000000996 additive effect Effects 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 33
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 32
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 31
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims description 20
- 159000000002 lithium salts Chemical class 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 125000000623 heterocyclic group Chemical group 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 125000001424 substituent group Chemical group 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229920000307 polymer substrate Polymers 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- -1 cyano, phenyl Chemical group 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 125000003003 spiro group Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 238000011160 research Methods 0.000 abstract description 3
- 239000002000 Electrolyte additive Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229920000620 organic polymer Polymers 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229960003299 ketamine Drugs 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 7
- YQEZLKZALYSWHR-UHFFFAOYSA-N Ketamine Chemical compound C=1C=CC=C(Cl)C=1C1(NC)CCCCC1=O YQEZLKZALYSWHR-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000012634 fragment Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000962 poly(amidoamine) Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- WLLGXSLBOPFWQV-UHFFFAOYSA-N MGK 264 Chemical compound C1=CC2CC1C1C2C(=O)N(CC(CC)CCCC)C1=O WLLGXSLBOPFWQV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Chemical compound 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000011068 loading method Methods 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
- 238000000465 moulding Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Images
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention belongs toIn the field of solid state battery technology, in particular to a solid state electrolyte additive which is provided with
Structural polymers. The invention also includes the preparation and application of the additive. Further, a solid electrolyte and a solid battery to which the additive is added are also included. The research of the invention shows that the solid electrolyte added with the additive has excellent conductivity, the thermal stability is improved, and when the temperature reaches 140 ℃, the solid electrolyte does not generate the thermal shrinkage phenomenon, and the prepared electrolyte can still circulate even at 100 ℃.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an electrolyte of a solid-state battery.
Background
With the wider application of various electronic products and new energy automobiles, people are more and more widely applied to the aspect of power safety, a traditional liquid battery consists of a positive electrode diaphragm, a negative electrode diaphragm and electrolyte, but the organic electrolyte used by the liquid battery is easy to cause thermal runaway of the battery, the battery is easy to generate bulge and gas-expanding combustion phenomena, the safety performance of the battery is reduced, the diaphragm and electrolyte of the liquid electrolyte are replaced by the appearance of solid electrolyte, the safety of the lithium ion battery is improved, in the solid electrolyte, the PEO-based solid electrolyte has better flexibility, materials are cheap and easily available and are widely applied to the polymer solid electrolyte, however, the PEO polymer is easy to crystallize at room temperature by virtue of the movement of an amorphous segment in an amorphous area, the transmission performance of the segment to lithium ions is reduced after crystallization, the ionic conductivity is reduced, the PEO-based solid electrolyte is poor in thermal stability at high temperature, and a large amount of water and carbon oxides are contained in a thermal decomposition product, and the PEO-based solid electrolyte can undergo side reaction with an electrolyte body, and the interface impedance is increased instead. These problems limit the application of solid state lithium ion batteries. Therefore, the development of a safe and reliable method for preparing the porous solid electrolyte has important practical significance.
Disclosure of Invention
A first object of the present invention is to provide a solid electrolyte additive (also referred to herein simply as an additive, or as porous polycarboxylamine) aimed at improving the thermal stability, electrical conductivity and electrochemical performance of the solid electrolyte.
The second object of the present invention is to provide a process for the preparation of said additive.
A third object of the present invention is to provide the use of said additive as solid electrolyte additive for the preparation of lithium secondary batteries.
A fourth object of the present invention is to provide a modified solid electrolyte to which the additive is added.
A fifth object of the present invention is to provide a method for producing the modified solid electrolyte and a solid lithium secondary battery assembled by the method.
A solid electrolyte additive which is a porous polymer having a repeating segment of formula 1:
R 1 、R 2 independently H, alkyl, cycloalkyl, heterocyclyl, aryl or heteroaryl;
the alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl groups are allowed to bear substituents; the substituent is at least one of alkyl, halogen, alkoxy, ester, cyano, phenyl or phosphate.
According to the invention, the porous polymer of the fragment of the formula 1 is used as an additive, so that the thermal stability and the conductivity of the solid electrolyte can be obviously improved, and the electrochemical performance of the assembled solid battery can be improved.
In the present invention, the alkyl group may be C 1 ～C 10 Alkyl of (a); further preferably C 1 ～C 4 Is a hydrocarbon group. The alkyl group may be a straight or branched chain alkyl group.
Preferably, the cycloalkyl is a three-to ten-membered monocyclic, bridged or spiro ring group.
