CN114843590A - Preparation and application of ultrathin organic-inorganic composite solid electrolyte membrane - Google Patents
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Abstract
A preparation and application of an ultrathin organic-inorganic composite solid electrolyte membrane belong to the technical field of lithium ion battery electrolytes. Firstly, selecting high molecular polymer and highly dispersed inorganic nano particles, preparing an ultrathin composite electrolyte self-supporting base membrane with controllable thickness by a casting method, then selecting a carbonate-based polymer electrolyte with high ionic conductivity, and preparing an ultrathin organic-inorganic composite electrolyte membrane by a solution casting method. The thickness of the ultrathin organic-inorganic composite electrolyte membrane prepared by the invention can be reduced to below 10 mu m, and the ultrathin organic-inorganic composite electrolyte membrane has high ionic conductivity, wide electrochemical stability window and excellent mechanical properties. The preparation method is simple in preparation process, convenient for large-scale production and suitable for commercial lithium ion solid-state batteries.
Description
Technical Field
The invention relates to a lithium ion battery solid electrolyte, in particular to preparation and application of an ultrathin organic-inorganic composite solid electrolyte membrane, belonging to the technical field of lithium ion battery electrolytes.
Background
Lithium ion batteries are widely used as novel electrochemical energy storage devices in the fields of mobile electronic devices, electric automobiles, emergency power supplies and the like, and are gradually popularized and used in the fields of energy storage power stations, rail transit, aerospace and the like. So far, most of commercial lithium ion batteries use conventional organic liquid electrolytes, such as ethylene carbonate, propylene carbonate, and the like. However, the lithium ion battery using the organic liquid electrolyte has a huge safety problem, which seriously hinders the further popularization and wider application of the lithium ion battery, mainly because the organic electrolyte generally has high chemical activity, volatility, easy ignition, explosion and other safety defects. Therefore, the use of solid electrolyte instead of conventional organic electrolyte is one of the effective approaches to solve the above safety problems of lithium ion batteries. Meanwhile, the solid electrolyte also has the advantages of high ionic conductivity, wide electrochemical window, wide working temperature, random cutting or change and the like.
For solid electrolytes, Li + The diffusion time of (a) is closely related to the thickness of the solid electrolyte. According to the equation τ ═ l 2 Where τ is the diffusion time, l is the solid electrolyte thickness, and D is the diffusion constant, it can be seen that decreasing the thickness l of the solid electrolyte membrane is effective in shortening the lithium ion transport distance and transport time. In addition, reducing the thickness of the solid electrolyte also helps to increase the energy density and power density of the solid-state battery. In addition, reducing the thickness of the solid electrolyte can reduce the manufacturing cost of the solid-state battery, which is of great significance in promoting the commercialization of the battery. It is noted that, in addition to reducing the thickness of the solid electrolyte membrane, the structure of the electrolyte needs to be designed to achieve interface matching with the positive and negative electrode materials. The oxidation resistance of the solid electrolyte membrane needs to be considered if it is on the positive electrode side; on the other hand, the negative electrode side, particularly, the lithium metal negative electrode, needs to have an action of suppressing the growth of lithium dendrites. Chinese patent (cn202111078836.x) discloses cellulose aerogel as skeleton and colloidal guar gum electrolyte as filler. Preparing cellulose aerogel through the step 1; step 2, preparing colloidal guar gum electrolyte; step 3, preparing a solid electrolyte film: and (3) doping the colloidal guar gum electrolyte into the cellulose aerogel to prepare a solid electrolyte. In thin film all-solid-state batteries, which are limited by the low ionic conductivity of the solid electrolyte, the narrow electrochemical window, and the severe interface problem between the electrolyte and the electrode material, the all-solid-state batteries cannot be matched with the high-voltage positive electrode material, have poor cycle performance and low power density, and the application thereofIs limited to some extent.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing an ultrathin organic-inorganic composite solid electrolyte membrane by combining a tape casting method with a solution casting method, and a lithium ion secondary all-solid-state battery is constructed by using the membrane electrolyte.
