CN114267870B - Cellulose composite solid electrolyte and preparation method and application thereof - Google Patents
Cellulose composite solid electrolyte and preparation method and application thereof Download PDFInfo
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- 239000001913 cellulose Substances 0.000 title claims abstract description 75
- 229920002678 cellulose Polymers 0.000 title claims abstract description 75
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 58
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000010416 ion conductor Substances 0.000 claims abstract description 45
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 22
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 20
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 21
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 17
- 239000003792 electrolyte Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000004745 nonwoven fabric Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000005518 polymer electrolyte Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- 229910003480 inorganic solid Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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- Conductive Materials (AREA)
- Primary Cells (AREA)
Abstract
The invention discloses a cellulose composite solid electrolyte, a preparation method and application thereof, wherein the cellulose composite solid electrolyte comprises a lithium fast ion conductor electrostatic spinning film, a cellulose film and a succinonitrile coating; the lithium fast ion conductor electrostatic spinning film is mainly prepared by electrostatic spinning of polyvinyl butyral and a lithium fast ion conductor, and the succinonitrile coating comprises succinonitrile, polyethylene oxide and lithium salt. The invention has the advantages of simple reaction process, easy operation of steps and low cost; the prepared cellulose composite solid electrolyte has higher ionic conductivity and cycle stability; the solid electrolyte used as the lithium ion battery has the characteristics of high efficiency, stability, high specific capacity, good safety performance and the like.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a cellulose composite solid electrolyte, and a preparation method and application thereof.
Background
Lithium ion batteries have received attention for their wide use in various applications, such as energy storage devices, portable electronic devices, and electric vehicles. This is due to the relatively low electrode potential of lithium metal (-3.04V vs. standard hydrogen electrode) and high theoretical specific capacity (3860 mAh g -1), however, the cycle life of the cell is typically less than a few hundred cycles due to the high energy density of the cell and rapid growth of lithium dendrites on the anode surface during cell cycling. In addition, when lithium metal is used as an anode, dendrites formed may penetrate the separator to short-circuit the battery and cause serious safety problems. Changing the organic liquid electrolyte with the solid electrolyte and developing the all-solid-state battery are considered to fundamentally solve the safety problems common to conventional batteries and achieve higher energy density because the solid electrolyte has many advantages such as high thermal stability, wide electrochemical window, low flammability, less volatility and leakage compared to the liquid electrolyte. In addition, the use of solid state electrolytes can provide for the application of high voltage cathodes and lithium metal cathodes, not only to prevent the growth of lithium dendrites, but also to increase the energy density of solid state lithium batteries.
In general, solid electrolytes can be classified into two types, inorganic solid electrolytes and solid polymer electrolytes. Common inorganic solid state electrolytes are mainly NASICON-type, garnet-type and perovskite-type, and have a broad voltage window (5 v vs. li+/Li), high ionic conductivity (> 10 -4S cm-1) and Li + migration number (≡1). However, poor interfacial contact between the inorganic solid electrolyte and the electrode results in a large interfacial resistance, which hinders its wide application. The polymer electrolyte mainly comprises poly (vinylidene fluoride-hexafluoropropylene), poly (vinylidene fluoride), poly (ethylene oxide) and poly (acrylonitrile). Solid polymer electrolytes are softer and easier to mass produce than inorganic solid electrolytes. However, polymer electrolytes generally exhibit low ionic conductivity (10 -7 S/cm) and poor mechanical properties at room temperature. Much research into polymer electrolytes has been focused mainly on improving electrochemical stability and ionic conductivity. A common solution is to use inorganic fillers, plasticizers and cross-linking copolymerization to enhance the properties of the polymer electrolyte.