Preferably, the heterocyclic group is five-membered to ten-membered heterocyclic group containing one or more hetero atoms; the heteroatom is preferably at least one of O, N, S, P. More preferably, the heterocyclic group is a five-membered or six-membered ring group containing 1 to 3 hetero atoms.
The aryl group is, for example, a phenyl group or a polycyclic aryl group formed by combining two or more benzene rings.
In the present invention, the heteroaryl group is preferably a five-membered heteroaryl group having 1 to 3 hetero atoms, a six-membered heterocyclic ring system, or a fused heterocyclic ring formed by the fusion of two or more aromatic rings in the five-membered heteroaryl group, the six-membered heterocyclic ring system, and the benzene ring.
In the present invention, the alkyl, cycloalkyl, heterocyclic, aryl or heterocyclic aryl substituents Xu Hanyou are substituted alkyl, substituted cycloalkyl, substituted heterocyclic, substituted aryl or substituted heterocyclic aryl respectively.
Preferably, the substituent may be at least one of halogen, alkoxy (RaO-), ester (RaOCO-), cyano, phenyl or phosphoester. Ra is, for example, a C1-C6 alkyl group. The halogen is at least one of F, cl and Br;
the invention researches find that the porous polymer can have hydrogen bond action with a polymer matrix and lithium salt in the solid electrolyte, and can improve the performance of the solid electrolyte. Based on the innovation of the porous polymer, R is further calculated 1 、R 2 The control can further promote the dissociation of lithium salt, accelerate the movement of lithium ions in the matrix, improve the ion conductivity,in addition, the heat stability can be improved by further cooperating with the rigidity of the triazine ring framework in the polymer.
Said R is 1 、R 2 At least one substituent is aryl, heteroaryl, cycloalkyl or a hybrid;
further preferably, said R 1 、R 2 At least one of the substituents is phenyl or phenyl with substituent groups, and the substituent groups are at least one of C1-C3 alkyl, C1-C3 alkoxy, halogen and cyano; the remaining substituents are H, alkyl or aromatic groups.
Preferably, the specific surface area of the additive is 346-745 m 2 /g；
The additive provided by the invention has a porous structure with an amorphous shape, and is large in specific surface area, light in powder mass and easy to disperse.
The invention also provides a preparation method of the solid electrolyte additive, which is characterized in that the monomer 1 with the formula 2 and the monomer 2 with the structure of the formula 3 are polymerized to prepare the porous polymer;
in the present invention, the molar ratio of formula 2 to formula 3 is 3:4 to 5;
preferably, the solvent of the polymerization process is at least one of DMSO and DMF;
preferably, the polymerization process is carried out under a protective atmosphere, preferably a nitrogen, argon atmosphere.
The polymerization process of the invention is preferably carried out by adopting a program temperature control mode:
the program temperature control program is as follows: heating the initial temperature to T1 in a first gradient, then heating the initial temperature to T2 in a second gradient, and finally heating the initial temperature to T3 in a third gradient;
in the first gradient heating stage, the initial temperature is 20-60 ℃, the temperature gradient of the adjacent sections is 10-20 ℃, and the time interval of the adjacent sections is 1-3 h; t1 is 120-130 ℃;
in the second gradient heating stage, 2-3 heating gradients are included, wherein the temperature gradient of the adjacent sections is 10-15 ℃, and the time interval of the adjacent sections is 5-7 h;
in the third gradient heating stage, 2-3 heating gradients are included, wherein the temperature gradient of the adjacent sections is 10-15 ℃, and the time interval of the adjacent sections is 10-14 h.
The present inventors have found that under the preferred temperature control mechanism, polymerization of formulas 2 and 3 is facilitated and the properties of the resulting additive are facilitated.
The program temperature control stage comprises three temperature control intervals, wherein each temperature control interval adopts a multi-stage temperature control mode, the first gradient temperature control process is an interval from the initial temperature to the T1 temperature, the temperature gradient of gradient temperature control is 10-20 ℃, and the time interval of the adjacent sections is 1-3 h; the initial temperature can be 20-60 ℃; t1 is 120-130 ℃. The second temperature control interval is a temperature rising interval from T1 to T2, and the interval preferably comprises 2 to 3 temperature rising gradients, wherein the temperature gradient of the adjacent sections is 10 to 15 ℃, and the time interval of the adjacent sections is 5 to 7 hours. The third gradient is heated to a heating interval from T2 to T3, and the heating interval preferably comprises 2 to 3 heating gradients, wherein the temperature gradient of the adjacent sections is 10 to 15 ℃, and the time interval of the adjacent sections is 10 to 14 hours.