The technical scheme of the invention is as follows:
firstly, dispersing high molecular polymer (20 wt% -80 wt%) and highly dispersed inorganic nano particles (20 wt% -80 wt%, and adding up to 100% of high molecular polymer) in an organic solvent, preparing an ultrathin composite electrolyte self-supporting base membrane with controllable thickness and containing a large number of pores in the interior by a casting method, then selecting a carbonate-based polymer electrolyte precursor solution with high ionic conductivity, pouring the solution into the interior of the base membrane by a solution casting method to reach a saturated state, and polymerizing at high temperature (60-120 ℃) to obtain the ultrathin organic-inorganic composite electrolyte membrane.
The selected high molecular polymer includes but is not limited to one or more of polyethylene oxide (PEO) and derivatives thereof, polyvinylidene fluoride (PVDF) and derivatives thereof, Polyacrylonitrile (PAN) and derivatives thereof, polysiloxane and derivatives thereof, and the like. The selected organic solvent is one or more of the following: n-methylpyrrolidone (NMP), ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethylene carbonate, methyl ethyl carbonate, gamma-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, 1, 2-dimethoxyethane, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethyl sulfoxide;
highly dispersed inorganic nanoparticles include, but are not limited to, garnet-type Li 7 La 3 Zr 2 O 12 And doping modified solid electrolyte nano-particles and perovskite LiLaTiO 3 And doped modified solid electrolyte nanoparticles, NASICON type Li 1+x Al x Ti 2-x (PO 4 ) 3 And doping modified solid electrolyte nano-particles, LISICON type Li 14 Zn(GeO 4 ) 4 And doping modified solid electrolyte nano-particles and debris type LiTaSiO 5 And mixingHetero-modified solid electrolyte nanoparticles, sulfide Li 10 GeP 2 S 12 Solid electrolyte nanoparticles, halide Li 3 InCl 6 Solid electrolyte nanoparticles, montmorillonite nanoparticles, silica nanoparticles, zirconia nanoparticles, barium titanate nanoparticles, calcium carbonate nanoparticles, alumina nanoparticles, titania nanoparticles, silicon carbide nanoparticles, Li 14 Zn(GeO 4 ) 4 Nanoparticles, LiZr 2 (PO 4 ) 3 Nanoparticles, LiPON nanoparticles, and the like.
The carbonate-based polymer electrolyte precursor is a precursor capable of forming a carbonate-based polymer electrolyte, and includes, but is not limited to, one or more of a polycarbonate precursor solution (including carbonate + lithium salt + initiator), a polyethylene carbonate precursor solution (ethylene carbonate + lithium salt + initiator), a polyallylmethyl carbonate precursor solution (allyl methyl carbonate + lithium salt + initiator), a polyethylene carbonate precursor solution (ethylene carbonate + lithium salt + initiator), a polyvinyl fluoride carbonate precursor solution (fluoroethylene carbonate + lithium salt + initiator), and the like.
The thickness of the prepared ultrathin organic-inorganic composite electrolyte membrane can be reduced to below 10 mu m, and the ultrathin organic-inorganic composite electrolyte membrane has good mechanical properties.
The prepared ultrathin organic-inorganic composite electrolyte membrane has high room-temperature ionic conductivity and high room-temperature ionic conductivity (>1.0×10 -3 S/cm), wide electrochemically stable window (> 5.5V (vs. li) + /Li)) and high ion transport number (f: (Li))>0.65) and has good stability with lithium metal electrodes.
