CN109346767A - A solid polymer electrolyte and its application in lithium metal batteries - Google Patents
A solid polymer electrolyte and its application in lithium metal batteries Download PDFInfo
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- CN109346767A CN109346767A CN201811292552.9A CN201811292552A CN109346767A CN 109346767 A CN109346767 A CN 109346767A CN 201811292552 A CN201811292552 A CN 201811292552A CN 109346767 A CN109346767 A CN 109346767A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 56
- 239000007787 solid Substances 0.000 title claims abstract description 56
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 49
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 26
- 239000010416 ion conductor Substances 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 229920000570 polyether Polymers 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 9
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 6
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 229960002645 boric acid Drugs 0.000 claims description 5
- 235000010338 boric acid Nutrition 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims description 4
- PQYORWUWYBPJLQ-UHFFFAOYSA-N buta-1,3-diene;sulfurous acid Chemical compound C=CC=C.OS(O)=O PQYORWUWYBPJLQ-UHFFFAOYSA-N 0.000 claims description 4
- 150000007517 lewis acids Chemical class 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- YHLVIDQQTOMBGN-UHFFFAOYSA-N methyl prop-2-enyl carbonate Chemical compound COC(=O)OCC=C YHLVIDQQTOMBGN-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000002482 conductive additive Substances 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000005077 polysulfide Substances 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- 150000008117 polysulfides Polymers 0.000 claims description 3
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 3
- 125000006091 1,3-dioxolane group Chemical group 0.000 claims description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- YKOWROBULMNQMD-UHFFFAOYSA-N [Li].[SH2]=N.FC Chemical compound [Li].[SH2]=N.FC YKOWROBULMNQMD-UHFFFAOYSA-N 0.000 claims 1
- 239000004020 conductor Substances 0.000 claims 1
- 150000002240 furans Chemical class 0.000 claims 1
- 210000001787 dendrite Anatomy 0.000 abstract description 3
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- 230000009036 growth inhibition Effects 0.000 abstract 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 description 19
- 210000004027 cell Anatomy 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- MWQJGSUQGMJVCS-UHFFFAOYSA-N N=[S+]C(F)(F)F.[Li] Chemical compound N=[S+]C(F)(F)F.[Li] MWQJGSUQGMJVCS-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000867 polyelectrolyte Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 230000022131 cell cycle Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000012704 polymeric precursor Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910001544 silver hexafluoroantimonate(V) Inorganic materials 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
本发明涉及一种固态聚合物电解质及其在锂金属电池中的应用，它包括聚合物基体以及形成在所述聚合物基体中的锂离子导体，所述聚合物基体为选自聚醚、聚碳酸酯、聚硫酸酯中的一种或多种。通过在特定种类的聚合物基体中负载锂离子导体而获得固态电解质，不仅具有优异的枝晶生长抑制、安全性和可靠性提高的优点，还表现出易加工性、高柔韧性、轻重量和高离子电导率、低界面电阻的优点，适用于在锂金属电池中的大规模应用。
The present invention relates to a solid polymer electrolyte and its application in lithium metal batteries, comprising a polymer matrix and a lithium ion conductor formed in the polymer matrix, wherein the polymer matrix is selected from polyether, polyether One or more of carbonate and polysulfate. Solid-state electrolytes obtained by supporting lithium ion conductors in a specific kind of polymer matrix not only have the advantages of excellent dendrite growth inhibition, improved safety and reliability, but also exhibit ease of processing, high flexibility, light weight and The advantages of high ionic conductivity and low interfacial resistance are suitable for large-scale applications in lithium metal batteries.
Description
Technical field
The invention belongs to field of lithium, are related to a kind of electrolyte, and in particular to a kind of solid polymer electrolyte and its
Application in lithium metal battery.
Background technique
Lithium ion battery due to having many advantages, such as high-energy density, having extended cycle life is widely used in electronic power supply,
Occupy leading market status.When lithium ion battery by supper-fast charging, discharge or overcharge etc. abuse conditions when, electricity
The high-energy-density density in pond would generally cause energy response, generate huge heat, therefore use the normal of non-aqueous electrolyte
The security risk for advising lithium ion battery is still an important challenge and unsolved obstacle, especially in large scale and high energy
In metric density application system.This is because being grown on lithium anode caused by lithium metal nonuniform deposition after repeated charge
Space between Li dendrite meeting bridged electrodes, leads to internal short-circuit of battery.In volatile electrolyte, by a system of these short circuit generations
Column exothermic reaction may cause overheat and thermal runaway, then further increase internal battery-temperature and pressure, generate catastrophic
Fire or explosion danger；And a possibility that thermal failure it is significant increase with the increase of battery size, be unfavorable for lithium-ion electric
The commercialization of pond group.
