CN117855582A - Flexible composite solid electrolyte and preparation and application thereof - Google Patents
Flexible composite solid electrolyte and preparation and application thereof Download PDFInfo
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- CN117855582A CN117855582A CN202410263514.XA CN202410263514A CN117855582A CN 117855582 A CN117855582 A CN 117855582A CN 202410263514 A CN202410263514 A CN 202410263514A CN 117855582 A CN117855582 A CN 117855582A
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 229920000307 polymer substrate Polymers 0.000 claims abstract description 10
- 239000011256 inorganic filler Substances 0.000 claims abstract description 9
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 28
- 239000000945 filler Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 239000002033 PVDF binder Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 11
- 239000004814 polyurethane Substances 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002228 NASICON Substances 0.000 claims description 4
- 239000002223 garnet Substances 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 229920001774 Perfluoroether Polymers 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000005452 bending Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 abstract 1
- 239000010405 anode material Substances 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000011572 manganese Substances 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 210000001787 dendrite Anatomy 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 229910003480 inorganic solid Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229920001780 ECTFE Polymers 0.000 description 2
- 229910009511 Li1.5Al0.5Ge1.5(PO4)3 Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- NDZWKTKXYOWZML-UHFFFAOYSA-N trilithium;difluoro oxalate;borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FOC(=O)C(=O)OF NDZWKTKXYOWZML-UHFFFAOYSA-N 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
Abstract
The invention discloses a flexible composite solid electrolyte, a preparation method and application thereof, wherein the flexible composite solid electrolyte is prepared from the following raw materials in percentage by weight: 5-30 wt% of solute salt; 5-80 wt% of inorganic filler; 10-80 wt% of a polymer substrate, wherein the polymer substrate consists of a polymer A and a polymer B in a mass ratio of 1-10:1; the invention also specifically discloses a preparation method of the flexible composite solid electrolyte and application of the flexible composite solid electrolyte in lithium metal batteries. The flexible composite solid electrolyte prepared by the invention has a high voltage window of 5.0V, and can be completely matched with a high voltage anode material; the assembled lithium iron phosphate/nickel cobalt manganese battery has high specific capacity and can realize stable circulation; the composite solid electrolyte material provided by the invention has the characteristic of flexibility and bending, so that the composite solid electrolyte material can be tightly contacted with an electrode material, and is expected to be applied to wearable electronic equipment.
Description
Technical Field
The invention belongs to the technical field of solid electrolytes of lithium metal batteries, and particularly relates to a flexible composite solid electrolyte, a preparation method and application thereof.
Background
At present, the negative electrode of the mainstream lithium ion battery in the energy storage market is graphite, the energy density is close to the limit, and the rapid development of society is difficult to keep up. While lithium metal has a high specific capacity (3800 mAh g) -1 ) And low redox potential (-3.040V) are expected to achieve higher energy density, thus making lithium metal batteries one of the most promising secondary batteries.
However, the electrolyte used in the lithium metal battery widely studied at the present stage is mostly liquid, so that the safety problems of easy leakage, inflammability and the like of the electrolyte inevitably occur in practical application, and lithium dendrites are easy to form when lithium metal is used as a negative electrode, thereby affecting the performance of the lithium metal battery and even causing short circuit. Compared with liquid electrolyte, the solid electrolyte is safer, has more excellent mechanical properties, can effectively inhibit the growth of lithium dendrites, and is expected to realize large-scale production and application of lithium metal batteries in the early days.
In the prior art, commonly used solid electrolytes can be classified into three main categories, namely inorganic solid electrolytes, polymer solid electrolytes and composite solid electrolytes. The inorganic solid electrolyte has the advantages of high ionic conductivity and wide voltage window, but has poor contact with the electrode, and side reaction exists between part of the electrolyte and lithium metal, so that the application of the inorganic solid electrolyte is limited. The polymer solid electrolyte has good interface contact performance, but has low voltage window and low ion conductivity, and can not well meet market demands. The organic-inorganic composite solid electrolyte can make up for the advantages of the electrolyte, and has better interface contact performance and improved ionic conductivity. In addition, for the flexible wearable battery technology which is emerging at present, the organic-inorganic composite solid electrolyte has the characteristic of flexibility and bending, and has more practicability. In addition, compared with the traditional liquid wearable battery, the solid flexible wearable battery not only improves the performance and safety of the wearable equipment, but also opens up a new way for innovation and application of the wearable technology. However, when facing high-voltage positive electrode materials, the organic-inorganic composite solid electrolyte still has the problem of easy oxidation; in addition, due to the high crystallinity of the polymer component, lithium ions are unevenly deposited, thereby causing uncontrollable dendrite growth, and thus stable circulation cannot be realized.