A lithium ion secondary all-solid-state battery is constructed by adopting the solid electrolyte film provided by the invention:
the positive electrode active material of the lithium ion battery is lithium cobaltate (LiCoO) 2 ) Lithium nickelate (LiNiO) 2 ) Lithium ion lithium fluorophosphate, lithium manganate, lithium-rich manganese-based layered oxide, lithium manganese iron phosphate, and lithium nickel cobalt aluminate(NCA), lithium nickel cobalt manganese oxide, lithium iron phosphate (LiFeO) 4 ) Lithium vanadium phosphate (Li) 3 V 2 (PO 4 ) 3 ) One or more of the above; the negative active material is one or more of metallic lithium, lithium alloy, graphite, hard carbon, lithium metal nitride, antimony oxide, carbon-germanium composite material, carbon-silicon composite material, lithium titanate and lithium-titanium oxide. The initiator or catalyst is one of the following: dibutyl tin dilaurate, dibutyl tin bis (acetylacetonate), Azobisisoheptonitrile (ABVN), Azobisisobutyronitrile (AIBN), dimethyl Azobisisobutyrate (AIBME), Benzoyl Peroxide (BPO), platinum water (Pt);
the preparation method of the lithium ion battery anode material comprises the following steps: grinding and mixing 50-90% of positive electrode active material and 5-30% of conductive agent acetylene black; adding polyvinylidene fluoride (PVDF) accounting for 1-15% of the mass fraction, polycarbonate-based organic-inorganic composite solid electrolyte accounting for 1-15% (adding 100%) and 1-methyl-2-pyrrolidone (NMP), grinding and mixing; coating on the surface of the aluminum foil, and drying; the metal lithium and the metal lithium alloy can be directly used as corresponding negative electrode materials; the preparation of other anode materials comprises the following steps: grinding and mixing a negative electrode active material accounting for 50-90% by mass and a conductive agent acetylene black accounting for 5-30% by mass, adding polyvinylidene fluoride (PVDF) accounting for 5-25% by mass (the above substances are added up to 100%), and grinding and mixing 1-methyl-2-pyrrolidone (NMP); coating the copper foil on the surface of the copper foil, and drying;
the lithium ion battery assembly comprises a button cell and a soft package cell, and the stacking sequence in the solid-state cell is a positive electrode, an ultrathin organic-inorganic composite solid-state electrolyte membrane of the invention and a negative electrode.
The invention has the novelty and the practicability that:
1. the thickness of the ultrathin organic-inorganic composite solid electrolyte membrane prepared by the invention can be reduced to below 10 mu m, and the ultrathin organic-inorganic composite solid electrolyte membrane has good flexibility and machining performance.
2. The ultrathin organic-inorganic composite solid electrolyte membrane prepared by the invention has good electrochemical performance and high room-temperature ionic conductivity>1.0×10 -3 S/cm), wide electrochemically stable window (> 5.5V (vs. li) + /Li)) and high ion transport number (f: (Li))>0.65) and has good stability with a lithium metal electrode.
3. The ultrathin organic-inorganic composite solid electrolyte membrane prepared by the invention has simple preparation process and can be produced in a quantitative manner.
Drawings
FIG. 1 is a photograph showing the optical morphology of a base film in example 2 of an ultrathin organic-inorganic composite solid electrolyte membrane.
Fig. 2 the resulting ultrathin organic-inorganic composite solid electrolyte membrane of example 2 was assembled with a charge-discharge curve of a lithium cobaltate positive electrode solid-state battery according to example 6.
Detailed Description
The present invention is illustrated below by specific examples, which are provided for better understanding of the present invention and are not intended to limit the scope of the present invention in any way.
Preparing an electrolyte:
example 1
Firstly, 1g of polyvinylidene fluoride (PVDF) is dispersed and dissolved in an NMP organic solvent, fully stirred and completely dissolved, and garnet type Li with the same quantity as the PVDF is added 6.6 La 2.9 Ca 0.1 Zr 1.75 W 0.25 O 12 Vigorously stirring solid electrolyte nano particles for 12 hours and carrying out ultrasonic treatment for 2 hours to obtain slurry with uniformly dispersed particles, and preparing an ultrathin composite electrolyte base film by a casting method to obtain a thin film electrolyte base film; then, a polyethylene carbonate electrolyte precursor solution (ethylene carbonate (76%) + LiTFSI (23.99%) + azobisisobutyronitrile (0.01%)) with high ionic conductivity is selected and poured into the thin film electrolyte basal membrane by a solution pouring method, and the ultrathin organic-inorganic composite electrolyte membrane with excellent performance is obtained by high-temperature curing at 80 ℃.
