CN105609873A - Branched structure type lithium bis(fluorosulfonyl) imide polymer(R-(PFSILi)n) and synthesis method and application thereof - Google Patents
Branched structure type lithium bis(fluorosulfonyl) imide polymer(R-(PFSILi)n) and synthesis method and application thereof Download PDFInfo
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- CN105609873A CN105609873A CN201510989794.3A CN201510989794A CN105609873A CN 105609873 A CN105609873 A CN 105609873A CN 201510989794 A CN201510989794 A CN 201510989794A CN 105609873 A CN105609873 A CN 105609873A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 64
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 title abstract 2
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 41
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 5
- 150000008442 polyphenolic compounds Chemical class 0.000 claims abstract description 5
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 5
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 99
- 229910052731 fluorine Inorganic materials 0.000 claims description 30
- 239000011737 fluorine Substances 0.000 claims description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 17
- -1 anion lithium salts Chemical class 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910006074 SO2NH2 Inorganic materials 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229910020364 ClSO2 Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 4
- 229960001553 phloroglucinol Drugs 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 239000005518 polymer electrolyte Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims 1
- 108010052322 limitin Proteins 0.000 claims 1
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 abstract 1
- 229920005862 polyol Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 8
- 238000010025 steaming Methods 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 239000007784 solid electrolyte Substances 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- QRMHDYCPNIVCBO-UHFFFAOYSA-N [SH2]=N.[F] Chemical compound [SH2]=N.[F] QRMHDYCPNIVCBO-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 229920000447 polyanionic polymer Polymers 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- IDGCBXSROJHVOG-UHFFFAOYSA-N [Li].[SH2]=N.[F] Chemical compound [Li].[SH2]=N.[F] IDGCBXSROJHVOG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 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 discloses a branched structure type lithium bis(fluorosulfonyl) imide polymer(R-(PFSILi)n) and a synthesis method and application thereof. The polymer is a polyanionic lithium salt polymer with a starlike or treelike structure and the molecular structure of the polymer is as shown in the formula (I). The structuring method of the structure comprises the following steps: selecting different polyphenols or polyols as a substrate; carrying out condensation reaction on a fluorinated monomer and the substrate under the action of an acid-binding agent; and then carrying out lithium ion exchange through a lithium salt to obtain a target molecule. Compared with a one-dimensional direct-chain fluoroalkyl sulfimide structure type polymer, the branched structure type polymer disclosed by the invention has better conductivity and excellent compatibility with anode and cathode materials with high electrochemical activity, also has high lithium ion transference number (t<+> is greater than 0.9) and high electrochemical window (>6V), and further has excellent charge and discharge performance and service life.
Description
Technical field
The invention belongs to the technical field of macromolecular material, relate to the poly-fluorine sulphonyl of a kind of branched structure type AsiaAmine anion lithium salts and synthetic method thereof and application.
Background technology
Lithium ion battery has that specific energy is high, reserve of electricity is large, memory-less effect, long circulation life, volumeThe advantage such as little is the study hotspot of novel power supply technology. Lithium-ion battery system mainly uses liquid at presentState electrolyte, as EC (ethylene carbonate), DEC (diethyl carbonate), PC (propene carbonate),DMC (dimethyl carbonate) and their mixture. These organic electrolytes exist poisonous, volatileWith many potential safety hazards such as inflammable, have a strong impact on the security of battery system. Polymer dielectric canPlay the effect of electrolyte and battery diaphragm simultaneously, therefore do not have free flowable electrolyte solution,Therefore fundamentally eliminated by the many safety such as poisonous, volatile and inflammable that uses electrolyte to bringPotential problem.
At present, the solid polymer that polymer dielectric forms with polyoxyethylene (PEO) and little molecule lithium saltsElectrolyte is the main object of research always. The polyanion structural molecule that comprises fluoroalkyl sulfimideGain a special interest, this mainly has benefited from the electronegative delocalization that is highly dispersed on nitrogen-atoms, shortEnter dissociating of Li+, be conducive to further improve ionic conductivity. In addition the introducing of fluoro-containing group,Also the electrochemical stability to solid electrolyte and heat endurance aspect have played positive role. FranceStyrene side chain introduced by fluoroalkyl sulfimide lithium salts by Bonnet seminar, prepares polystyrene-based fluorineAlkyl sulfonyl imine lithium ionomer P (STFSILi), study this polymer and PEO blend barrier film withCopolymerization membrane properties, found that P (STFSILi)-PEO copolymerization dielectric film has better electricity and leadsRate. P (STFSILi)-b-PEO-b-P (STFSILi) triblock copolymer type electrolysis that research is prepared intoMatter lithium ion transference number is that 0.85,60 DEG C of lithium ion conductivity is 1.3*10-5S/cm, have stablize goodGood cycle performance.