Therefore, there is an urgent need to develop a flexible composite solid electrolyte having a wide voltage window and capable of effectively suppressing lithium dendrites to meet the demands of the current energy market.
Disclosure of Invention
The invention aims to provide a flexible composite solid electrolyte and a preparation method thereof, so as to effectively improve a voltage window of the electrolyte.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the flexible composite solid electrolyte is characterized by being prepared from the following raw materials in percentage by weight:
5-30 wt% of solute salt, wherein the solute salt is lithium bis (trifluoromethylsulfonyl) imide (LiTFSI) or lithium hexafluorophosphate (LiPF) 6 ) Lithium difluorooxalato borate (LiDFOB), lithium nitrate (LiNO) 3 ) Or lithium tetrafluoroborate (LiBF) 4 ) One or more of the following;
5-80 wt% of inorganic filler, wherein the inorganic filler is one or more of active filler or inert filler, the active filler is one or more of NASICON type filler, garnet type filler or perovskite type filler, and the inert filler is SiO 2 、Al 2 O 3 、TiO 2 Or ZrO(s) 2 One or more of the following;
10-80 wt% of a polymer substrate, wherein the polymer substrate consists of a polymer A and a polymer B in a mass ratio of 1-10:1, the polymer A is one or more of polyether polyurethane or polyester polyurethane, and the polymer B is one or more of fluorine-containing polymer ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy resin (PFA), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF) or polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP).
In the technical scheme of the invention, the polymer A and the polymer B respectively have sites combined with lithium ions, can conduct lithium ions, can reduce crystallinity after being blended, and can promote ion transmission; the active filler also plays a role of conducting ions, so that the prepared composite solid electrolyte has a plurality of ion transmission channels at the same time and has higher ion conductivity at room temperature. In addition, the structure of the polymer A is divided into a soft segment and a hard segment, and hydrogen bonds exist between the soft segment and the hard segment, so that the polymer A has excellent mechanical properties, and the finally prepared composite solid electrolyte can keep enough mechanical properties by controlling the content of each component in the composite solid electrolyte, so that the growth of lithium dendrites can be inhibited in the battery cycle process. In addition, the two polymers have interaction after being blended, so that the voltage window is further improved, and the electrolyte can be prevented from being oxidized under high pressure.
Preferably, the flexible composite solid electrolyte is prepared from the following raw materials in percentage by weight: 10-20wt% of solute salt, 10-40wt% of inorganic filler and the balance of polymer substrate.
Preferably, the NASICON type filler is Li 1+x Al x Ti 2-x (PO 4 ) 3 (LATP) or Li 1+x Al x Ge 2-x (PO 4 ) 3 One or more of (LAGP); garnet type filler is Li 7 La 3 Zr 2 O 12 (LLZO); the perovskite filler is Li 3x La 2/3- x TiO 3 （LLTO）。
Preferably, the mass ratio of the polymer A to the polymer B in the polymer substrate is 2-8:1.
A preparation method of a flexible composite solid electrolyte is characterized by comprising the following specific steps:
step S1: dissolving a polymer A in a solvent C, heating and stirring until the polymer A is dissolved to obtain slurry;
step S2: adding the polymer B into the slurry obtained in the step S1, heating, stirring and mixing uniformly;
step S3: adding solute salt into the slurry obtained in the step S2, and continuously heating, stirring and uniformly mixing;
step S4: adding inorganic filler into the slurry obtained in the step S3, stirring, transferring to a ball milling tank, ball milling, uniformly mixing, coating on a die, immersing in a solvent D to replace a solvent C in the slurry, standing, taking out and drying to obtain the flexible composite solid electrolyte, wherein the finally prepared flexible composite solid electrolyte has a wide voltage window and excellent capability of inhibiting lithium dendrite.
Preferably, the solvent C in step S1 is one or more of N-methylpyrrolidone, N-dimethylformamide or dimethylsulfoxide, and the solvent D in step S4 is one or more of acetone or ethanol.