Example 2
Firstly, 1g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) is dispersed and dissolved in NMP organic solvent, fully stirred and completely dissolved, and garnet type Li equal to the PVDF-HFP is added 6.6 La 2.9 Ca 0.1 Zr 1.75 W 0.25 O 12 Solid electrolyte nanoparticlesViolently stirring for 12 hours and carrying out ultrasound for 2 hours to obtain slurry with uniformly dispersed particles, and preparing an ultrathin composite electrolyte base film by a casting method to obtain a thin film electrolyte base film; then, high-ion polyethylene carbonate electrolyte precursor solution (ethylene carbonate (76%) + LiTFSI (23.99%) + azobisisobutyronitrile (0.01%)) is selected and poured into the thin-film electrolyte basal membrane by a solution pouring method, and the ultrathin organic-inorganic composite electrolyte membrane with excellent performance is obtained by high-temperature curing at 80 ℃.
Example 3
Firstly, dispersing and dissolving 1g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) in an NMP organic solvent, fully stirring and completely dissolving, adding silicon dioxide nano particles which are equal to the PVDF-HFP, violently stirring for 12 hours and carrying out ultrasound for 2 hours to obtain slurry with uniformly dispersed particles, and preparing an ultrathin composite electrolyte base film by a casting method to obtain a thin film electrolyte base film; the preparation method comprises the following steps of pouring a polyethylene carbonate electrolyte precursor solution (ethylene carbonate (76%) + LiTFSI (23.99%) + azobisisobutyronitrile (0.01%)) into a thin film electrolyte base film by a solution pouring method, and curing at high temperature to obtain the ultrathin organic-inorganic composite electrolyte film with excellent performance.
Example 4
Firstly, 1g of Polyacrylonitrile (PAN) is dispersed and dissolved in an NMP organic solvent, fully stirred and completely dissolved, added with silica nanoparticles which are equal to the PAN and stirred vigorously for 12 hours and subjected to ultrasound treatment for 2 hours to obtain slurry with uniformly dispersed particles, and an ultrathin composite electrolyte base film is prepared by a casting method to obtain a thin film electrolyte base film; and (2) pouring a polyethylene carbonate electrolyte precursor solution (ethylene carbonate (76%) + LiTFSI (23.99%) + azobisisobutyronitrile (0.01%)) into the thin film electrolyte base film by a solution casting method, and curing at a high temperature of 80 ℃ to obtain the ultrathin organic-inorganic composite electrolyte film with excellent performance.
Example 5
First, 1g of polyethylene oxide (PEO) was dispersed and dissolved in an NMP organic solvent, and thoroughly stirred and dissolved, and garnet-type Li equivalent to PEO was added 6.6 La 2.9 Ca 0.1 Zr 1.75 W 0.25 O 12 Solid electrolyte nanoparticle compositionsVigorously stirring for 12h and ultrasonically treating for 2h to obtain slurry with uniformly dispersed particles, and preparing an ultrathin composite electrolyte base membrane by a casting method to obtain a thin-film electrolyte base membrane; and (2) pouring a polyethylene carbonate electrolyte precursor solution (ethylene carbonate (76%) + LiTFSI (23.99%) + azobisisobutyronitrile (0.01%)) into the thin film electrolyte base film by a solution casting method, and curing at a high temperature of 80 ℃ to obtain the ultrathin organic-inorganic composite electrolyte film with excellent performance.
Thickness of electrolyte: the thickness of the ultrathin organic-inorganic composite electrolyte membrane is measured by a micrometer (the precision is 0.01 mm), 3 points on the membrane are randomly measured, and the average value is calculated.
Ionic conductivity: two stainless steel gaskets are adopted to clamp the polymer electrolyte, and the R2032 button cell is assembled to measure the impedance according to the formula
Wherein L is the thickness of the polymer electrolyte, S is the area of the stainless steel gasket, and R is the measured resistance value.
Electrochemical window: a polymer electrolyte is clamped by stainless steel and a lithium sheet, a button cell of R2032 is assembled, and linear voltammetry scanning (LSV) measurement is carried out, wherein the initial voltage is 2.8V, the maximum potential is 6.5V, and the scanning speed is 1 mV/S.