Among the numerous methods, the addition of an inorganic filler is the best way to improve the performance of the polymer electrolyte, because it is easy to synthesize, widely available and simple in composition. Can effectively improve the mobility of lithium ions and the amorphous phase area and establish a rapid lithium ion conductive channel in the polymer electrolyte. The plasticized composite solid electrolyte not only greatly improves lithium ion conductivity at lower temperature (< 60 ℃) but also has lower interface resistance, which is important for improving the cycle performance of the all-solid battery.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the composite solid electrolyte which not only can consider the advantages of the inorganic solid electrolyte and the polymer solid electrolyte, but also can improve the chemical compatibility with electrode materials and has low cost and higher safety coefficient, and the preparation method and the application thereof.
The invention prepares a LATP lithium fast ion conductor by a hydrothermal method, prepares a polyvinyl butyral-LATP film by an electrostatic spinning method, and finally compounds the polyvinyl butyral-LATP film and a cellulose film after being soaked in succinonitrile mixed solution to prepare the cellulose compound solid electrolyte.
In order to achieve the above purpose, the specific technical scheme adopted is that;
The invention aims to provide a cellulose composite solid electrolyte, which comprises a lithium fast ion conductor electrostatic spinning film, a cellulose film and a succinonitrile coating, wherein the lithium fast ion conductor electrostatic spinning film is mainly prepared by electrostatic spinning of polyvinyl butyral and a lithium fast ion conductor, and the succinonitrile coating comprises succinonitrile, polyethylene oxide and lithium salt.
Further, the composition specifically comprises the following components: polyvinyl butyral; a lithium fast ion conductor; succinonitrile (succinonitrile); polyethylene oxide; a lithium salt; a cellulose film; the lithium fast ion conductor comprises Li 1.3Al0.3A1.7(XO4)3, wherein a is at least one of Zr, sn, hf, ge, ti, al and X is at least one of P, si.
Further, the mass ratio of the polyvinyl butyral to the lithium fast ion conductor is 1:1-4, and the mass ratio of the succinonitrile, the polyethylene oxide and the lithium salt is 10-20:3-5:1-3.
Further, the lithium salt includes at least one of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxaborate, lithium trifluoromethane sulfonate, lithium bis (trifluoromethane sulfonate) imide, and lithium tris (trifluoromethane sulfonate) methyl.
Further, the cellulose membrane comprises one or two of filter paper and cellulose non-woven fabric.
The second object of the present invention is to provide a preparation method of the above cellulose composite solid electrolyte, comprising the following steps:
(1) Preparing a lithium fast ion conductor, wherein the lithium fast ion conductor is derived from Li 1.3Al0.3A1.7(XO4)3, wherein a is at least one of Zr, sn, hf, ge, ti, al and X is at least one of P, si;
(2) Transferring the lithium fast ion conductor powder into a ball milling tank, and continuously ball milling for 10-24 hours under the condition of 200-400 rpm. Mixing 0.5g-4g of ball-milled lithium fast ion conductor powder with 0.5g-1g of polyvinyl butyral, adding the mixture into a beaker together with 5-10 ml of absolute ethyl alcohol, and magnetically stirring for 10-24 hours;
(3) Preparing the slurry uniformly stirred in the step (2) into a film with the thickness of 20-100 mu m by an electrostatic spinning mode, drying and cutting into a disc with the diameter of 10-18 mm;
(4) Succinonitrile, polyethylene oxide (5-20wt%) and lithium salt (0.5-2 mol/L) are mixed according to a proportion in a beaker, and the mixture is uniformly mixed under the conditions of 40-70 ℃ and magnetic stirring;
(5) Cutting a cellulose film with the thickness of 20-200 mu m into a disc with the same size as the lithium fast ion conductor film, soaking the cellulose film and the lithium fast ion conductor film in succinonitrile mixed solution prepared in the step (4) at the temperature of 40-70 ℃, and then paving the soaked lithium fast ion conductor film on the cellulose film to be cooled at room temperature, thus obtaining the cellulose composite solid electrolyte.