The polyanion lithium salts of future development new structure, particularly has low ionic dissociation energy and branchingThe fluorine-containing sulfimide polyanion of structure lithium salts system, for promoting solid polymer electrolyte performance sideFace has great significance.
Summary of the invention
An object of the present invention is for the deficiencies in the prior art, provide a kind of branched structure type to gather fluorineSulfimide anion lithium salts. The branched structure that it is unique and group move its electrical conductivity, lithium ionShift, electrochemical stability, heat endurance and electrode material compatibility are all significantly improved.
The object of the present invention is achieved like this:
The invention provides as the fluorine-containing sulfimide anion of a kind of branched structure type lithium salts polymerR-(PFSILi) n, wherein branched structure includes but not limited to two-dimentional star structure and 3-d tree-like structure.
The molecular structure of described R-(PFSILi) n includes but not limited to suc as formula (I) Chinese style (a)～(e)Shown several structures:
In formula (I), m, n, p and o are number of repeat unit, are the integer that is greater than zero, preferably 20000～ 50000；
Another object of the present invention is to provide the preparation method of above-mentioned novel polymer material.
With fluorochemical monomer and substrate, condensation reaction under acid binding agent effect obtains branched structure polymerization to the methodThing, further uses inorganic lithium salt to carry out metal exchange, finally obtains the macromolecular material of lithium salt form,Its reaction equation is suc as formula shown in (IV), in formulaFor polyphenolic substance,For polyalcohol:
The concrete steps of synthetic method of the present invention are as follows:
Step (1): substrate and fluorochemical monomer are dissolved in dry acetonitrile, add acid binding agent, be placed inUnder 0～200 DEG C of condition, react 1d～10d, obtain branching type gathering containing poly-fluorine sulfimide base salt structureCompound R-(PFSIM)n；
The mol ratio of described substrate, fluorochemical monomer and the acid binding agent of step (1) be 1:3～100:3～100, every gram of fluorochemical monomer is dissolved in 5～20mL acetonitrile;
Acid binding agent described in step (1) includes but not limited to CsF, KF, Cs2CO3、K2CO3、Na2CO3In one.
Branching type described in step (1) is containing the polymer R-(PFSIM) of poly-fluorine sulfimide base salt structurenIn M represent metal cation, its source for acid binding agent, includes but not limited to Cs+、K+、Na+InA kind of.
The described fluorochemical monomer of step (1) is ClSO2CF2CF2OCF2CF2SO2NH2；
The described branching type of step (1) contains poly-fluorine sulfimide base salt polymer R-(PFSIM)nMolecular formulaInclude but not limited to suc as formula several structures shown in (f) in (II)～(j):
In formula (II), m, n, p and o are number of repeat unit, are the integer that is greater than zero, be preferably 20000～50000; M is metal ion, includes but not limited to Se ﹑ potassium or sodium;
Substrate described in step (1) is polyphenol or polyalcohol, includes but not limited to phloroglucin, manyOne or more in three phenolic compounds of aromatic ring structure, season penta triol, pentaerythrite, glycerine,Its molecular structure includes but not limited to suc as formula several structures shown in (III):
Step (2): the polymer of the metal ion salt form that step (1) is obtained is dissolved in organic solvent,Then add lithium salts, at 0～50 DEG C, carry out lithium ion exchanged reaction 1h～24h, obtain branching type and containPoly-fluorine sulfimide base lithium salts polymer R-(PFSILi)n, the polymer that this polymer is lithium salt form;
In lithium salts described in step (2), in lithium ion and step (I), the mol ratio of fluorochemical monomer is 1:1; OftenThe polymer dissolution of gram metal ion form is in 1～10mL organic solvent;
The described organic solvent of step (2) includes but not limited to acetonitrile, chloroform, carrene, tetrahydrochysene furanMutter, ether.
