CN117276639A - High-conductivity battery electrolyte, preparation method thereof and solid-state lithium-sulfur battery - Google Patents
High-conductivity battery electrolyte, preparation method thereof and solid-state lithium-sulfur battery Download PDFInfo
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- CN117276639A CN117276639A CN202310828489.0A CN202310828489A CN117276639A CN 117276639 A CN117276639 A CN 117276639A CN 202310828489 A CN202310828489 A CN 202310828489A CN 117276639 A CN117276639 A CN 117276639A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 92
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 49
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 44
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 41
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 26
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 26
- 239000002228 NASICON Substances 0.000 claims abstract description 25
- NPDXHCPLBBTVKX-UHFFFAOYSA-K [Zr+4].P(=O)([O-])([O-])[O-].[Li+] Chemical group [Zr+4].P(=O)([O-])([O-])[O-].[Li+] NPDXHCPLBBTVKX-UHFFFAOYSA-K 0.000 claims abstract description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 20
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- -1 lithium zirconium iron phosphate Chemical compound 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000000807 solvent casting Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- PVAKBHJQBIKTDC-UHFFFAOYSA-N gallium lithium Chemical compound [Li].[Ga] PVAKBHJQBIKTDC-UHFFFAOYSA-N 0.000 claims 1
- IWPSJDKRBIAWLY-UHFFFAOYSA-N gallium zirconium Chemical compound [Ga].[Zr] IWPSJDKRBIAWLY-UHFFFAOYSA-N 0.000 claims 1
- 229910001386 lithium phosphate Inorganic materials 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 29
- 230000000694 effects Effects 0.000 abstract description 13
- 238000013508 migration Methods 0.000 abstract description 8
- 230000005012 migration Effects 0.000 abstract description 8
- 239000007784 solid electrolyte Substances 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 5
- 239000005518 polymer electrolyte Substances 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 4
- 238000005520 cutting process Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 238000012360 testing method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 239000002245 particle Substances 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910013439 LiZr Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- LFZYLAXEYRJERI-UHFFFAOYSA-N [Li].[Zr] Chemical compound [Li].[Zr] LFZYLAXEYRJERI-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910000154 gallium phosphate Inorganic materials 0.000 description 1
- LWFNJDOYCSNXDO-UHFFFAOYSA-K gallium;phosphate Chemical compound [Ga+3].[O-]P([O-])([O-])=O LWFNJDOYCSNXDO-UHFFFAOYSA-K 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- HZGFMPXURINDAW-UHFFFAOYSA-N iron zirconium Chemical compound [Fe].[Zr].[Zr] HZGFMPXURINDAW-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- 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
-
- 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
- H01M2300/0068—Solid electrolytes inorganic
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
A high-conductivity battery electrolyte, a preparation method thereof and a solid-state lithium sulfur battery, wherein the battery electrolyte comprises polyethylene oxide, inorganic ceramic powder with a NASICON structure, lithium nitrate and lithium salt; wherein, the inorganic ceramic powder with the NASICON structure accounts for 0 to 100 percent of the total mass of the battery electrolyte; the NASICON structure inorganic ceramic powder is lithium zirconium phosphate or lithium zirconium phosphate and doped products thereof. The high-conductivity battery electrolyte, the preparation method thereof and the solid-state lithium sulfur battery are reasonable in formula design, not only solve the problems of overcharging, low lithium ion conductivity, small lithium ion migration number, high local current density at high temperature and the like of the pure polymer electrolyte at room temperature caused by a shuttle effect, but also solve the problems of poor cutting processability, poor contact with an electrode interface and the like of the inorganic ceramic solid electrolyte, and have the characteristics of safety, ion conductivity, high power, stable SEI interface and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a high-conductivity battery electrolyte and a preparation method thereof, and a solid-state lithium-sulfur battery.