Further, the preparation method of the lithium fast ion conductor comprises the following steps:
(1) Adding ammonium dihydrogen phosphate and lithium hydroxide into a certain amount of distilled water according to stoichiometric ratio, and stirring uniformly. And adding isopropyl titanate in stoichiometric ratio into the mixed solution, stirring uniformly, and adding aluminum nitrate into the white solution according to a certain metering ratio. Adjusting the pH value of the mixed solution to be 7 by ammonia water, and continuously stirring for 3 hours;
(2) The final slurry was transferred to a stainless steel lined polytetrafluoroethylene autoclave and incubated at 190℃for 24 hours. The white powder obtained after suction filtration is dried for 24 hours at 80 ℃, and after drying, the white powder is transferred into a tube furnace to be presintered for 4 hours at 500 ℃, and then is calcined for 6 hours at 800 ℃ to obtain LATP powder.
Further, the thickness of the cellulose composite solid electrolyte is 40 μm to 400 μm.
The invention further aims to provide an application of the cellulose composite solid electrolyte in a lithium battery.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a cellulose composite solid electrolyte, which not only solves the problems of poor interface contact and large grain boundary impedance between the electrolyte and an electrode, but also maintains higher ionic conductivity, has the advantages of good safety performance, low cost and the like, and has wide application prospect in the field of solid lithium batteries.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a lithium fast-ion conductor provided in accordance with an embodiment of the invention;
FIG. 2 is an AC impedance curve of a cellulose composite solid-state electrolyte provided in accordance with an embodiment of the present invention;
fig. 3 is a linear sweep voltammogram of a cellulose composite solid state electrolyte provided in accordance with an embodiment of the present invention.
Fig. 4 is a graph of capacitive cycling performance of a cellulose composite solid-state electrolyte provided in accordance with an embodiment of the present invention.
Detailed Description
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
The cellulose composite solid electrolyte provided in the first embodiment is composed of polyvinyl butyral; li 1.3Al0.3Ti1.7(PO4)3 (hereinafter referred to as LATP); succinonitrile (succinonitrile); polyethylene oxide; lithium bis (trifluoromethylsulfonate) imide; filter paper composition. The thickness of the cellulose composite solid electrolyte is 120um, and the ionic conductivity at room temperature is 8.2X10 -4 S/cm.
Wherein the mass of the polyvinyl butyral is 0.5g, and the mass of the LATP is 0.5g.
The mass ratio of succinonitrile, polyethylene oxide and lithium bis (trifluoromethylsulfonate) imide is 15:4:1.
The embodiment also provides a preparation method and application of the cellulose composite solid electrolyte. The specific preparation method of the cellulose composite solid electrolyte provided by the embodiment is as follows: comprises a step of preparing a lithium fast ion conductor, an electrostatic spinning film forming step and a compounding step, wherein,
The preparation of the lithium fast ion conductor comprises the following steps:
(1) Adding ammonium dihydrogen phosphate and lithium hydroxide into a certain amount of distilled water according to stoichiometric ratio, and stirring uniformly. And adding isopropyl titanate in stoichiometric ratio into the mixed solution, stirring uniformly, and adding aluminum nitrate into the white solution according to a certain metering ratio. Adjusting the pH value of the mixed solution to be 7 by ammonia water, and continuously stirring for 3 hours;
(2) The final slurry was transferred to a stainless steel lined polytetrafluoroethylene autoclave and incubated at 190℃for 24 hours. The white powder obtained after suction filtration is dried for 24 hours at 80 ℃, and after drying, the white powder is transferred into a tube furnace to be presintered for 4 hours at 500 ℃, and then is calcined for 6 hours at 800 ℃ to obtain LATP powder.
And (3) electrostatic spinning film forming step:
(3) The LATP powder was transferred to a ball milling pot and ball milled continuously at 360 rpm for 10 hours. Adding the ball-milled LATP powder and polyvinyl butyral into a beaker filled with 10ml of absolute ethyl alcohol according to the mass ratio of 2:1, and magnetically stirring for 24 hours;
(4) The evenly stirred slurry is made into a film with the thickness of 50 mu m by an electrostatic spinning mode, and the film is dried and cut into a disc with the diameter of 16 mm.