Lithium salts Li described in step (2)zIn X, X includes but not limited to Cl-、Br-、I-、NO3 -、ClO4 -、BF4 -、PF6 3-, z is 1 or 3.
What step (2) was described obtains the polymer of branching type containing poly-fluorine sulfimide base lithium salts structureR-(PFSILi)n, molecular structure includes but not limited to several structures shown in (a) suc as formula (I)～(e):
In formula (I), m, n, p and o are number of repeat unit, are the integer that is greater than zero, preferably 20000～50000。
Another object of the present invention is to provide the poly-fluorine sulfimide lithium salts polymer of above-mentioned branching typeR-(PFSILi)nIn the application of preparing in lithium battery. Positive electrode in lithium battery is LiFePO4, cobaltThe composite material of one or more in acid lithium, lithium nickelate, LiMn2O4; Negative material is lithium metalSheet or graphitic carbonaceous materials.
A further object of the present invention is to provide the poly-fluorine sulfimide lithium salts polymer of above-mentioned branching typeR-(PFSILi)nWith polyethylene glycol oxide PEO (Mn: 100,000～600,000) blend is prepared all solid stateThe method of polymer dielectric film. The method is by poly-branching type fluorine sulfimide lithium R-(PFSILi)nBe dissolved in respectively in a certain amount of acetonitrile according to the mol ratio of 1:8～30 with polyethylene glycol oxide PEO, willThis solution mix and blend 24h, in the Teflon culture dish that Injection Level is placed in drier, castingFilm forming. Be placed in 30～60 DEG C of dry 24～48h of vacuum drying oven, obtain solid polyelectrolyte film.
Beneficial effect of the present invention is as follows:
Be substrate by introducing polyphenol and polyalcohol, multiple the poly-of star and tree structure that have synthesized in designFluoroalkyl sulfimide lithium salts polymer R-(PFSILi)n, the positive and negative pole material of itself and high electrochemical activityThere is good compatibility, possess good electrical conductivity, high-lithium ion transport number, high electrochemical window(> 6V), good charge-discharge performance and life-span under high temperature, high safety factor etc.
The reason of its above-mentioned advantage is, is that polyanion molecule stable makes moving of lithium ion on the one handShift significantly improves, and has reduced the internal polarization in cyclic process, thereby has optimized electrolytical circulationSpecific capacity and life-span; On the other hand, P (FSILi)nBe added in solid state electrolysis plastidome and can form 2-DOr 3-D ionomer structure, increase ion channel, be beneficial to lithium ion transporting therein, improveElectrical conductivity.
Brief description of the drawings
Fig. 1 is that branching type prepared by embodiment 5 contains the polymer that gathers fluorine sulfimide base lithium salts structureR-(PFSILi)nThe photo of film.
Fig. 2 is that branching type prepared by embodiment 5 contains the polymer core that gathers fluorine sulfimide base lithium salts structureMagnetic resonance spectrogram.
Fig. 3 is branching type R-(PFSILi) prepared by embodiment 5nWith PEO blend and one-dimension typeP(FSILi)nWith polyethylene glycol oxide PEO blend dielectric film electrical conductivity comparison diagram within the specific limits.
Fig. 4 be in embodiment 5, make branching type polymer R-(PFSILi)nThe solid state electrolysis of makingThe circulating battery high rate performance of plasma membrane.
Detailed description of the invention
Below with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail: should be appreciated thatPreferred embodiment is only for the present invention is described, instead of in order to limit the scope of the invention.
Example 1～8 relates to the polymer R-(PFSILi) of branching type containing poly-fluorine sulfimide base salt structurenPreparation method.
Embodiment 1:
Step 1: in inert atmosphere, by fluorochemical monomerClSO2CF2CF2OCF2CF2SO2NH2(Mn=395.5,7.1g, 18mmol) be dissolved in acetonitrile (100mL) whenIn, in this solution, add CsF (Mn=152,12.2g, 80mmol), phloroglucin (Mn＝126,0.76G, 6mmol) be heated to after 50 DEG C of stirring reaction 4d, reacting liquid filtering, revolves steaming by filtrate, obtainsThe branched structure R-(PFSICs) of cesium salt formnPolymer, its molecular structural formula is suc as formula shown in (r).