In the technical scheme of the invention, a non-solvent induced phase inversion method is adopted, a solvent C is used for dissolving a polymer to form a single-phase solution, the single-phase solution is immersed into a solvent D after being prepared into a diaphragm, and then the single-phase (thermodynamically stable) polymer solution is converted into a polymer rich phase (high polymer concentration) and a polymer lean phase (high solvent concentration), so that the mixing Gibbs free energy (delta Gm) of the system is minimized, and liquid-liquid phase separation occurs. In addition, the solvent D replaces the solvent C which is difficult to volatilize in the polymer, so that the problems of performance reduction and the like caused by incomplete volatilization of the solvent in the follow-up process are avoided.
Preferably, the heating and stirring in the step S1, the step S2 and the step S3 are all carried out in a magnetic stirring oil bath, and the heating and stirring temperature is 50-120 ℃.
A lithium metal battery characterized in that: and assembling the lithium iron phosphate or nickel cobalt manganese anode and the lithium metal cathode into the button cell by utilizing the flexible composite solid electrolyte.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the lithium metal battery assembled by the flexible solid electrolyte prepared by the invention has a high voltage window of 5.0V, which exceeds most of composite solid electrolytes in the prior researches, so that the lithium metal battery can normally work under high pressure; the preferred two polymers are blended to effectively reduce crystallinity. Meanwhile, the two polymers have sites combined with lithium ions, and can participate in ion transmission in the charge and discharge processes, so that the ion conduction is facilitated; in addition, the composite solid electrolyte also maintains certain mechanical strength and flexibility, can buffer the volume expansion of the electrode, can inhibit the growth of dendrite while ensuring good contact between the electrode and the electrolyte in the charge and discharge process, and ensures the stability of the circulation process; the solid lithium metal battery prepared by the invention has excellent cycle stability performance due to the inclusion of the composite solid electrolyte with excellent performance; can normally operate even under high voltage of 4.3V and has higher specific capacity.
Drawings
Fig. 1 is an optical photograph of the composite solid electrolyte prepared in example 1.
Fig. 2 is a stress-strain curve of the composite solid electrolyte prepared in example 1.
Fig. 3 is a linear sweep voltammogram of the composite solid state electrolyte prepared in example 1 and comparative example 1, comparative example 2.
Fig. 4 is a cycle comparison curve of the composite solid electrolyte prepared in example 1 and comparative example 1, comparative example 2 applied to 0.5C in lfp||li battery system.
Fig. 5 is a charge-discharge curve of 0.2C applied to an NCM811 Li battery system of the composite solid electrolyte prepared in example 1.
Fig. 6 is a cycle curve of 0.2C at 60 ℃ for application of the composite solid electrolyte prepared in example 1 to NCM811 Li battery system.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Example 1
Step S1: 2.0g of polyether polyurethane (tabacco WHT-8190 RV) is weighed into a solventHeating and stirring in DMF at 80 ℃ until the polyvinylidene fluoride (PVDF) is completely dissolved, weighing polyvinylidene fluoride (PVDF) with the mass ratio of the PVDF to the polyether polyurethane of 2:1, adding the PVDF into the slurry, continuously heating and stirring at 80 ℃ for uniform mixing, adding solute salt lithium bistrifluoromethylsulfonylimide accounting for 20wt% of the total weight of the composite solid electrolyte, stirring for uniform mixing, and adding filler Li accounting for 30wt% of the total weight of the composite solid electrolyte 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 Stirring, transferring to a ball milling tank, ball milling, mixing uniformly, coating on a die, immersing in absolute ethyl alcohol solvent to replace DMF solvent in the slurry, standing, taking out, and drying to obtain the composite solid electrolyte.
Step S2: cutting the completely dried composite solid electrolyte prepared in the step S1 into solid electrolyte wafers with the diameter of 19mm, and respectively assembling the solid electrolyte wafers into Li SS, LFP Li and NCM811 Li button cells in a glove box for subsequent testing.
Example 2
The preparation method of this example is the same as that of example 1, except that: the mass ratio in the step S1 is replaced by 4:1, the solute salt is replaced by lithium hexafluorophosphate, and the filler Li is 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 The ratio was replaced by 20wt% and the solvent DMF was replaced by N-methylpyrrolidone.