Background
In order to provide a continuous supply of electricity for our daily lives, it is important to efficiently store the electrical energy generated by renewable and clean energy sources using advanced energy storage systems. However, for the last 30 years, lithium ion batteries have been occupying the small electronic product market, and cannot provide high energy to meet the demands of new energy storage and electric automobiles. This is because conventional lithium ion batteries rely on intercalation electrode materials, and lithium ions can only topologically intercalate to specific locations, limiting the charge storage capacity and energy density of lithium ions. Therefore, the search for new batteries other than the current lithium ion batteries as soon as possible is very important for future sustainable development.
Lithium sulfur batteries are as high as 2600 Wh kg -1 The theoretical energy density of the battery is considered to be one of candidate batteries which most hopefully meet the energy storage requirements of electric automobiles and portable electronic equipment, and the characteristics of low cost, rich resources, environmental friendliness and the like. In the past few decades, research into lithium sulfur batteries has focused on solving problems associated with active materials, such as polysulfide shuttle effects, volume changes during charge/discharge, and the like. Among them, a composite electrolyte membrane composed of a polymer matrix and a ceramic filler has been receiving attention because of its flexibility, good interface compatibility, and high ionic conductivity comparable to that of a liquid electrolyte.
Polyethylene oxide as a polymer matrix material has excellent electrochemical stability and good interface compatibility with an electrode, and is widely applied. However, since polyethylene oxide is in a semi-molten state at an operating temperature (60 to 70 ℃) and has properties similar to those of an ether-based liquid electrolyte, a shuttle effect is remarkable, severely affecting battery performance.
For this purpose, ceramic powder with adsorption performance and lithium nitrate which can form a passivation protection layer with the lithium sheet are added to inhibit the shuttle effect.
Therefore, finding a high conductivity battery electrolyte based on polyethylene oxide that can suppress the shuttle effect is of great importance for solid state lithium sulfur batteries. According to the invention, by adding the NASICON structure inorganic ceramic powder with adsorption performance, and the ceramic powder is zirconium lithium phosphate or zirconium lithium phosphate and doped products thereof, the lithium nitrate and the lithium sheet can form a passivation protection layer, so that the shuttle effect is effectively inhibited.
Disclosure of Invention
The invention aims to: in order to overcome the defects, the invention aims to provide the high-ion conductivity battery electrolyte and the solid lithium sulfur battery thereof, the formula design is reasonable, the problems of overcharge, low lithium ion conductivity, small lithium ion migration number, high local current density at high temperature and the like caused by a shuttle effect at room temperature of the pure polymer electrolyte are solved, the problems of poor machinability, poor contact with an electrode interface and the like of the inorganic ceramic solid electrolyte are solved, and the solid electrolyte has the characteristics of safety, high ion conductivity, high power, stable SEI interface and wide application prospect.
The invention aims at realizing the following technical scheme:
a high-conductivity battery electrolyte, which comprises polyethylene oxide, inorganic ceramic powder with a NASICON structure, lithium nitrate and lithium salt; wherein, the inorganic ceramic powder with the NASICON structure accounts for 0 to 100 percent of the total mass of the battery electrolyte; the NASICON structure inorganic ceramic powder is lithium zirconium phosphate or lithium zirconium phosphate and doped products thereof.
Polyethylene oxide is used as a polymer matrix material, has excellent electrochemical stability and good interface compatibility with an electrode, but is in a semi-molten state at the working temperature (60-70 ℃), so that the shuttle effect is obvious, and the battery performance is seriously affected.
In order to solve the problem, the ceramic powder with adsorption performance is added into the battery electrolyte formula, and the ceramic powder is zirconium lithium phosphate or zirconium lithium phosphate and doped products thereof, and lithium nitrate can form a passivation protection layer with a lithium sheet to inhibit the occurrence of a shuttle effect. In addition, the positive pentavalent phosphorus element in the NASICON structure can be doped or replaced by other high-valence ions, and different elements realize different functions in the structure, so that not only the ionic conductivity is improved, but also the environmental stability is better, and meanwhile, the 'induction effect' of the material has strong X-O covalent bonds in the structure, so that the M-O covalent bonds are promoted to generate higher ionization degree, thereby inducing the oxidation-reduction of transition metal, increasing the oxidation-reduction voltage of the transition metal, and further improving the working voltage.