In formula (r), m, n, p are the integer that is greater than zero, are preferably 20000～50000.
Step 2: the branched structure R-(PFSICs) of the cesium salt form that step 1 is obtainedn(6g) poly-Compound is dissolved in acetonitrile (16mL), by LiClO4(1.9g, 18mmol) uses acetonitrile (2mL)Dissolve, dropwise join in the middle of the acetonitrile solution that contains polymer, be placed at 0 DEG C and stir after 24h,Filtration obtains lithium salt form polymer R-(PFSILi)n, its molecular structural formula is suc as formula shown in (a).
In formula (a), m, n, p are the integer that is greater than zero, are preferably 20000～50000.
Embodiment 2:
Step 1: in inert atmosphere, by fluorochemical monomerClSO2CF2CF2OCF2CF2SO2NH2(Mn=395.5,8g, 20mmol) be dissolved in the middle of acetonitrile (100mL),In this solution, add KF (Mn=58,2.4g, 40mmol), phloroglucin (Mn＝126,0.76g,6mmol)Be heated to after 60 DEG C of stirring reaction 5d, reacting liquid filtering, revolves steaming by filtrate, obtains potassium salt formBranched structure R-(PFSIK)nPolymer, its molecular structural formula is suc as formula shown in (s).
In formula (s), m, n, p are the integer that is greater than zero, are preferably 20000～50000.
Step 2: the branched structure R-(PFSIK) of the potassium salt form that step 1 is obtainedn(6g) polymerizationThing is dissolved in oxolane (20mL), by LiClO4(2.13g, 20mmol) uses oxolane(10mL) dissolve, dropwise join in the middle of the tetrahydrofuran solution that contains polymer, be placed in 20 DEG CAfter lower stirring 20h, filter and obtain lithium salt form polymer R-(PFSILi)n, its molecular structural formula suc as formula(a) shown in.
In formula (a), m, n, p are the integer that is greater than zero, are preferably 20000～50000.
Embodiment 3:
Step 1: in inert atmosphere, by fluorochemical monomer ClSO2CF2CF2OCF2CF2SO2NH2(Mn＝395.5,4G, 10mmol) be dissolved in the middle of acetonitrile (80mL), in this solution, add Cs2CO3(Mn＝326,13g,40Mmol), season penta triol (Mn=120,0.36g, 3mmol) be heated to after 100 DEG C of stirring reaction 1d,Reacting liquid filtering, revolves steaming by filtrate, obtains the branched structure R-(PFSICs) of cesium salt formnPolymer,Its molecular structural formula is as shown in (t) formula.
In formula (t), m, n, p are the integer that is greater than zero, are preferably 20000～50000.
Step 2: the branched structure R-(PFSICs) of the cesium salt form that step 1 is obtainedn(7g) poly-Compound is dissolved in acetonitrile (16mL), by LiBF4(1g, 10mmol) is molten with acetonitrile (2mL)Separate, dropwise join in the middle of the acetonitrile solution that contains polymer, be placed at 30 DEG C and stir after 20h, mistakeFilter obtains lithium salt form polymer, and its molecular structural formula is as shown in (k) formula.
In formula (k), m, n, p are the integer that is greater than zero, are preferably 20000～50000.
Embodiment 4:
Step 1: in inert atmosphere, by fluorochemical monomer ClSO2CF2CF2OCF2CF2SO2NH2(Mn＝395.5,4G, 10mmol) be dissolved in the middle of acetonitrile (80mL), in this solution, add K2CO3(Mn＝138,5.6g,40Mmol), tertiary butantriol (Mn=100,0.3g, 3mmol) be heated to after 100 DEG C of stirring reaction 1d,Reacting liquid filtering, revolves steaming by filtrate, obtains the branched structure R-(PFSIK) of potassium salt formnPolymer,Its molecular structural formula is as shown in (u) formula.
In formula (u), m, n, p are the integer that is greater than zero, are preferably 20000～50000.
Step 2: the branched structure R-(PFSIK) of the potassium salt form that step 1 is obtainedn(7g) polymerizationThing is dissolved in acetonitrile (16mL), by LiBF4(1g, 10mmol) dissolves with acetonitrile (2mL),Dropwise join in the middle of the acetonitrile solution that contains polymer, be placed at 30 DEG C and stir after 20h, filterTo lithium salt form polymer, its molecular structural formula is as shown in (l) formula.