More specific temperature-controlled polymerization conditions of the present invention are, for example: the temperature is raised by 10 ℃ every 2-3 hours between 50 ℃ and 130 ℃, 10 ℃ every 5-7 hours between 130 ℃ and 150 ℃, and 10 ℃ every 10-14 hours between 150 ℃ and 170 ℃.
Preferably, after polymerization, the product is suction filtered with dimethyl sulfoxide, N-dimethylformamide, dichloromethane, tetrahydrofuran, and then dried to obtain the additive.
In the present invention, the drying treatment may be performed by an existing method, for example, vacuum drying.
The invention also provides application of the solid electrolyte additive, and the solid electrolyte additive is used as a solid electrolyte additive for preparing a solid lithium secondary battery.
In the present invention, the additive of the present invention may be added to a solid electrolyte system well known in the industry, thereby improving the thermal stability, conductivity, and electrochemical performance of the solid electrolyte.
In the application according to the invention, the additives may be added to known solid electrolyte systems based on existing methods.
The invention also provides a modified solid electrolyte comprising a polymer matrix, and a conductive lithium salt dispersed therein and an additive according to the invention.
In the present invention, the polymer substrate may be a component well known in the industry, for example, may be at least one of PEO, PEG, PVDF, PVDF-HFP;
in the present invention, the conductive lithium salt may be at least one of components known to those skilled in the lithium battery art, for example LITFSI, LIFSI, LIFTFSI;
preferably, in the modified solid electrolyte, the additive is 1 to 10wt%, preferably 1 to 5wt%, and more preferably 2 to 4wt% of the mass of the polymer substrate; most preferably 3 to 3.5wt%; the molar ratio of lithium in the conductive lithium salt to repeating units in the polymer substrate was 1:10 to 20.
It was found that under the monomers of the formulas 2 and 3, further control of the temperature programming mechanism, successful polymerization of formulas 2 and 3 can be achieved, and not only, a polymer having an adaptive pore structure can be obtained. The research shows that the product obtained by the preparation method can be used as an additive of the solid electrolyte, can effectively improve the thermal stability and the electrical conductivity of the solid electrolyte, and is beneficial to improving the performance of the assembled solid battery.
It was found that better thermal stability, conductivity and electrochemical performance of the solid-state battery can be obtained at the preferred additive addition ratio.
In the present invention, the thickness of the modified solid electrolyte may be adjusted as required, and may be, for example, 150 μm to 200 μm.
The invention also provides a preparation method of the modified solid electrolyte, which comprises slurrying the polymer substrate, the conductive lithium salt and the additive with a solvent, and then forming and curing to obtain the modified solid electrolyte;
the solvent is a solvent capable of dissolving the polymer substrate, and is preferably at least one of acetonitrile, N-dimethylformamide and tetrahydrofuran.
In the invention, the slurried system is poured into a mould by adopting a solution pouring method to carry out vacuum drying, so as to realize molding and solidification, and the modified solid electrolyte is prepared.
For example, in the preparation process of the modified solid electrolyte, polyethylene oxide, lithium salt and acetonitrile are dissolved to obtain the electrolyte dispersion liquid; adding the additive into the electrolyte dispersion liquid, and stirring and dispersing to obtain a mixture; and carrying out vacuum drying on the mixture by a solution pouring method to obtain the solid electrolyte.
The invention also provides a solid-state lithium secondary battery, which comprises a positive electrode, the modified solid electrolyte and a negative electrode which are compounded in sequence.
In the present invention, both the positive electrode and the negative electrode may be materials well known in the industry.
The beneficial effects are that:
1. the novel porous polymer of the repeated segment of the formula 1 is provided, and the porous polymer is used as an additive of solid electrolyte, so that the crystallinity of the solid electrolyte can be reduced, the ionic conductivity and the thermal stability can be improved, and the electrochemical performance of the assembled solid battery can be improved. For example, the conductivity of the modified solid electrolyte of the invention can reach 3.36×10 - 4 S/cm。
2. Control of R1, R2 of the repeating segment of formula 1, particularly control of rigid structures such as cyclic, heterocyclic, aryl, heterocyclic aryl, etc., helps to further synergistically improve ionic conductivity, thermal stability, and electrochemical performance of the solid state electrolyte;
3. in the invention, the polymerization is carried out under the controlled temperature by adopting the formula 2 and the formula 3 in combination with the procedure, which is more beneficial to the polymerization and improves the performance of the additive modified solid electrolyte obtained by the polymerization.