Further, the high-conductivity battery electrolyte comprises the following raw materials in parts by weight:
50-150 parts of polyethylene oxide;
0-50 parts of NASICON structure inorganic ceramic powder;
1-50 parts of lithium nitrate;
1-50 parts of lithium salt.
The formula design of the battery electrolyte is reasonable, the added NASICON structure inorganic ceramic powder has certain lithium ion conductivity, high lithium ion migration capacity and good thermal stability, the mechanical property of a high polymer material can be enhanced, the crystallinity of the polymer is reduced, and a good and stable interface is formed with a lithium metal anode. The solid electrolyte obtained by mixing the materials with lithium salt has good safety performance and machining performance, and the lithium ion conductivity and the lithium ion migration number are high.
Further, in the high-conductivity battery electrolyte, the molecular weight of the polyethylene oxide is 1000-10000000; the size of the NASICON structure inorganic ceramic powder is in the range of 5nm-10 mu m.
Further, in the high-conductivity battery electrolyte, the lithium zirconium phosphate and the doped product thereof are selected from one of zirconium-site iron-doped lithium zirconium iron phosphate and zirconium-site gallium-doped lithium zirconium gallium phosphate.
Zirconium-site doped lithium zirconium iron phosphate (Li) is added into battery electrolyte 1+X Fe X Zr 2-X (PO 4 ) 3 ) Compared with the adding of lithium zirconium phosphate, the zirconium-doped iron can effectively inhibit the structural change of the electrode material in the charge-discharge process of the battery, and reduce the interaction between the electrode material and electrolyte, thereby prolonging the cycle life of the battery. Meanwhile, the zirconium-site iron doping can increase the electron conductivity of the electrode material, improve the energy density and the power density of the battery, improve the electrochemical stability of the battery and reduce the safety of the battery in overcharging and overdischarging statesFull risk. (here, retrieved data)
Zirconium gallium doped lithium zirconium phosphate (Li) with zirconium position doped with gallium is added into battery electrolyte 1+X Ga X Zr 2-X (PO 4 ) 3 ) Compared with the addition of lithium zirconium phosphate, the introduction of gallium in the battery electrolyte stabilizes the NASICON structure of lithium ion transmission, reduces the strength of impurity phases and improves Li + Concentration. The unit cell can introduce extra lithium ions, so that the concentration of charge carriers is increased, and the ion conductivity of the material is improved.
Further, the high-conductivity battery electrolyte is selected from LiPF 6 、LiClO 4 、LiTFSI、LiFSI、LiTf、LiBF 4 LiBOB, liDFOB, liTDI or a derivative thereof.
Further, in the high-conductivity battery electrolyte, the lithium salt and Li of polyethylene oxide + : the molar ratio of O is 1: (0-100).
The invention also relates to a preparation method of the high-conductivity battery electrolyte, which is prepared by adopting a hot solvent casting method or a hot pressing process.
Further, according to the preparation method of the high-conductivity battery electrolyte, the thickness of the high-conductivity battery electrolyte is 0-3000 mu m.
Further, the preparation method of the high-conductivity battery electrolyte comprises the following steps:
s1: placing polyethylene oxide and NASICON structure inorganic ceramic powder and lithium salt into a vacuum drying oven respectively for full drying;
s2: adding polyethylene oxide, inorganic ceramic powder with a NASICON structure, lithium nitrate and lithium salt into a solvent, and uniformly stirring under the protection of inert atmosphere to obtain a uniform phase solution; the solvent is one selected from DMC, DMF, NMP, acetonitrile, N-dimethylformamide, dimethyl sulfoxide, anisole, chloroform, dichloroethane, acetone and tetrahydrofuran;
s3: and coating the homogeneous phase solution on a glass plate or pouring the homogeneous phase solution on a polytetrafluoroethylene mould, volatilizing the solution at 20-200 ℃ to remove the solvent, and obtaining the battery electrolyte with the membranous structure.