Example 6
Uniformly grinding 240mg of lithium cobaltate anode and 45mg of acetylene black serving as a conductive agent for 40 min; adding 15mg of binder polyvinylidene fluoride, 15mg of electrolyte mixed solution and 150 mu L of 1-methyl-2-pyrrolidone, and uniformly grinding for 40 min; coating on the surface of an aluminum foil, and drying for 8 hours at 80 ℃ under a vacuum condition; the electrode sheet was cut into a 12mm round piece, and the ultrathin organic-inorganic composite electrolyte membrane of example 2 was used, and a solid lithium ion battery was assembled using metal lithium as the negative electrode. The assembled solid battery can be charged to 4.6V, can stably circulate for 200 circles under the charging cut-off voltage of 4.5V at room temperature, and has the capacity retention rate of over 74 percent.
TABLE 1
Claims (10)
1. The preparation method of the ultrathin organic-inorganic composite solid electrolyte membrane is characterized by comprising the following steps of: firstly, dispersing high molecular polymer and highly dispersed inorganic nano particles in an organic solvent, preparing an ultrathin composite electrolyte self-supporting base membrane with controllable thickness and a large number of pores in the interior by a casting method, then selecting a carbonate-based polymer electrolyte precursor solution with high ionic conductivity, pouring the solution into the base membrane by a solution casting method to reach a saturated state, and polymerizing at a high temperature of 60-120 ℃ to obtain an ultrathin organic-inorganic composite electrolyte membrane; 20-80 wt% of high molecular polymer, 20-80 wt% of highly dispersed inorganic nano particles, and 100% of inorganic nano particles and high molecular polymer.
2. The method for preparing an ultra-thin organic-inorganic composite solid electrolyte membrane according to claim 1, wherein the selected high molecular polymer is one or more selected from the group consisting of polyethylene oxide (PEO) and its derivatives, polyvinylidene fluoride (PVDF) and its derivatives, Polyacrylonitrile (PAN) and its derivatives, and polysiloxane and its derivatives.
3. The method for preparing an ultrathin organic-inorganic composite solid electrolyte membrane according to claim 1, wherein the organic solvent is one or more of the following: n-methylpyrrolidone (NMP), ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethylene carbonate, methyl ethyl carbonate, gamma-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, acetonitrile, 1, 2-dimethoxyethane, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethyl sulfoxide.
4. The method for preparing an ultra-thin organic-inorganic composite solid electrolyte membrane according to claim 1, wherein the highly dispersed inorganic nanoparticles are selected from garnet-type Li 7 La 3 Zr 2 O 12 And doping modified solid electrolyteRice particle, perovskite type LiLaTiO 3 And doped modified solid electrolyte nanoparticles, NASICON type Li 1+x Al x Ti 2-x (PO 4 ) 3 And doping modified solid electrolyte nano-particles, LISICON type Li 14 Zn(GeO 4 ) 4 And doping modified solid electrolyte nano-particles and debris LiTaSiO 5 And doping modified solid electrolyte nano-particles and sulfide Li 10 GeP 2 S 12 Solid electrolyte nanoparticles, halide Li 3 InCl 6 Solid electrolyte nanoparticles, montmorillonite nanoparticles, silica nanoparticles, zirconia nanoparticles, barium titanate nanoparticles, calcium carbonate nanoparticles, alumina nanoparticles, titania nanoparticles, silicon carbide nanoparticles, Li 14 Zn(GeO 4 ) 4 Nanoparticles, LiZr 2 (PO 4 ) 3 One or more of nanoparticles and LiPON nanoparticles.
5. The method for preparing an ultra-thin organic-inorganic composite solid electrolyte membrane according to claim 1, the preparation method is characterized in that a carbonate-based polymer electrolyte precursor is a precursor capable of forming a carbonate-based polymer electrolyte, and is selected from one or more of a polycarbonate precursor solution (comprising carbonate + lithium salt + initiator), a polyethylene carbonate precursor solution (comprising carbonate + lithium salt + initiator), a polyethylene ethylene carbonate precursor solution (comprising ethylene carbonate + lithium salt + initiator), a polyallyl methyl carbonate precursor solution (comprising allyl methyl carbonate + lithium salt + initiator), a polyethylene carbonate precursor solution (comprising ethylene carbonate + lithium salt + initiator), and a polyvinyl fluoride carbonate precursor solution (comprising fluoroethylene carbonate + lithium salt + initiator).