And (3) compounding:
(5) Mixing succinonitrile, polyethylene oxide and lithium bis (trifluoromethylsulfonate) imide according to a mass ratio of 15:4:1 in a beaker, and uniformly mixing under the condition of magnetic stirring at 60 ℃;
(6) The filter paper (thickness 70 μm) was cut into discs of the same size as the electrospun film, and the filter paper and LATP film were immersed in succinonitrile mixture at 60 ℃. And paving the soaked LATP film on filter paper, and cooling at room temperature to obtain the solid electrolyte.
Fig. 1 shows the XRD pattern of LATP prepared in this example one, showing that the process produces substantially pure phase LATP, free of other significant impurities.
The cellulose composite solid electrolyte prepared in the first example was assembled into a symmetrical blocking battery, and the alternating current impedance spectrum obtained by using a stainless steel gasket as a blocking electrode was shown in FIG. 2, and the ion conductivity of the cellulose composite solid electrolyte was calculated to be 8.1X10 -4 S/cm.
The cellulose composite solid electrolyte prepared in the first embodiment is punched into a wafer with the diameter of 16mm, the wafer is used as an electrolyte, a stainless steel gasket is used as an anode, a metal lithium sheet is used as a cathode, and a battery is assembled, and an electrochemical window is measured by a linear scanning voltammetry method, as shown in fig. 3, and the lowest oxidation potential is about 4.05V.
The cellulose composite solid electrolyte prepared in the first embodiment is punched into a wafer with the diameter of 16mm, and the wafer is used as the electrolyte to assemble the solid lithium ion battery. The anode consists of lithium iron phosphate, superconducting carbon black, polyvinylidene fluoride, polyethylene oxide and lithium bis (trifluoromethylsulfonate) imide according to the mass ratio of 80:10:7:1:2, the cathode is a metal lithium sheet, and the battery is assembled in a glove box filled with argon. And (3) carrying out constant-current charge-discharge cycle test on the solid-state lithium ion battery, wherein the capacity can still be kept at 136mAh/g after the solid-state lithium ion battery is cycled for 135 weeks under the current density of 1C.
Example two
The cellulose composite solid electrolyte provided in the second embodiment is composed of polyvinyl butyral; LATP; succinonitrile (succinonitrile); polyethylene oxide; lithium bis (trifluoromethylsulfonate) imide; a cellulose non-woven fabric. The thickness of the cellulose composite solid electrolyte is 130um, and the ionic conductivity at room temperature is 8 multiplied by 10 -4 S/cm.
Wherein the mass of the polyvinyl butyral is 0.5g and the mass of the LATP is 1g.
The mass ratio of succinonitrile, polyethylene oxide and lithium bis (trifluoromethylsulfonate) imide is 12:5:3.
The second embodiment also provides a preparation method and application of the cellulose composite solid electrolyte. The specific preparation method of the cellulose composite solid electrolyte provided by the embodiment is as follows: comprises a step of preparing a lithium fast ion conductor, an electrostatic spinning film forming step and a compounding step, wherein,
Lithium fast ion conductor step:
(1) Adding ammonium dihydrogen phosphate and lithium hydroxide into a certain amount of distilled water according to stoichiometric ratio, and stirring uniformly. And adding isopropyl titanate in stoichiometric ratio into the mixed solution, stirring uniformly, and adding aluminum nitrate into the white solution according to a certain metering ratio. Adjusting the pH value of the mixed solution to be 7 by ammonia water, and continuously stirring for 3 hours;
(2) The final slurry was transferred to a stainless steel lined polytetrafluoroethylene autoclave and incubated at 190℃for 24 hours. The white powder obtained after suction filtration is dried for 24 hours at 80 ℃, and after drying, the white powder is transferred into a tube furnace to be presintered for 4 hours at 500 ℃, and then is calcined for 6 hours at 800 ℃ to obtain LATP powder.