4. The invention has the advantages of simple process, short process period, rich raw materials, low cost, environmental protection and the like.
5. The solid electrolyte provided by the invention is free from liquid leakage, nonflammable and high in safety.
Drawings
FIG. 1 is a powder infrared spectrum, a powder SEM image, a solid electrolyte Nyquist plot, a solid electrolyte XRD image, and an electrochemical test image at 100deg.C of solid electrolyte according to example 1 of the present invention
FIG. 2 is a powder infrared spectrum, a powder SEM image, a solid electrolyte Nyquist plot, and a solid electrolyte XRD image of example 2 of the present invention;
FIG. 3 is a graph of a solid electrolyte at 60-140℃for 1h in example 1 of the present invention;
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
The first aspect of the present invention provides a method for preparing a solid electrolyte, which may specifically include the steps of:
step S100, preparation of the poly (carbonylamine). Polymerizing the monomer of formula 2 and the monomer of formula 3 to obtain the poly (carbonylamine) powder. And (3) placing the monomer of the formula 2 and the monomer of the formula 3 in pure dimethyl sulfoxide (DMSO) under inert gas atmosphere, programming to reach a target temperature, maintaining for a set time, filtering the turbid liquid with dimethyl sulfoxide, N-dimethylformamide, dichloromethane and tetrahydrofuran after the solution becomes opaque turbid liquid, and drying in vacuum at 100 ℃ to obtain the poly (carboximide) powder. In some embodiments, the target temperature may be set to 100-170 ℃; the set time can be 72 hours or more; the inert gas is nitrogen or argon.
And step S200, mixing the poly (carbol-amide) with electrolyte dispersion liquid and drying to obtain the solid electrolyte. In some embodiments, polyethylene oxide (PEO), lithium salt, and acetonitrile are dissolved to obtain the electrolyte dispersion; adding the polyion salt into the electrolyte dispersion liquid, and stirring and dispersing to obtain a mixture; and pouring the mixture into a mould, and drying by a solution pouring method to obtain the solid electrolyte.
According to the embodiment of the invention, the prepared poly (ketamine) is added into electrolyte dispersion liquid prepared from polyethylene oxide, lithium salt and acetonitrile, a solid electrolyte can be obtained after drying treatment, and the solid electrolyte can be prepared into a lithium ion battery.
In an exemplary embodiment, step S200 may specifically include: weighing a certain mass of lithium salt, and mixing polyethylene oxide according to the molar ratio of the repeating units in the polyethylene oxide to lithium in the lithium salt of 10:1, adding the poly (carbol) ammonia according to the mass percentage of the polyethylene oxide of 1-5%, weighing acetonitrile which is 19 times of the mass of the polyethylene oxide to dissolve the polyethylene oxide, the lithium salt and the poly (carbol) ammonia, stirring, dispersing and uniformly mixing, pouring the uniformly mixed mixture into a mould, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the solid electrolyte. In the embodiment of the present invention, the sequential addition sequence of the poly (carbonylamine), the poly (ethylene oxide) (PEO), the lithium salt and the acetonitrile should not form a limitation on the technical scheme of the present invention in the process of preparing the solid electrolyte of the present invention.
A second aspect of the present invention provides a solid state electrolyte comprising: a copoly (ketamine) and an electrolyte dispersion; wherein the electrolyte dispersion comprises polyethylene oxide, lithium salt, and acetonitrile; the molar ratio of the repeating units in the polyethylene oxide to lithium in the lithium salt is 10:1, wherein the mass ratio of the acetonitrile to the polyethylene oxide is 19:1; the mass percentage of the poly (carbol-amide) and the polyethylene oxide is 1-5%.
In some embodiments, the poly (carborundum) prepared by the embodiment of the invention has the characteristics of rich structure and simple design, and the structure can be selected according to the strength of different skeletons and the required functional groups.
In some embodiments, the prepared polycarboxylamine, polyethylene oxide, lithium salt and acetonitrile can be assembled into a battery after being prepared into an electrolyte.