The polymer electrolyte and the inorganic ceramic powder with the NASICON structure are stirred and mixed uniformly at a high speed in a protective atmosphere, so that the obtained battery electrolyte not only can enhance the mechanical property of a polymer material, but also can improve the lithium ion conductivity and the lithium ion migration number, reduce the crystallinity of the polymer, form a stable SEI interface with a lithium metal anode, stabilize the local current density and prevent lithium dendrites from penetrating through the solid electrolyte at a high speed.
The invention also relates to a solid-state lithium sulfur battery, which comprises a positive pole piece, a negative pole piece and the battery electrolyte.
Compared with the prior art, the invention has the following beneficial effects:
(1) The high-conductivity battery electrolyte disclosed by the invention has reasonable formula design, comprises polyethylene oxide, inorganic ceramic powder with a NASICON structure, lithium nitrate, lithium salt, and the inorganic ceramic powder with the NASICON structure adopts zirconium lithium phosphate or zirconium lithium phosphate and doped products thereof, has certain lithium ion conductivity, high lithium ion migration capacity and good thermal stability, can enhance the mechanical property of a high polymer material, reduce the crystallinity of a polymer, form a good stable interface with a lithium metal anode, and not only solves the problems of overcharging, lithium metal corrosion, low lithium ion conductivity at room temperature, small lithium ion migration number, large local current density at high temperature and the like caused by a shuttle effect, but also solves the problems of poor cutting processability, poor contact with an electrode interface and the like of an inorganic ceramic solid electrolyte, and has the characteristics of safety, ion conductivity, high power and stable SEI interface;
(2) According to the preparation method of the high-conductivity battery electrolyte, disclosed by the invention, the polymer electrolyte and the inorganic ceramic powder with the NASICON structure are stirred and mixed uniformly at a high speed in a protective atmosphere, so that the obtained battery electrolyte not only can enhance the mechanical property of a polymer material, but also can improve the lithium ion conductivity and the lithium ion migration number, and reduce the crystallinity of the polymer;
(3) The solid-state lithium sulfur battery disclosed by the invention can avoid a series of problems of battery overcharge and the like caused by a shuttle effect of the traditional liquid-state lithium sulfur battery by adopting the battery electrolyte, has a certain self-repairing function, and has higher ionic conductivity and excellent cycle stability.
Drawings
FIG. 1 is a diagram of Li according to the present invention 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 XRD patterns of the battery electrolytes of example 1, example 2, example 3, example 1, comparative example 2;
fig. 2 is an SEM image of the battery electrolyte of example 3 of the present invention;
fig. 3 is a graph of CA and EIS test data for the battery electrolyte of example 3 of the present invention.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in reference to comparative example 1, comparative example 2, example 1, example 2, example 3, and example 4 in conjunction with specific experimental data and fig. 1 to 3, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The battery electrolyte of the invention can be applied to solid-state batteries including solid-state lithium-sulfur batteries.
The following comparative examples 1, 2, 3 and 4 provide a battery electrolyte and a preparation method thereof, and raw materials used in comparative examples 1, 2, 3 and 4 are all commercially available common raw materials.
Comparative example 1
The battery electrolyte of comparative example 1 includes polyethylene oxide particles, lithium salt LiTFSI, lithium nitrate, and its preparation method is as follows:
and respectively placing polyethylene oxide particles and lithium salt LiTFSI into a vacuum drying oven for full drying, and then adopting a hot solvent coating method to prepare the battery electrolyte. Weighing 0.5g of polyethylene oxide according to a lithium-oxygen ratio of 1:20, adding a proper amount of acetonitrile 10mL into a clean small bottle of lithium nitrate 0.033g,LiTFSI 0.16g, stirring uniformly under the protection of inert atmosphere to obtain a uniform phase solution, coating the uniform phase solution on a glass plate, setting a scraper at 1500 mu m, and drying at room temperature to obtain the battery electrolyte of the comparative example 1.