Example 3
The preparation method of this example is the same as that of example 1, except that: the mass ratio in the step S1 is replaced by 7:1, the solute salt is replaced by lithium difluoro oxalate borate, and the filler Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 The ratio was replaced by 30wt% and the solvent DMF was replaced by dimethyl sulfoxide.
Example 4
The preparation method of this example is the same as that of example 1, except that: the solute salt in step S1 was replaced with lithium difluorooxalato borate, the solute salt ratio was replaced with 20wt%, and the solvent absolute ethanol was replaced with acetone.
Example 5
The preparation method of this example is the same as that of example 1, except that: the polyether polyurethane in step S1 was replaced with a polyester polyurethane (smoke counter vanity WHT-1495 RV) and the mass ratio was replaced with 8:1.
Example 6
The preparation method of this example is the same as that of example 1, except that polyvinylidene fluoride in step S1 is replaced with polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), the mass ratio is replaced with 5:1, and the filler Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 The proportion is replaced by 40% by weight.
Example 7
The preparation method of this example is the same as that of example 1, except that polyvinylidene fluoride in step S1 is replaced with polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), and solvent DMF is replaced with dimethyl sulfoxide.
Comparative example 1
Step S1: weighing 2.0g of polyether polyurethane, adding the polyether polyurethane into a solvent DMF, heating and stirring until the polyether polyurethane is completely dissolved, adding solute salt lithium bistrifluoromethylsulfonyl imide accounting for 10 weight percent of the total weight of the composite solid electrolyte, stirring and mixing uniformly, and adding filler Li accounting for 10 weight percent of the total weight of the composite solid electrolyte 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 Stirring, transferring to a ball milling tank, ball milling, mixing uniformly, coating on a die, immersing in absolute ethyl alcohol solvent to replace DMF solvent in the slurry, standing, taking out, and drying to obtain the composite solid electrolyte.
Step S2: cutting the completely dried composite solid electrolyte prepared in the step S1 into solid electrolyte wafers with the diameter of 19mm, and respectively assembling the solid electrolyte wafers into Li I SS and LFP I Li button cells in a glove box for subsequent testing.
Comparative example 2
Step S1: weighing 2.0g of polyvinylidene fluoride (PVDF), adding into solvent DMF, heating and stirring to dissolve completely, adding solute salt lithium bistrifluoromethylsulfonyl imide accounting for 20wt% of the total weight of the composite solid electrolyte, stirring and mixing uniformly, and adding filler Li accounting for 30wt% of the total weight of the composite solid electrolyte 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 Stirring, transferring to ball milling tank, ball milling, mixing, coating on mold, soaking in absolute ethanolAnd replacing the solvent DMF in the slurry, standing, taking out, and drying to obtain the composite solid electrolyte.
Step S2: cutting the completely dried composite solid electrolyte prepared in the step S1 into solid electrolyte wafers with the diameter of 19mm, and respectively assembling the solid electrolyte wafers into Li I SS and LFP I Li button cells in a glove box for subsequent testing.
Performance test:
1. test method
(1) The Li SS button cell prepared from example 1, comparative example 2 was subjected to a linear sweep voltammetry test, and its oxidation potential was analyzed.
(2) The lfp||li button cell prepared from example 1, comparative example 2 was subjected to constant current charge and discharge test in blue electric test software at a rate of 0.5C (1c=170 mAh/g).
(3) The NCM811 Li button cell prepared from example 1 was subjected to constant current charge and discharge test in blue electric test software at a rate of 0.2C (1c=200 mAh/g).
2. Test results
As shown in fig. 1, the composite solid electrolyte prepared in embodiment 1 has high flexibility and high mechanical strength, can realize bending and folding operations, and has obvious advantages when applied to wearable electronic equipment.
As shown in fig. 2, the composite solid electrolyte prepared in example 1 had a high mechanical strength of 4.79 Mpa.
As shown in fig. 3, the composite solid electrolyte prepared in example 1 began to rise significantly after 5.0V, indicating that decomposition began to occur, whereas the composite solid electrolytes prepared in comparative examples 1 and 2 began to decompose significantly at 4.5V.
As shown in fig. 4, the LFP Li button cell assembled in example 1 was able to stably cycle for 200 cycles at a rate of 0.5C with a capacity retention rate of 95.5%, whereas the LFP Li button cells assembled in comparative examples 1 and 2 were significantly reduced in capacity or coulombic efficiency when cycled for no more than 100 cycles.