In order to inhibit the cause dendritic growth of fever, solid polymer electrolyte is undoubtedly considered as a kind of ideal solution
Certainly scheme.Compared with liquid electrolyte, it has the advantages that excellent dendritic growth inhibits, safety and reliability improves；With
Inorganic ceramic electrolyte phase ratio, makes it at the advantages of also showing workability, high-flexibility, light weight and low interfacial resistance
Suitable for the large-scale application lithium ion battery.Under normal conditions, the polymeric matrix of solid polymer electrolyte is answered
With high dielectric constant, to separate enough lithium salts as lithium ion conductor.
Summary of the invention
One kind is provided the invention aims to overcome the deficiencies in the prior art has room temperature high ionic conductivity and energy
Inhibit the solid polymer electrolyte of lithium dendrite growth.
In order to achieve the above objectives, the technical solution adopted by the present invention is that: a kind of solid polymer electrolyte, it include polymerization
The lithium ion conductor of object matrix and formation in the polymer matrix, the polymeric matrix are selected from polyethers, poly- carbonic acid
One of ester, polysulfide acid esters are a variety of.
Optimally, the polymeric matrix carries out polymerization reaction by liquid monomer under the action of catalyst or initiator and obtains
, the liquid monomer is selected from 1,3-dioxolane, tetrahydrofuran, fourth oxygen ring, vinylene carbonate, ethylene carbonate Asia second
Ester, diallyl carbonate, Allyl methyl carbonate, in bis- (2- methacrylic) carbonic esters and vinyl ethylene sulfite
One or more.Specifically, the catalyst be one of strong protonic acid, solid acid, precious metal salt and lewis acid or
It is several；The initiator is selected from one of azo-initiator, organic peroxy class initiator and inorganic peroxy class initiator
Or it is several.
Optimally, it is lithium ion conductor to be dissolved in liquid monomer, then carry out polymerization reaction acquisition；Specifically, lithium
Content of the ion conductor in liquid monomer is 1~2mol/L.
Optimally, the lithium ion conductor is selected from bis trifluoromethyl sulfimide lithium, lithium hexafluoro phosphate, dioxalic acid boric acid
One of lithium, lithium perchlorate, difluorine oxalic acid boracic acid lithium, LiBF4 and trifluoromethyl sulfonic acid lithium or a variety of combinations.
Another object of the present invention is to provide a kind of application of above-mentioned solid polymer electrolyte in lithium metal battery,
The solid polymer electrolyte and anode, cathode are subjected to assembling and form battery, the anode is lithium metal, and the cathode is
Selected from one of LiFePO4, ternary material, nickel ion doped and sulphur carbon material or a variety of.
Optimally, the battery be button cell, the solid polymer electrolyte be assembled with iris-diaphragm, or
Person carries out in-situ polymerization after injecting with liquid.
Optimally, the cathode also includes conductive additive and binder.
Due to the above technical solutions, the present invention has the following advantages over the prior art: solid-state polymerization of the present invention
Object electrolyte obtains solid electrolyte and loading lithium ion conductor in particular kind of polymeric matrix, not only has
The advantages of excellent dendritic growth inhibits, safety and reliability improves, also shows workability, high-flexibility, light weight
The advantages of with high ionic conductivity, low interfacial resistance, suitable for the large-scale application lithium metal battery；It can use original
Position polymerization methods obtain, to realize good contact and the compatibility between solid electrolyte and cathode/anode；It is used for lithium
Metal secondary batteries can greatly improve its cycle performance and security performance.
Detailed description of the invention
Fig. 1 is the scanning electron microscope image of polymer dielectric in-situ polymerization in lithium piece made from embodiment 1；
Fig. 2 is the ionic conductivity figure of solid polyelectrolyte made from embodiment 1；
Fig. 3 is that 1 in-situ polymerization object electrolyte of embodiment assembles lithium Symmetrical cells cyclic polarization curve；
Fig. 4 is that the polymer dielectric of in-situ polymerization prepared by embodiment 1 is applied to the secondary electricity of LiFePO4 // lithium metal
The cycle performance figure in pond；
Fig. 5 is that the polymer dielectric of in-situ polymerization prepared by embodiment 1 is applied to the cycle performance figure of lithium-sulfur cell；
Fig. 6 is the scanning electron microscope image of polymer dielectric in-situ polymerization in lithium piece made from embodiment 14；
Fig. 7 is the ionic conductivity figure of solid polyelectrolyte made from embodiment 14；
Fig. 8 is that 14 in-situ polymerization object electrolyte of embodiment assembles lithium Symmetrical cells cyclic polarization curve；
Fig. 9 is that the polymer dielectric of in-situ polymerization prepared by embodiment 14 is applied to the secondary electricity of LiFePO4 // lithium metal
The cycle performance figure in pond.