And (3) electrostatic spinning film forming step:
(3) The LATP powder was transferred to a ball milling pot and ball milled continuously at 300 rpm for 15 hours. Adding the ball-milled LATP powder and polyvinyl butyral into a beaker filled with 10ml of absolute ethyl alcohol according to the mass ratio of 1:1, and magnetically stirring for 24 hours;
(4) The evenly stirred slurry is made into a film with the thickness of 50 mu m by an electrostatic spinning mode, and the film is dried and cut into a disc with the diameter of 16 mm.
And (3) compounding:
(5) Mixing succinonitrile, polyethylene oxide and lithium bis (trifluoromethylsulfonate) imide according to a mass ratio of 12:5:3 in a beaker, and uniformly mixing under the condition of magnetic stirring at 60 ℃;
(6) The cellulose nonwoven fabric (thickness 80 μm) was cut into a disk having the same size as the electrospun film, and the cellulose nonwoven fabric and the LATP film were immersed in a succinonitrile mixed solution at 60 ℃. And paving the soaked LATP film on a cellulose non-woven fabric, and cooling at room temperature to obtain the prepared solid electrolyte.
The cellulose composite solid electrolyte prepared in the second example was assembled into a symmetrical blocking battery, and an alternating current impedance test was performed using a stainless steel gasket as a blocking electrode, and the ion conductivity of the obtained cellulose composite solid electrolyte was calculated to be 8×10 -4 S/cm.
Example III
The cellulose composite solid electrolyte provided in the third embodiment is composed of polyvinyl butyral; LATP; succinonitrile (succinonitrile); polyethylene oxide; lithium triflate; filter paper composition. The thickness of the cellulose composite solid electrolyte is 120um, and the ionic conductivity at room temperature is 8.05X10 -4 S/cm.
Wherein the mass of the polyvinyl butyral is 0.5g, and the mass of the LATP is 1.5g.
The mass ratio of succinonitrile, polyethylene oxide and lithium triflate is 13:4:3.
The third embodiment also provides a preparation method and application of the cellulose composite solid electrolyte. The specific preparation method of the cellulose composite solid electrolyte provided by the embodiment is as follows: comprises a step of preparing a lithium fast ion conductor, an electrostatic spinning film forming step and a compounding step, wherein,
Lithium fast ion conductor step:
(1) Adding ammonium dihydrogen phosphate and lithium hydroxide into a certain amount of distilled water according to stoichiometric ratio, and stirring uniformly. And adding isopropyl titanate in stoichiometric ratio into the mixed solution, stirring uniformly, and adding aluminum nitrate into the white solution according to a certain metering ratio. Adjusting the pH value of the mixed solution to be 7 by ammonia water, and continuously stirring for 3 hours;
(2) The final slurry was transferred to a stainless steel lined polytetrafluoroethylene autoclave and incubated at 190℃for 24 hours. The white powder obtained after suction filtration is dried for 24 hours at 80 ℃, and after drying, the white powder is transferred into a tube furnace to be presintered for 4 hours at 500 ℃, and then is calcined for 6 hours at 800 ℃ to obtain LATP powder.
And (3) electrostatic spinning film forming step:
(3) The LATP powder was transferred to a ball milling pot and ball milled continuously at 360 rpm for 10 hours. Adding the ball-milled LATP powder and polyvinyl butyral into a beaker filled with 10ml of absolute ethyl alcohol according to the mass ratio of 1:2, and magnetically stirring for 24 hours;
(4) The evenly stirred slurry is made into a film with the thickness of 50 mu m by an electrostatic spinning mode, and the film is dried and cut into a disc with the diameter of 16 mm.
And (3) compounding:
(5) Mixing succinonitrile, polyethylene oxide and lithium trifluoromethane sulfonate according to a mass ratio of 13:4:3 in a beaker, and uniformly mixing under the conditions of 60 ℃ and magnetic stirring;
(6) A cellulose nonwoven fabric (thickness: 70 μm) was cut into a disk having a size identical to that of the electrospun film, and the cellulose nonwoven fabric and the LATP film were immersed in a succinonitrile mixed solution at 60 ℃. And paving the soaked LATP film on a cellulose non-woven fabric, and cooling at room temperature to obtain the prepared solid electrolyte.