As shown in fig. 5, after the NCM811 Li button cell assembled in example 1 was stably cycled for 100 cycles at a rate of 0.2C, the capacity retention rate was 78%, and the first-cycle discharge specific capacity reached 186.2mAh/g, indicating that the composite solid electrolyte prepared in example 1 can also work normally under high pressure conditions.
As shown in fig. 6, the solid-state battery assembled based on the composite solid-state electrolyte prepared in example 1 was subjected to performance test at 60 ℃ with NCM811 as a cathode material. The results showed that the solid-state battery having the composite solid electrolyte membrane prepared in example 1 was able to stably circulate for 100 cycles even at a high cut-off voltage of 4.3V with a capacity retention of 78% (0.2C).
The detailed process equipment and process flow of the present invention are described by the above embodiments, but the present invention is not limited to, i.e., it does not mean that the present invention must be practiced depending on the detailed process equipment and process flow. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (8)
1. The flexible composite solid electrolyte is characterized by being prepared from the following raw materials in percentage by weight:
5-30 wt% of solute salt, wherein the solute salt is one or more of lithium bistrifluoromethylsulfonyl imide, lithium hexafluorophosphate, lithium difluorooxalato borate, lithium nitrate or lithium tetrafluoroborate;
5-80 wt% of inorganic filler, wherein the inorganic filler is one or more of active filler or inert filler, the active filler is one or more of NASICON type filler, garnet type filler or perovskite type filler, and the inert filler is SiO 2 、Al 2 O 3 、TiO 2 Or ZrO(s) 2 One or more of the following;
10-80 wt% of a polymer substrate, wherein the polymer substrate consists of a polymer A and a polymer B in a mass ratio of 1-10:1, the polymer A is one or more of polyether polyurethane or polyester polyurethane, and the polymer B is one or more of fluorine-containing polymer ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene, fluorinated ethylene-propylene copolymer, perfluoroalkoxy resin, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride or polyvinylidene fluoride-hexafluoropropylene.
2. The flexible composite solid electrolyte according to claim 1, which is characterized by being prepared from the following raw materials in percentage by weight: 10-20wt% of solute salt, 10-40wt% of inorganic filler and the balance of polymer substrate.
3. The flexible composite solid state electrolyte of claim 1, wherein: the NASICON type filler is Li 1+x Al x Ti 2-x (PO 4 ) 3 Or Li (lithium) 1+x Al x Ge 2-x (PO 4 ) 3 One or more of the following; the garnet type filler is Li 7 La 3 Zr 2 O 12 The method comprises the steps of carrying out a first treatment on the surface of the The perovskite filler is Li 3x La 2/3-x TiO 3 。
4. The flexible composite solid state electrolyte of claim 1, wherein: the mass ratio of the polymer A to the polymer B in the polymer substrate is 2-8:1.
5. A method for preparing the flexible composite solid electrolyte according to any one of claims 1 to 4, which is characterized by comprising the following specific steps:
step S1: dissolving a polymer A in a solvent C, heating and stirring until the polymer A is dissolved to obtain slurry;
step S2: adding the polymer B into the slurry obtained in the step S1, heating, stirring and mixing uniformly;
step S3: adding solute salt into the slurry obtained in the step S2, and continuously heating, stirring and uniformly mixing;
step S4: and (3) adding inorganic filler into the slurry obtained in the step (S3), stirring, transferring to a ball milling tank, ball milling, uniformly mixing, coating on a die, immersing in a solvent D to replace the solvent C in the slurry, standing, taking out and drying to obtain the flexible composite solid electrolyte.
6. The method for producing a flexible composite solid electrolyte according to claim 5, characterized in that: the solvent C in the step S1 is one or more of N-methyl pyrrolidone, N-dimethylformamide or dimethyl sulfoxide, and the solvent D in the step S4 is one or more of acetone or ethanol.
7. The method for producing a flexible composite solid electrolyte according to claim 5, characterized in that: and in the step S1, the step S2 and the step S3, heating and stirring are performed in a magnetic stirring oil bath pot, and the heating and stirring temperature is 50-120 ℃.
8. A lithium metal battery characterized in that: a button cell is assembled by using the flexible composite solid electrolyte as defined in any one of claims 1 to 4, a lithium iron phosphate or nickel cobalt manganese positive electrode and a lithium metal negative electrode.
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