In formula (l), m, n, p are the integer that is greater than zero, are preferably 20000～50000.
Embodiment 5:
Step 1: in inert atmosphere, by fluorochemical monomerClSO2CF2CF2OCF2CF2SO2NH2(Mn=395.5,197.7g, 500mmol) be dissolved in acetonitrile (100mL)In the middle of, in this solution, add Cs2CO3(Mn=326,163g, 500mmol), pentaerythrite(Mn=136,0.7g, 5mmol) be heated to after 200 DEG C of stirring reaction 10d, reacting liquid filtering, will filterLiquid revolves steaming, obtains the branched structure R-(PFSICS) of cesium salt formnPolymer, its molecular structural formula is as (v)Shown in formula.
In formula (v), m, n, p and o are the integer that is greater than zero, are preferably 20000～50000.
Step 2: the branched structure R-(PFSICS) of the cesium salt form that step 1 is obtainedn(198g)Polymer dissolution is in acetonitrile (400mL), by LiNO3(34.5g, 500mmol) uses acetonitrile (70mL)Dissolve, dropwise join in the middle of the acetonitrile solution that contains polymer, be placed at 50 DEG C and stir after 1h,Filtration obtains lithium salt form polymer, and its molecular structural formula is as shown in (c) formula.
In formula (c), m, n, p and o are the integer that is greater than zero, are preferably 20000～50000.
Fig. 1 is that branching type prepared by embodiment 5 contains the polymer that gathers fluorine sulfimide base lithium salts structureR-(PFSILi)nThe photo of film.
Fig. 2 is that branching type prepared by embodiment 5 contains the polymer core that gathers fluorine sulfimide base lithium salts structureMagnetic resonance spectrogram.
Poly-prepared branching type fluorine sulfimide lithium R-(PFSILi) n is dissolved in to a certain amount of acetonitrileIn, by this solution mix and blend 24h, in the Teflon culture dish that Injection Level is placed in drier,Casting film. Be placed in 30 DEG C of dry 48h of vacuum drying oven, obtain solid polyelectrolyte film, figure4 is prepared solid electrolyte membrane.
Embodiment 6:
Step 1: in inert atmosphere, by fluorochemical monomer ClSO2CF2CF2OCF2CF2SO2NH2(Mn＝395.5,4G, 10mmol) be dissolved in the middle of acetonitrile (80mL), in this solution, add K2CO3(Mn＝138,5.52g,40Mmol), glycerine (Mn=87,0.26g, 3mmol) be heated to after 0 DEG C of stirring reaction 24d reactionLiquid filters, and filtrate is revolved to steaming, obtains the branched structure R-(PFSIK) of potassium salt formnPolymer, its pointMinor structure formula is as shown in (w) formula.
In formula (w), m, n, p are the integer that is greater than zero, are preferably 20000～50000.
Step 2: the branched structure R-(PFSIK) of the potassium salt form that step 1 is obtainedn(4g) polymerizationThing is dissolved in chloroform (16mL), by molten chloroform (2mL) for LiI (1.34g, 10mmol)Separate, dropwise join in the middle of the chloroformic solution that contains polymer, be placed at 30 DEG C and stir after 20h, mistakeFilter obtains lithium salt form polymer R-(PFSILi)n, its molecular structural formula is as shown in (d) formula.
In formula (d), m, n, p are the integer that is greater than zero, are preferably 20000～50000.
Embodiment 7:
Step 1: in inert atmosphere, by fluorochemical monomerClSO2CF2CF2OCF2CF2SO2NH2(Mn=395.5,6g, 15mmol) be dissolved in the middle of acetonitrile (100mL),In this solution, add Na2CO3(Mn=106,8g, 75mmol), 4,4', 4 "-trihydroxy triphenylamine(Mn=293,1.5g, 5mmol) be heated to after 180 DEG C of stirring reaction 7d, reacting liquid filtering, will filterLiquid revolves steaming, obtains the branched structure R-(PFSINa) of sodium-salt formnPolymer, its molecular structural formula is as (x)Shown in formula.