Example 1:
monomers of formula 2-A are employed:
mixing formula 2-A (0.12 mol/L) and formula 3 (0.16 mol/L) in DMSO distilled under reduced pressure, controlling temperature by adopting a temperature programming mode, heating from 50 ℃ to 170 ℃, heating 10 ℃ every 2 hours between 50 ℃ and 130 ℃, heating 10 ℃ every 6 hours between 130 ℃ and 150 ℃ and 10 ℃ every 12 hours between 150 ℃ and 170 ℃, reacting to obtain turbid liquid, carrying out suction filtration on the turbid liquid by dimethyl sulfoxide, N-dimethylformamide, dichloromethane and tetrahydrofuran, and vacuum drying at 100 ℃ to obtain the porous poly-condensed ammonia powder of the repeating segment of formula 1-A.
The infrared diagram of the prepared porous organic polymer of the formula 1-A poly (carbonylamino) is shown in figure 1 (a).
The SEM diagram of the prepared porous organic polymer of the formula 1-A poly (carbonylamino) is shown in figure 1 (b). The polymer exhibits a porous structure as shown.
The resulting poly (ketamine) was added to an electrolyte dispersion at 3% by mass of PEO to prepare a poly (ketamine) -containing solid electrolyte having a thickness of 150 μm to 200 μm, which was then assembled into a battery, the positive and negative electrodes of which were connected to an electrochemical workstation, and the ac impedance of the battery at 25 to 60 ℃ was measured to obtain a Nyquist diagram of the electrolyte. As shown in fig. 1 (c), wherein the coordinate axis corresponds to a complex plane, the abscissa on the complex plane represents the real part, corresponds to the resistance of the electrolyte, the ordinate represents the imaginary part, and corresponds to the reactance of the electrolyte.
In this figure, the ac impedance is composed of a semicircle and a straight line having an inclination of about 45 °, wherein the intersection of both ends of the semicircle with the x-axis is represented as the resistance value of the electrolyte.
The lithium ion conductivity can be calculated by the following formula.
Where σ represents ion conductivity, S represents the working electrode area of the battery (refers to the area of the positive electrode of the battery or the area of the negative electrode of the battery), and is 2.01cm in this embodiment 2 Indicating the thickness of the solid polymer electrolyte membrane, R b The resistance of the electrolyte is shown.
Obtained by the above formula: in the test environment, the resistance value of the electrolyte is about 30Ω and the lithium ion conductivity is 3.36×10 when the temperature outside the battery is 60deg.C -4 S/cm。
And it was confirmed by XRD diffraction experiments that the addition of the porous organic polymer of the formula 1-A polyamidoamine reduced the crystallinity of the polymer solid electrolyte, as shown in FIG. 1 (d).
The battery is assembled in a glove box, wherein the water oxygen content in the glove box is lower than 0.01ppm, and the battery is assembled according to the sequence of the positive electrode shell, the positive electrode plate, the solid electrolyte membrane, the metal lithium negative electrode, the gasket, the elastic sheet and the negative electrode shell. After the battery is assembled, the battery is clamped by using plastic tweezers and placed on a seal for pressing, the battery is placed in a cabin door of a box after the pressing is finished, and then the battery is taken out for electrochemical performance test, the assembled button battery has the positive electrode of lithium iron phosphate, the negative electrode of lithium metal, and the loading amount of the lithium iron phosphate is 1.5-2.5mg/cm 2 . Under the test condition of 100 ℃ and 1C, as shown in FIG. 1 (e), the initial capacity is 160mAh g -1 After 50 cycles, the battery capacity is 152.5mAh g -1 The capacity retention was 95.3%.
While the initial capacity of the pure PEO solid electrolyte under the test condition of 100 ℃ and 1C is 108.9mAh g as shown in the figure 1 (e) -1 After 23 cycles, the battery capacity is 99.7mAh g -1 The coulombic efficiency was reduced from 99.7% to 84.7% with a capacity retention of 91.8%.
And as shown in fig. 3, the composite solid electrolyte does not shrink after heat preservation for 1h at 60-140 ℃, which proves that the heat stability of the electrolyte membrane is improved after the addition of the poly (carbonylamine) porous organic polymer.