Specific embodiment
Solid polymer electrolyte of the present invention, it includes the lithium of polymeric matrix and formation in the polymer matrix
Ion conductor, the polymeric matrix are selected from one of polyethers, polycarbonate, polysulfide acid esters or a variety of.By specific
Lithium ion conductor is loaded in the polymeric matrix of type and obtains solid electrolyte, not only inhibit with excellent dendritic growth,
The advantages of safety and reliability improves, also shows workability, high-flexibility, light weight and high ionic conductivity, lower bound
The advantages of surface resistance, suitable for the large-scale application lithium metal battery；It can use in-situ polymerization mode and obtains, thus
Realize good contact and the compatibility between solid electrolyte and cathode/anode；It is used for lithium metal secondary cell, it can be substantially
Improve its cycle performance and security performance.
Above-mentioned polymeric matrix is usually carried out polymerization reaction acquisition by liquid monomer under the action of catalyst or initiator
(first lithium ion conductor can be dissolved in liquid monomer and form uniform mixed solution, then make mixed solution in catalyst or
Under the action of initiator occur polymerization reaction obtain), the liquid monomer be preferably selected from 1,3-dioxolane, tetrahydrofuran,
Fourth oxygen ring, vinylene carbonate, vinylethylene carbonate, diallyl carbonate, Allyl methyl carbonate, bis- (2- methyl alkene
Propyl) one or more of carbonic ester and vinyl ethylene sulfite.The lithium ion conductor is selected from bis trifluoromethyl
Sulfimide lithium, lithium hexafluoro phosphate, dioxalic acid lithium borate, lithium perchlorate, difluorine oxalic acid boracic acid lithium, LiBF4 and fluoroform
One of base Sulfonic Lithium or a variety of combinations.The catalyst is in strong protonic acid, solid acid, precious metal salt and lewis acid
One or more.The initiator is selected from azo-initiator, organic peroxy class initiator and inorganic peroxy class initiator
One or more of.When lithium ion conductor is dissolved in form uniform mixed solution in liquid monomer when, can to mix
The concentration of lithium ion conductor is 1~2mol/L in solution.
Application of the above-mentioned solid polymer electrolyte in lithium metal battery is by the solid polymer electrolyte and sun
Pole, cathode carry out assembling and form battery, and the anode is lithium metal, and the cathode is selected from LiFePO4, ternary material, nickel manganese
One of sour lithium and sulphur carbon material are a variety of.Above-mentioned battery is usually button cell, the solid polymer electrolyte be with
Iris-diaphragm is assembled, or carries out in-situ polymerization assembling after injecting with liquid.The cathode is usually also comprising conductive addition
Agent and binder；Conductive additive is generally selected from one in carbon black, natural graphite, synthetic graphite, graphene and metallic particles etc.
Kind is a variety of；Binder is then selected from one of Kynoar, polytetrafluoroethylene (PTFE) and carboxymethyl cellulose etc. or a variety of.
Below in conjunction with embodiment, invention is further explained.