In formula (e), m, n, p are the integer that is greater than zero, are preferably 20000～50000.
Step 2: the branched structure R-(PFSINa) of the sodium-salt form that step 1 is obtainedn(7.4g)Polymer dissolution is in acetonitrile (16mL), by LiNO3(1g, 15mmol) uses acetonitrile (5mL)Dissolve, dropwise join in the middle of the acetonitrile solution that contains polymer, be placed at 50 DEG C and stir after 1h,Filtration obtains lithium salt form polymer, and its molecular structural formula is as shown in (e) formula.
In formula (e), m, n, p are the integer that is greater than zero, are preferably 20000～50000.
Embodiment 8:
Step 1: in inert atmosphere, by fluorochemical monomerClSO2CF2CF2OCF2CF2SO2NH2(Mn=395.5,4g, 10mmol) be dissolved in the middle of acetonitrile (80mL),In this solution, add K2CO3(Mn=138,5.52g, 40mmol), glycerine (Mn＝87,0.13g,1.5Mmol), pentaerythrite (Mn=136,0.2g, 1.5mmol) is heated to after 150 DEG C of stirring reaction 3d,Reacting liquid filtering, revolves steaming by filtrate, obtains the branched structure R-(PFSIK) of potassium salt formnPolymer,Its molecular structural formula is the mixture suc as formula two kinds of polymer shown in (y) and formula (w).
In formula (c) and formula (d), m, n, p are the integer that is greater than zero, are preferably 20000～50000.
Step 2: the branched structure R-(PFSIK) of the potassium salt form that step 1 is obtainedn(5g) polymerizationThing is dissolved in chloroform (16mL), by molten chloroform (2mL) for LiI (1.34g, 10mmol)Separate, dropwise join in the middle of the chloroformic solution that contains polymer, be placed at 30 DEG C and stir after 20h, mistakeFilter obtains lithium salt form polymer R-(PFSILi)n, its molecular structural formula is suc as formula shown in (c) and formula (d)The mixture of two kinds of polymer.
In formula (c) and formula (d), m, n, p are the integer that is greater than zero, are preferably 20000～50000.
Example 9～10 relates to the polymer P (FSILi) of branching type containing poly-fluorine sulfimide base salt structurenPrepare the preparation method of polymer dielectric film with polyethylene glycol oxide PEO blend.
Embodiment 9: the two-dimentional star structure lithium salt form polymer that embodiment 1 is obtainedR-(PFSILi)nWith polyethylene glycol oxide PEO (Mn=100,000) be dissolved in respectively according to the proportioning of 1:30In a certain amount of acetonitrile, by this solution mix and blend 24h, in drier, Injection Level is placedIn Teflon culture dish, casting film. With 60 DEG C of dry 24h in vacuum drying oven, obtain polymer solidState dielectric film.
Embodiment 10: the poly-fluorine sulfimide lithium of large molecule tree that embodiment 3 is obtainedR-(PFSILi)nWith polyethylene glycol oxide PEO (Mn=600,000) be dissolved in respectively according to the proportioning of 1:8In a certain amount of acetonitrile, by this solution mix and blend 24h, in drier, Injection Level is placedIn Teflon culture dish, casting film. With 30 DEG C of dry 48h in vacuum drying oven, obtain polymer solidState dielectric film.
Embodiment 11～13 relates to the polymer containing poly-fluorine sulfimide base salt structure based on branching typeR-(PFSILi)nThe application of solid electrolyte in lithium ion battery.
Embodiment 11:R-(PFSILi)nThe test of dielectric film ionic conductivity
In the present invention, use the AC impedance of ZahnerEL101 electrochemical workstation test solid electrolyteSpectrum, range of scanned frequencies is 100mHz～100KHz, disturbance voltage is 5mV, temperature range be room temperature～120 DEG C, at each temperature, battery constant temperature 4h. By solid electrolyte membrane group in glove box of preparationDress CR2032 type stainless steel substrates/dielectric film/stainless steel substrates battery, by the friendship of test solid electrolyteFlow impedance composes analytical calculation its body resistance R b (Ohm), in conjunction with dielectric film thickness d (cm) and filmWith electrode contact area (cm2) calculate ionic conductivity σ (S/cm) according to formula below, obtain fromElectron conductivity.