The cellulose composite solid electrolyte prepared in the third example is assembled into a symmetrical blocking battery, a stainless steel gasket is used as a blocking electrode, an alternating current impedance test is carried out, and the ion conductivity of the cellulose composite solid electrolyte is calculated to be 8.05X10 - 4 S/cm.
In conclusion, the cellulose composite solid electrolyte prepared by the invention not only solves the problems of poor interface contact and large grain boundary impedance between the electrolyte and the electrode, but also maintains higher ionic conductivity, has lower cost and extremely high safety, and has wide application prospect in the field of solid lithium batteries.
Although the invention has been described with reference to the preferred embodiments, it should be understood that the invention is not limited thereto, but rather may be modified and varied by those skilled in the art without departing from the spirit and scope of the invention.
Claims (9)
1. The cellulose composite solid electrolyte is characterized by comprising a lithium fast ion conductor electrostatic spinning film, a cellulose film and a succinonitrile coating, wherein the lithium fast ion conductor electrostatic spinning film is mainly prepared by mixing polyvinyl butyral with a lithium fast ion conductor and then carrying out electrostatic spinning, and the succinonitrile coating comprises succinonitrile, polyethylene oxide and lithium salt;
The preparation method of the cellulose composite solid electrolyte comprises the following steps:
(1) Preparing a lithium fast ion conductor, wherein the lithium fast ion conductor is derived from Li 1.3Al0.3A1.7(XO4)3, wherein a is at least one of Zr, sn, hf, ge, ti, al and X is at least one of P, si;
(2) Transferring the lithium fast ion conductor powder into a ball milling tank, continuously ball milling for 10-24 hours under the condition of 200-400 r/min, mixing 0.5-4 g of the ball milled lithium fast ion conductor powder with 0.5-1 g of polyvinyl butyral, adding the mixture into a beaker together with 5-10 ml of absolute ethyl alcohol, and magnetically stirring for 10-24 hours;
(3) Preparing the slurry uniformly stirred in the step (2) into a film with the thickness of 20-100 mu m by an electrostatic spinning mode, drying and cutting into a disc with the diameter of 10-18 mm;
(4) Succinonitrile, polyethylene oxide (5-20wt%) and lithium salt (0.5-2 mol/L) are mixed according to a proportion in a beaker, and the mixture is uniformly mixed under the conditions of 40-70 ℃ and magnetic stirring;
(5) Cutting a cellulose film with the thickness of 20-200 mu m into a disc with the same size as the lithium fast ion conductor film, soaking the cellulose film and the lithium fast ion conductor film in succinonitrile mixed solution prepared in the step (4) at the temperature of 40-70 ℃, paving the soaked lithium fast ion conductor film on the cellulose film, and cooling at room temperature to obtain the cellulose composite solid electrolyte.
2. The cellulose composite solid state electrolyte of claim 1, wherein the lithium fast ion conductor comprises Li 1.3Al0.3A1.7(XO4)3, wherein a is at least one of Zr, sn, hf, ge, ti, al and X is at least one of P, si.
3. The cellulose composite solid state electrolyte of claim 1, wherein the mass ratio of polyvinyl butyral to lithium fast ion conductor is 1:1-4, and the mass ratio of succinonitrile, polyethylene oxide and lithium salt is 10-20:3-5:1-3.
4. The cellulose composite solid state electrolyte of claim 1, wherein the lithium salt comprises at least one of lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate, lithium trifluoromethane sulfonate, lithium bis (trifluoromethane sulfonate) imide, and lithium tris (trifluoromethane sulfonate) methyl.