Embodiment 1
It is specific as follows the present embodiment provides a kind of solid polymer electrolyte and its application:
In the glove box full of argon gas, bis trifluoromethyl sulfimide lithium (LiTFSI) is dissolved with the concentration of 1mol/L
Homogeneous solution is formed in 1,3-dioxolane (i.e. liquid monomer), and the catalyst lewis acid BF of 1wt% is then added3(its
Mass fraction is using the quality of homogeneous solution as benchmark) it is uniformly mixed and forms polymeric precursor solution, carry out battery pack in situ
Fill to obtain button cell；
Specific assemble method are as follows:
By LiFePO4Material, acetylene black, the PVDF ratio uniform of 8:1:1 in mass ratio are dispersed in N-Methyl pyrrolidone
(NMP) slurry is made in, scratches on aluminium foil, it is the disk of 12mm as battery positive pole piece (pole piece that diameter is cut into after dry
Activity substance content be about 8.0mg/cm2)；Or uniformly, then business sulphur powder and carbon nanotube are ground with mass ratio 6:4
It is encapsulated in vial in 155 DEG C of heating, 24 hours obtained sulphur carbon materials；By sulphur carbon material, the PVDF ratio of 9:1 in mass ratio
It is dispersed in be uniformly dispersed in N-Methyl pyrrolidone (NMP) and slurry is made, be coated on aluminium foil, 24 hours are then heated at 60 DEG C extremely
Drying, as battery positive pole piece, (sulphur load capacity is about 1.2mg/cm2).Using metal lithium sheet as negative pole piece of battery.Assembling button
When formula battery, cathode and diaphragm are put well, precursor solution is injected in button cell, anode is put into, eventually forms button cell,
Specific performance and parameter are shown in Fig. 1 to Fig. 5.Fig. 1 is the scanning of the in-situ polymerization in lithium piece of polymer dielectric made from embodiment 1
Electron microscope image shows have the polymer dielectric of continuous structure attached securely by the in-situ polymerization in assembled battery
Arrive anode lithium on piece, therefore reduce the interface resistance come between self-electrode and electrolyte, be conducive to the electricity of lithium ion battery
Chemical stability.Fig. 2 is the ionic conductivity figure of solid polyelectrolyte made from embodiment 1, is demonstrated by the solid state electrolysis
The high ionic conductivity of matter.Fig. 3 is that 1 in-situ polymerization object electrolyte of embodiment assembles lithium Symmetrical cells cyclic polarization curve, from figure
In as can be seen that the Symmetrical cells can keep the polarization potential of very little for a long time.Fig. 4 is that original position prepared by embodiment 1 is poly-
The polymer dielectric of conjunction is applied to LiFePO4 // lithium metal secondary cell cycle performance figure, and Fig. 5 is prepared by embodiment 1
The polymer dielectric of in-situ polymerization is applied to the cycle performance figure of lithium-sulfur cell, it can be seen that Inventive polymers solid state electrolysis
Matter can maintain LiFePO4 // lithium metal battery and stablizing for lithium-sulfur cell to recycle.
Embodiment 2
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: the concentration of bis trifluoromethyl sulfimide lithium is 1.5mol/L.
Embodiment 3
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: the concentration of bis trifluoromethyl sulfimide lithium is 2mol/L.
Embodiment 4
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: the mass concentration of catalyst is 2%.
Embodiment 5
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: the mass concentration of catalyst is 5%.
Embodiment 6
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: the catalyst used is strong protonic acid fluosulfonic acid.
Embodiment 7
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: the catalyst used is precious metal salt AgSbF6。
Embodiment 8
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: the lithium ion conductor used is lithium perchlorate.
Embodiment 9
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: the lithium ion conductor used is dioxalic acid lithium borate.
Embodiment 10
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: the lithium ion conductor used is difluorine oxalic acid boracic acid lithium.
Embodiment 11
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: the lithium ion conductor used is trifluoromethyl sulfonic acid lithium.
Embodiment 12
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: liquid monomer uses tetrahydrofuran.
Embodiment 13
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: liquid monomer uses fourth oxygen ring.
Embodiment 14
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: liquid monomer uses diallyl carbonate, and initiator is that azodiisobutyronitrile (be shown in by the specific performance and parameter of final battery
Fig. 6 to Fig. 9).Fig. 6 is the scanning electron microscope diagram of the in-situ polymerization in lithium piece of polymer dielectric made from embodiment 14
Picture shows that the in-situ polymerization that again may be by assembled battery with the polymer dielectric is firmly adhered to anode lithium piece
On.Fig. 7 is the ionic conductivity figure of solid polyelectrolyte made from embodiment 14, be demonstrated by the solid electrolyte it is high from
Electron conductivity.Fig. 8 is that 14 in-situ polymerization object electrolyte of embodiment assembles lithium Symmetrical cells cyclic polarization curve, can therefrom be seen
Out, which generates voltage fluctuation in lithium deposition/stripping process almost without with time/period, this is attributed to solid
Stable interface between state polymeric dielectric and lithium metal surface.Moreover, not having after the long-term polarization at 100 hours yet
There is observable short circuit.Fig. 9 is that the polymer dielectric of in-situ polymerization prepared by embodiment 14 is applied to ferric phosphate
Lithium // lithium metal secondary cell cycle performance figure, it can be seen that Inventive polymers solid electrolyte can maintain ferric phosphate
Lithium // lithium metal battery circulation steady in a long-term.
Embodiment 15
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: the mass concentration of initiator is 2%.
Embodiment 16
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: the mass concentration of catalyst is 5%.