6. A method for manufacturing an ultra-thin organic-inorganic composite solid electrolyte membrane according to claim 1, wherein the ultra-thin organic-inorganic composite electrolyte membrane is manufactured to have a thickness of 10 μm or less.
7. An ultrathin organic-inorganic composite solid electrolyte membrane prepared by the method according to any one of claims 1 to 6.
8. An ultrathin organic-inorganic composite solid electrolyte membrane having room-temperature ionic conductivity, prepared by the method according to any one of claims 1 to 6>1.0×10 -3 S/cm, electrochemical stability window > 5.5V (vs. Li) + Per Li), ion transport number>0.65。
9. A lithium ion secondary all-solid battery comprising an ultrathin organic-inorganic composite solid electrolyte membrane prepared by the method of any one of claims 1 to 6.
10. The lithium ion secondary all-solid-state battery according to claim 9, wherein the positive active material of the lithium ion battery is lithium cobaltate (LiCoO) 2 ) Lithium nickelate (LiNiO) 2 ) Lithium ion fluorophosphate, lithium manganate, lithium-rich manganese-based layered oxide, lithium manganese iron phosphate, lithium Nickel Cobalt Aluminate (NCA), lithium nickel cobalt manganese oxide, lithium iron phosphate (LiFeO) 4 ) Lithium vanadium phosphate (Li) 3 V 2 (PO 4 ) 3 ) One or more of the above; the negative active material is one or more of metallic lithium, lithium alloy, graphite, hard carbon, lithium metal nitride, antimony oxide, carbon-germanium composite material, carbon-silicon composite material, lithium titanate and lithium-titanium oxide; the initiator or catalyst is one of the following: dibutyl tin dilaurate, dibutyl tin bis (acetylacetonate), Azobisisoheptonitrile (ABVN), Azobisisobutyronitrile (AIBN), dimethyl Azobisisobutyrate (AIBME), Benzoyl Peroxide (BPO), platinum water (Pt);
the preparation method of the lithium ion battery anode material comprises the following steps: grinding and mixing 50-90% of positive electrode active material and 5-30% of conductive agent acetylene black; adding polyvinylidene fluoride (PVDF) accounting for 1-15% of the mass fraction, polycarbonate-based organic-inorganic composite solid electrolyte accounting for 1-15% of the mass fraction and 1-methyl-2-pyrrolidone (NMP) for grinding and mixing; coating on the surface of the aluminum foil, and drying; the metal lithium and the metal lithium alloy are directly used as corresponding negative electrode materials; or other negative electrode materials are prepared by the following steps: grinding and mixing a negative electrode active material accounting for 50-90% by mass and a conductive agent acetylene black accounting for 5-30% by mass, adding polyvinylidene fluoride (PVDF) accounting for 5-25% by mass and 1-methyl-2-pyrrolidone (NMP), grinding and mixing; coating the copper foil on the surface of the copper foil, and drying;
the lithium ion battery assembly comprises a button cell and a soft package cell, and the stacking sequence in the solid-state cell is positive electrode-ultrathin organic-inorganic composite solid-state electrolyte membrane-negative electrode.
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|---|---|---|---|---|
| CN116345063A (en) * | 2023-05-31 | 2023-06-27 | 合肥长阳新能源科技有限公司 | Coated lithium battery diaphragm, preparation method thereof and lithium battery |
| CN117577930A (en) * | 2023-12-29 | 2024-02-20 | 国联汽车动力电池研究院有限责任公司 | Solid electrolyte membrane and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116345063A (en) * | 2023-05-31 | 2023-06-27 | 合肥长阳新能源科技有限公司 | Coated lithium battery diaphragm, preparation method thereof and lithium battery |
| CN116345063B (en) * | 2023-05-31 | 2023-08-29 | 合肥长阳新能源科技有限公司 | Coated lithium battery diaphragm, preparation method thereof and lithium battery |
| CN117577930A (en) * | 2023-12-29 | 2024-02-20 | 国联汽车动力电池研究院有限责任公司 | Solid electrolyte membrane and preparation method thereof |
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