Comparative example 2
The battery electrolyte of comparative example 1 includes polyethylene oxide particles, liZr 2 (PO 4 ) 3 Inorganic ceramic powder, lithium salt LiTFSI and lithium nitrate, and the preparation method comprises the following steps:
and respectively placing polyethylene oxide particles and lithium salt LiTFSI into a vacuum drying oven for full drying, and then adopting a hot solvent coating method to prepare the battery electrolyte. Weighing 0.5g of polyethylene oxide according to a lithium-oxygen ratio of 1:20, adding a proper amount of acetonitrile 10mL into a clean small bottle of lithium nitrate 0.033g,LiTFSI 0.16g, stirring until the polyethylene oxide is completely dissolved under the protection of inert atmosphere, and then adding 0.033g of LiZr 2 (PO 4 ) 3 The inorganic ceramic powder was subjected to ultrasonic treatment during stirring to obtain a homogeneous phase solution, which was then coated on a glass plate with a doctor blade set at 1500 μm and dried at room temperature to obtain a battery electrolyte of comparative example 2. The battery electrolyte of comparative example 2 was tested to have a lithium ion conductivity of 1.57×10 at 60 deg.c -5 S cm -1 。
Example 1
The battery electrolyte of example 1 includes polyethylene oxide particles, li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Inorganic ceramic powder, lithium salt LiTFSI and lithium nitrate, and the preparation method comprises the following steps:
and respectively placing polyethylene oxide particles and lithium salt LiTFSI into a vacuum drying oven for full drying, and then adopting a hot solvent coating method to prepare the battery electrolyte. Weighing 0.5g of polyethylene oxide according to a lithium-oxygen ratio of 1:20, adding 0.033g,LiTFSI 0.16g of lithium nitrate into a clean small bottle, adding 10mL of acetonitrile in proper amount, stirring under the protection of inert atmosphere until the polyethylene oxide is completely dissolved, and then adding 0.033g of Li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Inorganic ceramic powder, ultrasonic treatment during stirring,a homogeneous phase solution was obtained, which was then coated on a glass plate, set to 1500 μm with a doctor blade, and dried at room temperature to obtain the battery electrolyte of example 1. Li in the Battery electrolyte of example 1 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 The mass fraction of the inorganic ceramic powder is 5%, and the battery electrolyte is all solid, curled and provided with a self-repairing function, and the lithium ion conductivity of the battery electrolyte of the embodiment 1 is 7.15 multiplied by 10 at 60 ℃ after test -5 S cm -1 。
From the above, li is used 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Example 1 of inorganic ceramic powder compared with LiZr 2 (PO 4 ) 3 Comparative example 2 of the inorganic ceramic powder has higher conductivity with the same weight of each component of the formulation.