Embodiment 17
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: liquid monomer uses vinyl ethylene sulfite.
Embodiment 18
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: liquid monomer uses bis- (2- methacrylic) carbonic esters.
Embodiment 19
The present embodiment provides a kind of solid polymer electrolyte and its application, it and it is almost the same in embodiment 1, it is different
: liquid monomer uses Allyl methyl carbonate.
LiFePO4 of the table 1 based on 1~13 solid polymer electrolyte of embodiment // lithium metal battery chemical property is surveyed
Try performance table
Lithium-sulfur cell electrochemical property test performance table of the table 2 based on 1~13 solid polymer electrolyte of embodiment
| Initial capacity | Circulating ring number | Recycle conservation rate | |
| Embodiment 1 | 850 | 100 | 75% |
| Embodiment 2 | 860 | 100 | 72% |
| Embodiment 3 | 865 | 100 | 73% |
| Embodiment 4 | 800 | 100 | 70% |
| Embodiment 5 | 730 | 100 | 65% |
| Embodiment 6 | 500 | 100 | 50% |
| Embodiment 7 | 600 | 100 | 61% |
| Embodiment 8 | 810 | 100 | 70% |
| Embodiment 9 | 450 | 100 | 40% |
| Embodiment 10 | 400 | 100 | 38% |
| Embodiment 11 | 830 | 100 | 68% |
| Embodiment 12 | 730 | 100 | 67% |
| Embodiment 13 | 640 | 100 | 65% |
LiFePO4 of the table 3 based on 14~19 solid polymer electrolyte of embodiment // lithium metal battery chemical property is surveyed
Try performance table
| Initial capacity | Circulating ring number | Recycle conservation rate | |
| Embodiment 14 | 149 | 50 | 100% |
| Embodiment 15 | 142 | 50 | 93% |
| Embodiment 16 | 139 | 50 | 88% |
| Embodiment 17 | 110 | 50 | 85% |
| Embodiment 18 | 127 | 50 | 87% |
| Embodiment 19 | 129 | 50 | 77% |
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of solid polymer electrolyte, it includes the lithium ion of polymeric matrix and formation in the polymer matrix
Conductor, it is characterised in that: the polymeric matrix is selected from one of polyethers, polycarbonate, polysulfide acid esters or a variety of.
2. solid polymer electrolyte according to claim 1, it is characterised in that: the polymeric matrix is by liquid monomer
Polymerization reaction acquisition is carried out under the action of catalyst or initiator, the liquid monomer is selected from 1,3-dioxolane, tetrahydro
Furans, fourth oxygen ring, vinylene carbonate, vinylethylene carbonate, diallyl carbonate, Allyl methyl carbonate, bis- (2- first
Base allyl) one or more of carbonic ester and vinyl ethylene sulfite.
3. solid polymer electrolyte according to claim 1, it is characterised in that: it is that lithium ion conductor is dissolved in liquid
In state monomer, then carry out polymerization reaction acquisition.
4. solid polymer electrolyte according to claim 1, it is characterised in that: the lithium ion conductor is selected from double three
Methyl fluoride sulfimide lithium, lithium hexafluoro phosphate, dioxalic acid lithium borate, lithium perchlorate, difluorine oxalic acid boracic acid lithium, LiBF4 and
One of trifluoromethyl sulfonic acid lithium or a variety of combinations.
5. solid polymer electrolyte according to claim 2, it is characterised in that: the catalyst is strong protonic acid, admittedly
One or more of body acid, precious metal salt and lewis acid.
6. solid polymer electrolyte according to claim 2, it is characterised in that: the initiator is to draw selected from azo
Send out one or more of agent, organic peroxy class initiator and inorganic peroxy class initiator.
7. solid polymer electrolyte according to claim 3, it is characterised in that: the content of the lithium ion conductor be 1 ~
2mol/L。
8. application of any solid polymer electrolyte in lithium metal battery in claim 1 to 7, it is characterised in that:
The solid polymer electrolyte and anode, cathode are subjected to assembling and form battery, the anode is lithium metal, and the cathode is
Selected from one of LiFePO4, ternary material, nickel ion doped and sulphur carbon material or a variety of.
9. application of the solid polymer electrolyte in lithium metal battery according to claim 8, it is characterised in that: the electricity
Pond is button cell, and the solid polymer electrolyte is to be assembled with iris-diaphragm, or carry out after being injected with liquid former
Position polymerization.
10. application of the solid polymer electrolyte in lithium metal battery according to claim 8, it is characterised in that: described
Cathode also includes conductive additive and binder.
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