In formula, σ is polymer dielectric ionic conductivity (S/cm), RbFor this bulk resistor (Ω), dFor dielectric film thickness (cm), A is electrode and film contact area (cm2)。
As shown in Figure 3, branching type R-(PFSILi)nDielectric film is than P (FSILi)nWithPEO (Mn:600,000) polymer blend membrane conductivity height 2 orders of magnitude. Along with the rising of temperature,The electrical conductivity of two kinds of solid electrolyte membranes is improved.
Example 12:R-(PFSILi)nThe test of dielectric film transference number of ions
By the R-(PFSILi) of preparationnDielectric film is assembled into the symmetrical battery of button, and made battery is placed inConstant temperature 2h in 80 DEG C. Electrochemical workstation test ac impedance spectroscopy, test frequency scope 1mHz～1MHz, then constant voltage polarization mode again, a given voltage, carries out direct current polarization experiment. LogicalCross electric current and the impedance etc. of test polarization front and back and calculate lithium ion transference number. Should through measuring and calculationType R-(PFSILi)nThe lithium ion transference number of dielectric film can reach 0.95.
Example 13:R-(PFSILi)nThe test of dielectric film charge and discharge cycles
By LiFePO4, SuperP, PVDF be mixed with anode sizing agent by a certain percentage, evenly applyOn aluminium foil, heating, vacuum is dry, obtains the pole piece of level and smooth calculus. In negative electrode casing, put into successively notRust steel plate washer, cathode pole piece, R-(PFSILi)nDielectric film, anode pole piece, cover anode cover, envelopeDress up 2032 type button cells. The button cell of preparation is put into 80 DEG C of constant temperature 2h of baking oven; ThenConnect LandCT2001A battery test system, between 2.7～4.2V, carry out charge and discharge cycles test.
As shown in Figure 4, by the solid polymer cell of preparation 70 DEG C of multiplying powers be respectively 0.1C, 0.2C,Under 0.5C, 1C, 2C, 3C, circulate 50 times, total duration is 15 days. Can find out, 0.1Its capacity that discharges under multiplying power can remain on 140mAhg-1Above. Through 50 circulation different multiplyingAfter discharging and recharging, its capacity can remain on 60%. Can find out, its under 3C high-multiplying power discharge condition,Still can keep 90Ahg-1The capacity of electric discharge.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, obviously, thisThe technical staff in field can carry out various changes and modification and not depart from spirit of the present invention the present inventionAnd scope. Like this, if of the present invention these amendment and modification belong to the claims in the present invention and etc.Within scope with technology, the present invention be also intended to comprise these change and modification interior.
Claims (10)
1. the poly-fluorine sulfimide anion lithium salts of branched structure type, is the fluorine-containing sulphonyl of branched structure typeImines anion lithium salts polymer R-(PFSILi) n, is characterized in that its molecular structure comprises but do not limitIn suc as formula several structures shown in (I) Chinese style (a)～(e):
In formula (I), m, n, p and o are number of repeat unit, are the integer that is greater than zero.
2. the poly-fluorine sulfimide anion lithium salts of a kind of branched structure type as claimed in claim 1, itsBe characterised in that this branched structure comprises two-dimentional star structure and 3-d tree-like structure.
3. closing of the poly-fluorine sulfimide anion lithium salts of a kind of branched structure type as claimed in claim 1One-tenth method, is characterized in that condensation reaction under acid binding agent effect obtains the method with fluorochemical monomer and substrateObtain branched structure polymer, further use inorganic lithium salt to carry out metal exchange, finally obtain lithium salts shapeThe macromolecular material of formula; Wherein substrate is polyphenol or polyalcohol.
4. closing of the poly-fluorine sulfimide anion lithium salts of a kind of branched structure type as claimed in claim 3One-tenth method, is characterized in that the method specifically comprises the following steps:
Step (1): fluorochemical monomer and substrate are dissolved in dry acetonitrile, and add acid binding agent, putUnder 0～200 DEG C of condition, react 1d～10d, obtain branching type containing poly-fluorine sulfimide base salt structurePolymer; Wherein substrate is polyphenol or polyalcohol;
The use equivalent proportion of substrate, fluorochemical monomer and acid binding agent described in step (1) is 1:3～100:3～100, every gram of fluorochemical monomer is dissolved in 5～20mL acetonitrile;
Step (2): the polymer of the metal ion salt form that step (1) is obtained is dissolved in organic solventIn, then add lithium salts, at 0～50 DEG C, carry out lithium ion exchanged reaction 1h～24h, obtain branchingType is containing poly-fluorine sulfimide base lithium salts polymer R-(PFSILi)n, the polymerization that this polymer is lithium salt formThing.