Implementation example 2:
the only difference compared to example 1 is that formula 2-B is used as monomer:
mixing formula 2-B (0.12 mol/L) and formula 3 (0.16 mol/L) in DMSO distilled under reduced pressure according to a molar ratio, controlling the temperature by adopting a temperature programming mode, heating from 50 ℃ to 170 ℃, heating 10 ℃ every 2 hours between 50 ℃ and 130 ℃, heating 10 ℃ every 6 hours between 130 ℃ and 150 ℃ and heating 10 ℃ every 12 hours between 150 ℃ and 170 ℃, and reacting to obtain turbid liquid, wherein the turbid liquid is subjected to suction filtration washing by dimethyl sulfoxide, N-dimethylformamide, dichloromethane and tetrahydrofuran, and vacuum drying at 100 ℃ to obtain the poly-condensed-ammonia powder of the structural fragment of formula 1-B.
The infrared diagram of the prepared porous organic polymer of the formula 1-B poly (carbonylamino) is shown in figure 2 (a).
The SEM image of the prepared porous organic polymer of the formula 1-B poly (carbonylamino) is shown in figure 2 (B). The polymer exhibits a porous structure as shown.
The resulting poly (ketamine) was added to an electrolyte dispersion at 3% by mass of PEO to prepare a poly (ketamine) -containing solid electrolyte having a thickness of 150 μm to 200 μm, which was then assembled into a battery, the positive and negative electrodes of which were connected to an electrochemical workstation, the ac impedance of the battery was measured, and the ionic conductivity thereof was calculated by a formula to obtain an ionic conductivity map of the electrolyte.In the test environment, when the temperature outside the battery was 60 ℃, the resistance value was about 35. Omega. And the lithium ion conductivity was 2.09X 10 as shown in FIG. 2 (c) -4 S/cm。
And it was confirmed by XRD diffraction experiments that the addition of the porous organic polymer of the formula 2-B polyamidoamine reduces the crystallinity of the polymer solid electrolyte as shown in FIG. 2 (d).
The initial capacity was 139.2mAh g at 100℃under 1C test conditions for battery assembly and electrochemical performance measurement by the method of example 1 -1 After 50 cycles, the battery capacity is 137.1mAh g -1 。
Implementation example 3:
the main difference compared to example 1 is that, using formula 2-C as monomer,
the method comprises the following steps:
mixing formula 2-C and formula 3 in molar ratio, namely mixing formula 2-C (0.12 mol/L) and formula 3 (0.16 mol/L) in DMSO distilled under reduced pressure, heating to 170 ℃ from 50 ℃ to 130 ℃ in a temperature programming mode, heating to 10 ℃ every 2 hours between 50 ℃ and 130 ℃, heating to 10 ℃ every 6 hours between 130 ℃ and 150 ℃ and 10 ℃ every 12 hours between 150 ℃ and 170 ℃, and reacting to obtain turbid liquid, filtering and washing the turbid liquid with dimethyl sulfoxide, N-dimethylformamide, dichloromethane and tetrahydrofuran, and vacuum drying at 100 ℃ to obtain the poly (carbonyl-condensed ammonia) powder of the structural fragment of formula 1-C.
Adding the obtained polycarborundum of formula 1-C to electrolyte dispersion liquid according to 3% (optimal ratio) of PEO mass to obtain solid electrolyte containing polycarborundum, wherein the thickness of solid electrolyte is 150 μm-200 μm, assembling into a battery, connecting anode and cathode of the battery to electrochemical workstation, measuring AC impedance of the battery, and passing throughAnd calculating the ionic conductivity by using a formula to obtain the ionic conductivity of the electrolyte. Under the test environment, the resistance value is about 32.5 omega at the temperature of 60 ℃ outside the battery, and the lithium ion conductivity is 3.31 multiplied by 10 -4 S/cm。
The initial capacity of the battery was 149.2mAh g at 100℃under 1C test conditions, as determined by the method of example 1 -1 After 50 cycles, the battery capacity is 146mAh g -1 The capacity retention was 97.8%.
Implementation example 4:
the main difference compared with example 1 is that the compound of the formula 2-D structure is used as monomer, the steps are:
mixing formula 2-D (0.12 mol/L) and formula 3 (0.16 mol/L) in DMSO distilled under reduced pressure according to a molar ratio, controlling the temperature by adopting a temperature programming mode, heating from 50 ℃ to 170 ℃, heating 10 ℃ every 2 hours between 50 ℃ and 130 ℃, heating 10 ℃ every 6 hours between 130 ℃ and 150 ℃ and heating 10 ℃ every 12 hours between 150 ℃ and 170 ℃, and reacting to obtain turbid liquid, wherein the turbid liquid is subjected to suction filtration washing by dimethyl sulfoxide, N-dimethylformamide, dichloromethane and tetrahydrofuran, and vacuum drying at 100 ℃ to obtain the poly-condensed-ammonia powder with the repeating structure of formula 1-D.