Example 2
The battery electrolyte of example 2 includes polyethylene oxide particles, li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Inorganic ceramic powder, lithium salt LiTFSI and lithium nitrate, and the preparation method comprises the following steps:
and respectively placing polyethylene oxide particles and lithium salt LiTFSI into a vacuum drying oven for full drying, and then adopting a hot solvent coating method to prepare the battery electrolyte. Weighing 0.5g of polyethylene oxide according to a lithium-oxygen ratio of 1:20, adding 0.033g,LiTFSI 0.16g of lithium nitrate into a clean small bottle, adding 10mL of acetonitrile in proper amount, stirring under the protection of inert atmosphere until the polyethylene oxide is completely dissolved, and then adding 0.066g of Li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 The inorganic ceramic powder was subjected to ultrasonic treatment during stirring to obtain a homogeneous phase solution, which was then coated on a glass plate with a doctor blade set at 1500 μm and dried at room temperature to obtain the battery electrolyte of example 2. Li in the Battery electrolyte of example 2 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 The mass fraction of the inorganic ceramic powder is 10%, and the battery electrolyte is all solid, curled and provided with a self-repairing function, and the lithium ion conductivity of the battery electrolyte of the embodiment 1 is 1.03 multiplied by 10 at 60 ℃ after test -4 S cm -1 。
Example 3
The battery electrolyte of example 3 includes polyethylene oxide particles, li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Inorganic ceramic powder, lithium salt LiTFSI and lithium nitrate, and the preparation method comprises the following steps:
and respectively placing polyethylene oxide particles and lithium salt LiTFSI into a vacuum drying oven for full drying, and then adopting a hot solvent coating method to prepare the battery electrolyte. Weighing 0.5g of polyethylene oxide according to a lithium-oxygen ratio of 1:20, adding 0.033g,LiTFSI 0.16g of lithium nitrate into a clean small bottle, adding 10mL of acetonitrile in proper amount, stirring under the protection of inert atmosphere until the polyethylene oxide is completely dissolved, and then adding 0.099g of Li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 The inorganic ceramic powder was subjected to ultrasonic treatment during stirring to obtain a homogeneous phase solution, which was then coated on a glass plate with a doctor blade set at 1500 μm and dried at room temperature to obtain the battery electrolyte of example 3. Li in the Battery electrolyte of example 3 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 The mass fraction of the inorganic ceramic powder is 15%, and the battery electrolyte is in an all-solid state, can be curled, has a self-repairing function, and has lithium ion conductivity of 1.36 multiplied by 10 at 60 ℃ in the battery electrolyte of the embodiment 1 -4 S cm -1 。
Example 4
The battery electrolyte of example 4 includes polyethylene oxide particles, li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Inorganic ceramic powder, lithium salt LiTFSI and lithium nitrate, and the preparation method comprises the following steps:
and respectively placing polyethylene oxide particles and lithium salt LiTFSI into a vacuum drying oven for full drying, and then adopting a hot solvent coating method to prepare the battery electrolyte. Weighing 0.5g of polyethylene oxide according to a lithium-oxygen ratio of 1:20, adding 0.033g,LiTFSI 0.16g of lithium nitrate into a clean small bottle, adding 10mL of acetonitrile in proper amount, stirring under the protection of inert atmosphere until the polyethylene oxide is completely dissolved, and then adding 0.132g of Li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Inorganic ceramic powderFinally, a homogeneous phase solution was obtained with ultrasonic treatment during stirring, and then coated on a glass plate with a doctor blade set at 1500 μm, and dried at room temperature to obtain the battery electrolyte of example 4. Li in the Battery electrolyte of example 4 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 The mass fraction of the inorganic ceramic powder is 20%, and the battery electrolyte is all solid, curled and provided with a self-repairing function, and the lithium ion conductivity of the battery electrolyte of the embodiment 1 is 1.12 multiplied by 10 at 60 ℃ after test -4 S cm -1 。
From the above, li with different mass fractions is used 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Examples 1 to 4 of inorganic ceramic powders, li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Example 3, in which the mass fraction of the inorganic ceramic powder was 15%, had the highest electrical conductivity.
Effect verification
Li was measured according to the following test method 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 The battery electrolytes of comparative example 1 and examples 2 to 4 were subjected to an X-ray polycrystal diffraction test, and the test results are shown in fig. 1.
（1）Li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Is determined by the test of (a): li is mixed with 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 The sample is firstly and uniformly ground in a mortar, then is paved in a die, is tested by XRD, the testing angle range is 2θ=10-90 degrees, and the testing temperature is room temperature;
(2) Testing of battery electrolyte: the polymer electrolyte was stuck in a mold with double sided tape, tested by XRD with a test angle range of 2θ=10° -90 °, and a test temperature of room temperature.