5. the poly-fluorine sulfimide anion lithium salts of a kind of branched structure type as described in claim 3 or 4Synthetic method, it is characterized in that the mol ratio of described substrate, fluorochemical monomer and acid binding agent of step (1)For 1:3～100:3～100, every gram of fluorochemical monomer is dissolved in 5～20mL acetonitrile; Step (2) instituteIn the lithium salts of stating, in lithium ion and step (1), the mol ratio of fluorochemical monomer is 1:1, every gram of metal ion shapeThe polymer dissolution of formula is in 1～10mL organic solvent.
6. the poly-fluorine sulfimide anion lithium salts of a kind of branched structure type as described in claim 3 or 4Synthetic method, it is characterized in that the branching type described in step (1) is poly-containing poly-fluorine sulfimide base saltCompound R-(PFSIM)nMolecular formula includes but not limited to suc as formula several knots shown in (f) in (III)～(j)Structure:
In formula (III), m, n, p and o are number of repeat unit, are the integer that is greater than zero; M is goldBelong to ion.
7. the poly-fluorine sulfimide anion lithium salts of a kind of branched structure type as described in claim 3 or 4Synthetic method, it is characterized in that the described acid binding agent of step (1) include but not limited to CsF, KF,Cs2CO3、K2CO3、Na2CO3In one, described fluorochemical monomer is ClSO2CF2CF2OCF2CF2SO2NH2；Organic solvent described in step (2) includes but not limited to acetonitrile, chloroform, carrene, tetrahydrochysene furanMutter or ether, described lithium salts LizIn X, X includes but not limited to Cl-、Br-、I-、NO3 -、ClO4 -、BF4 -Or PF6 3-, z is 1 or 3.
8. the poly-fluorine sulfimide anion lithium salts of a kind of branched structure type as described in claim 3 or 4Synthetic method, it is characterized in that the substrate described in step (1) include but not limited to phloroglucin,A kind of or many in three phenolic compounds of many aromatic ring structures, season penta triol, pentaerythrite, glycerineKind, its molecular structure includes but not limited to suc as formula several structures shown in (IV):
9. the poly-fluorine sulfimide anion lithium salts of a kind of branched structure type as claimed in claim 1 is in systemApplication in standby lithium battery.
10. the poly-fluorine sulfimide anion lithium salts of a kind of branched structure type as claimed in claim 1, itsBe characterised in that poly-fluorine sulfimide lithium salts polymer R-(PFSILi) n of branching type and polyethylene glycol oxide PEOFull solid state polymer electrolyte film is prepared in blend.
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| CN111480256A (en) * | 2018-04-20 | 2020-07-31 | 株式会社Lg化学 | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
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| CN107459647A (en) * | 2016-06-02 | 2017-12-12 | 杭州聚力氢能科技有限公司 | The polyimide type single-ion conductor polymer of the double sulfimides of side chain graft and its application |
| CN107459647B (en) * | 2016-06-02 | 2020-04-14 | 杭州聚力氢能科技有限公司 | Polyimide type single ion conducting polymer with side chain grafted bis-sulfimide and application thereof |
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| CN105870499B (en) * | 2016-06-03 | 2020-09-08 | 宁波莲华环保科技股份有限公司 | Fluorine-containing sulfimide gel electrolyte and preparation method and application thereof |
| CN111480256A (en) * | 2018-04-20 | 2020-07-31 | 株式会社Lg化学 | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
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| CN111480256B (en) * | 2018-04-20 | 2023-10-10 | 株式会社Lg新能源 | Electrolyte for lithium secondary battery and lithium secondary battery including the same |
| CN109286040A (en) * | 2018-08-03 | 2019-01-29 | 南京理工大学 | Four arm branched polymeric ionic liquid gel electrolyte membrances and preparation method thereof |
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