The resulting poly (ketamine) of formula 1-D was added to an electrolyte dispersion at 3% by mass (optimal ratio) of PEO to prepare a poly (ketamine) -containing solid electrolyte having a thickness of 150 μm to 200 μm, which was then assembled into a battery, the positive and negative electrodes of the battery were connected to an electrochemical workstation, the ac impedance of the battery was measured, and the ionic conductivity thereof was calculated by the formula.
In the test environment, when the temperature outside the battery is 60 ℃,the resistance value is about 31 omega, and the lithium ion conductivity is 2.63 multiplied by 10 -4 S/cm。
The initial capacity of the battery was 137.7mAh g at 100℃under 1C test conditions, as determined by the method of example 1 -1 After 50 cycles, the battery capacity is 132.5mAh g -1 。
Example 5
The only difference compared to example 1 is that the poly (carbonylamine) is 1% of the PEO mass.
The initial capacity of the battery was 127.3mAh g at 100℃under 1C test conditions, as determined by the method of example 1 -1 After 50 cycles, the battery capacity is 120.3mAh g -1 The capacity retention was 94.5%.
Example 6
The only difference compared to example 1 is that the poly (carbonylamine) is 5% of the PEO mass.
The initial capacity of the battery was 122.4mAh g at 100℃under 1C test conditions, as determined by the method of example 1 -1 After 50 cycles, the battery capacity is 115.7mAh g -1 The capacity retention was 94%.
The technical scheme provided by the embodiment of the invention has at least the following beneficial technical effects:
1. the matrix of the polymeric matrix is modified by using the monomer of formula 2 to modify the matrix of the polymeric matrix such that the polymeric solid state battery can be improved in thermal stability after the polymeric porous organic polymer is added to the PEO matrix.
2. The solid electrolyte is used in a lithium ion battery, and can accelerate the movement of lithium ions in the PEO-based electrolyte through intermolecular interaction force, so that the ion conductivity of the PEO-based solid electrolyte is improved, and the conductivity of the solid electrolyte provided by the invention can reach 3.36 multiplied by 10 -4 S/cm。
3. The addition of the porous organic polymer of the poly (carbonylamine) can reduce the crystallinity of the solid electrolyte of the polymer.
4. The invention has the advantages of simple process, short process period, rich raw materials, low cost, environmental protection and the like.
5. The solid electrolyte provided by the invention is free from liquid leakage, nonflammable and high in safety.
6. The solid electrolyte provided by the invention can still stably circulate at high temperature.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Claims (30)
1. A solid electrolyte additive characterized by being a porous polymer having a repeating segment of formula 1:
R 1 、R 2 Independently H, alkyl, cycloalkyl, heterocyclyl, aryl or heteroaryl;
the alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl groups are allowed to bear substituents; the substituent is at least one of alkyl, halogen, alkoxy, ester, cyano, phenyl or phosphate.
2. The solid electrolyte additive of claim 1 wherein said alkyl group is C 1 ~C 10 Is a hydrocarbon group.
3. The solid electrolyte additive of claim 1 wherein said alkyl group is C 1 ~C 4 Is a hydrocarbon group.
4. The solid electrolyte additive of claim 1, wherein the cycloalkyl group is a three-to ten-membered monocyclic, bridged or spiro ring group.
5. The solid electrolyte additive according to claim 1, wherein the heterocyclic group is a five-membered to ten-membered heterocyclic group containing one or more hetero atoms; the heteroatom is at least one of O, N, S, P.
6. The solid electrolyte additive of claim 1 wherein said aryl is phenyl or a polycyclic aryl formed by the union of two or more benzene rings.
7. The solid electrolyte additive according to claim 1, wherein the heterocyclic aryl group is a five-membered heterocyclic aryl group containing 1 to 3 hetero atoms, a six-membered heterocyclic aryl group, and a condensed heterocyclic ring formed by combining two or more aromatic rings in the five-membered heterocyclic aryl group, the six-membered heterocyclic aryl group, and the benzene ring.
8. The solid electrolyte additive of claim 1 wherein said substituents are halogen, C 2 ~C 6 At least one of an ester group, a cyano group, a phosphate group and a C1-C3 alkoxy group.