5. The cellulose composite solid state electrolyte of claim 1, wherein the cellulose membrane comprises one or both of filter paper, cellulose nonwoven fabric.
6. A method for producing the cellulose composite solid electrolyte according to any one of claims 1 to 5, comprising the steps of:
(5) Preparing a lithium fast ion conductor, wherein the lithium fast ion conductor is derived from Li 1.3Al0.3A1.7(XO4)3, wherein a is at least one of Zr, sn, hf, ge, ti, al and X is at least one of P, si;
(6) Transferring the lithium fast ion conductor powder into a ball milling tank, continuously ball milling for 10-24 hours under the condition of 200-400 r/min, mixing 0.5-4 g of the ball milled lithium fast ion conductor powder with 0.5-1 g of polyvinyl butyral, adding the mixture into a beaker together with 5-10 ml of absolute ethyl alcohol, and magnetically stirring for 10-24 hours;
(7) Preparing the slurry uniformly stirred in the step (2) into a film with the thickness of 20-100 mu m by an electrostatic spinning mode, drying and cutting into a disc with the diameter of 10-18 mm;
(8) Succinonitrile, polyethylene oxide (5-20wt%) and lithium salt (0.5-2 mol/L) are mixed according to a proportion in a beaker, and the mixture is uniformly mixed under the conditions of 40-70 ℃ and magnetic stirring;
(5) Cutting a cellulose film with the thickness of 20-200 mu m into a disc with the same size as the lithium fast ion conductor film, soaking the cellulose film and the lithium fast ion conductor film in succinonitrile mixed solution prepared in the step (4) at the temperature of 40-70 ℃, paving the soaked lithium fast ion conductor film on the cellulose film, and cooling at room temperature to obtain the cellulose composite solid electrolyte.
7. The method for preparing a cellulose composite solid state electrolyte according to claim 6, wherein the method for preparing a lithium fast ion conductor according to step (1) comprises the steps of:
(1) Adding ammonium dihydrogen phosphate and lithium hydroxide into distilled water according to a stoichiometric ratio, stirring uniformly, adding isopropyl titanate according to the stoichiometric ratio into the mixed solution, stirring uniformly, adding aluminum nitrate according to a certain stoichiometric ratio, adjusting the pH value of the mixed solution to be 7 by using ammonia water, and continuously stirring for 3 hours;
(2) Transferring the final slurry into an autoclave, preserving heat at 190 ℃ for 24 hours, filtering to obtain white powder, drying at 80 ℃ for 24 hours, transferring into a tube furnace after drying, presintering at 500 ℃ for 4 hours, and calcining at 800 ℃ for 6 hours to obtain LATP powder.
8. The method for producing a cellulose composite solid state electrolyte according to claim 6, wherein the thickness of the cellulose composite solid state electrolyte is 40 μm to 400 μm.
9. Use of the cellulose composite solid-state electrolyte of any one of claims 1 to 5 in a lithium battery.
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| CN101707241A (en) * | 2009-11-27 | 2010-05-12 | 青岛生物能源与过程研究所 | Diaphragm for lithium-air battery and preparation method thereof |
| CN108736062A (en) * | 2018-04-28 | 2018-11-02 | 浙江天能能源科技股份有限公司 | A kind of lithium ion battery composite solid electrolyte and preparation method thereof |
| CN113782826A (en) * | 2021-08-25 | 2021-12-10 | 珠海冠宇电池股份有限公司 | Solid electrolyte and solid battery comprising same |
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| CN101707241A (en) * | 2009-11-27 | 2010-05-12 | 青岛生物能源与过程研究所 | Diaphragm for lithium-air battery and preparation method thereof |
| CN108736062A (en) * | 2018-04-28 | 2018-11-02 | 浙江天能能源科技股份有限公司 | A kind of lithium ion battery composite solid electrolyte and preparation method thereof |
| CN113782826A (en) * | 2021-08-25 | 2021-12-10 | 珠海冠宇电池股份有限公司 | Solid electrolyte and solid battery comprising same |
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