From a review of FIG. 1, li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 The corresponding protrusion on the curve is Li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Characteristic diffraction peaks of materials, curves corresponding to the battery electrolytes of examples 2-4Also has Li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Is proved to contain Li in the battery electrolytes of examples 2 to 4 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Simply add Li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Is different in mass fraction, peak area and height are different to a certain extent, and Li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Comparative example 1 having a mass fraction of 0% without Li 1.05 Fe 0.05 Zr 1.95 (PO 4 ) 3 Is a characteristic diffraction peak of (2).
Since the battery electrolyte of example 3 had the highest conductivity, SEM analysis was performed only on the battery electrolyte of example 3, and the test results are shown in fig. 2, and the distribution was also relatively uniform overall.
The battery electrolyte of example 3 was subjected to a CA test and an EIS test, and the test results are shown in fig. 3. As can be seen from the examination of FIG. 3, the battery electrolyte of example 3 had a conductivity of 1.35X 10 by AC impedance test -4 S cm -1 Calculated, the lithium ion mobility was found to be 0.345.
There are many ways in which the invention may be practiced, and what has been described above is merely a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that modifications may be made without departing from the principles of the invention, and such modifications are intended to be within the scope of the invention.
Claims (10)
1. The high-conductivity battery electrolyte is characterized by comprising polyethylene oxide, inorganic ceramic powder with a NASICON structure, lithium nitrate and lithium salt; wherein, the inorganic ceramic powder with the NASICON structure accounts for 0 to 100 percent of the total mass of the battery electrolyte; the NASICON structure inorganic ceramic powder is lithium zirconium phosphate or lithium zirconium phosphate and doped products thereof.
2. The high conductivity battery electrolyte of claim 1, wherein the battery electrolyte comprises the following raw materials in parts by weight:
50-150 parts of polyethylene oxide;
0-50 parts of NASICON structure inorganic ceramic powder;
1-50 parts of lithium nitrate;
1-50 parts of lithium salt.
3. The high conductivity battery electrolyte of claim 1, wherein the polyethylene oxide has a molecular weight of 10000-10000000; the size of the NASICON structure inorganic ceramic powder is in the range of 5nm-10 mu m.
4. The high conductivity battery electrolyte of claim 1, wherein the lithium zirconium phosphate and doped products thereof are selected from one of zirconium site-doped lithium zirconium iron phosphate, zirconium site-doped gallium zirconium gallium lithium phosphate.
5. The high conductivity battery electrolyte of claim 1 wherein the lithium salt is selected from LiPF 6 、LiClO 4 、LiTFSI、LiFSI、LiTf、LiBF 4 LiBOB, liDFOB, liTDI or a derivative thereof.
6. The high conductivity battery electrolyte of claim 1 wherein the lithium salt is with Li of polyethylene oxide + : the molar ratio of O is 1: (0-100).
7. The method for preparing a high-conductivity battery electrolyte according to any one of claims 1 to 6, which is prepared by a hot solvent casting method or a hot pressing process.
8. The method for preparing a high-conductivity battery electrolyte according to claim 7, wherein the thickness of the high-conductivity battery electrolyte is 0-3000 μm.
9. The method for preparing a high conductivity battery electrolyte according to claim 7, comprising the steps of:
s1: placing polyethylene oxide and NASICON structure inorganic ceramic powder and lithium salt into a vacuum drying oven respectively for full drying;
s2: adding polyethylene oxide, inorganic ceramic powder with a NASICON structure, lithium nitrate and lithium salt into a solvent, and uniformly stirring under the protection of inert atmosphere to obtain a uniform phase solution; the solvent is one selected from DMC, DMF, NMP, acetonitrile, N-dimethylformamide, dimethyl sulfoxide, anisole, chloroform, dichloroethane, acetone and tetrahydrofuran;
s3: and coating the homogeneous phase solution on a glass plate or pouring the homogeneous phase solution on a polytetrafluoroethylene mould, volatilizing the solution at 20-200 ℃ to remove the solvent, and obtaining the battery electrolyte with the membranous structure.
10. A solid state lithium sulfur battery comprising a positive electrode tab, a negative electrode tab, and the battery electrolyte of any one of claims 1 to 6.
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