9. The solid electrolyte additive of claim 1 wherein R 1 、R 2 At least one substituent is aryl, heteroaryl, cycloalkyl or a hybrid.
10. The solid electrolyte additive of claim 9 wherein R 1 、R 2 At least one phenyl or phenyl with substituent groups, wherein the substituent groups are at least one of C1-C3 alkyl, C1-C3 alkoxy, halogen and cyano.
11. The solid electrolyte additive of claim, wherein the specific surface area of the solid electrolyte additive is 346-745 mm per gram.
12. A method for preparing the solid electrolyte additive according to any one of claims 1 to 11, wherein the porous polymer is prepared by polymerizing a monomer 1 having a formula 2 and a monomer 2 having a structure of a formula 3;
13. The method of preparing a solid electrolyte additive according to claim 12, wherein the molar ratio of formula 2 to formula 3 is 3: 4-5.
14. The method of preparing a solid electrolyte additive according to claim 12, wherein the solvent in the polymerization process is at least one of DMSO and DMF.
15. The method of preparing a solid electrolyte additive according to claim 12, wherein the polymerization process is performed under a protective atmosphere.
16. The method of preparing a solid electrolyte additive according to claim 15, wherein the protective atmosphere is a nitrogen or argon atmosphere.
17. The method for preparing the solid electrolyte additive according to claim 12, wherein after polymerization, the product is filtered by suction using dimethyl sulfoxide, N-dimethylformamide, methylene chloride and tetrahydrofuran, and then dried, thereby preparing the additive.
18. The method for preparing a solid electrolyte additive according to claim 12, wherein the polymerization is performed by a programmed temperature control method.
19. The method of preparing a solid electrolyte additive according to claim 18, wherein the programmed temperature control program is: heating the initial temperature to T1 in a first gradient, then heating the initial temperature to T2 in a second gradient, and finally heating the initial temperature to T3 in a third gradient;
in the first gradient heating stage, the initial temperature is 20-60 ℃, the temperature gradient of the adjacent sections is 10-20 ℃, and the time interval of the adjacent sections is 1-3 h; t1 is 120-130 ℃;
in the second gradient heating stage, 2-3 heating gradients are included, wherein the temperature gradient of the adjacent sections is 10-15 ℃, and the time interval of the adjacent sections is 5-7 h;
in the third gradient heating stage, 2-3 heating gradients are included, wherein the temperature gradient of the adjacent sections is 10-15 ℃, and the time interval of the adjacent sections is 10-14 h.
20. Use of the solid electrolyte additive according to any one of claims 1 to 11 or the solid electrolyte additive produced by the production method according to any one of claims 12 to 19 as a solid electrolyte additive for producing a solid lithium secondary battery.
21. A modified solid electrolyte comprising a polymer matrix and a conductive lithium salt dispersed therein and an additive according to any one of claims 1 to 11 or prepared by a method according to any one of claims 12 to 19.
22. The modified solid state electrolyte of claim 21 wherein said polymer matrix material is at least one of PEO, PEG, PVDF, PVDF-HFP.
23. The modified solid state electrolyte of claim 21 wherein said conductive lithium salt is at least one of LITFSI, LIFSI, LIFTFSI.
24. The modified solid electrolyte of claim 21, wherein the additive is 1-10wt% of the mass of the polymer substrate in the modified solid electrolyte; the molar ratio of lithium in the conductive lithium salt to repeating units in the polymer substrate was 1: 10-20.
25. The modified solid electrolyte of claim 24 wherein the additive is 1 to 5wt% of the mass of the polymer substrate in the modified solid electrolyte.
26. The modified solid electrolyte of claim 25 wherein the additive comprises 2 to 4wt% of the mass of the polymer substrate.
27. The modified solid electrolyte of claim 21 wherein the modified solid electrolyte has a thickness of 150 μm to 200 μm.
28. A method for preparing the modified solid electrolyte according to any one of claims 21 to 27, wherein the polymer substrate, the conductive lithium salt and the additive are slurried with a solvent, and then molded and cured;
the solvent is a solvent capable of dissolving the polymer substrate.
29. The method of claim 28, wherein the solvent is at least one of acetonitrile, N-dimethylformamide, and tetrahydrofuran.
30. A solid-state lithium secondary battery comprising a positive electrode, the modified solid-state electrolyte according to any one of claims 21 to 27, and a negative electrode, which are sequentially combined.
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