CN115714201A - Electrode-electrolyte integrated composite material and preparation method and application thereof - Google Patents
Electrode-electrolyte integrated composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an electrode-electrolyte integrated composite material and a preparation method and application thereof, firstly, liFePO4, conductive carbon black, a polymer and a conductive lithium salt are dissolved in a solvent according to a certain proportion to prepare a composite spinning precursor solution; then carrying out electrostatic spinning on the composite spinning precursor solution to obtain a three-dimensional nanofiber anode; and finally, compounding the three-dimensional nanofiber positive electrode with a polymer-inorganic filler-conductive lithium salt system in a pouring mode to obtain the electrode-electrolyte integrated composite membrane with a three-dimensional structure. The composite material prepared by the invention has good mechanical flexibility, has good electrochemical performance when being used as a material of a solid-state lithium battery, can meet the requirement of a flexible battery, can be used as an electrode and an electrolyte material of the solid-state lithium battery, can be applied to the energy storage field represented by the flexible all-solid-state lithium battery, and has good safety.
Description
Technical Field
The invention relates to an energy storage functional material, in particular to an electrode-electrolyte integrated composite material and a preparation method and application thereof. Belongs to the technical field of energy storage functional materials.
Background
With the increasing demand of wearable intelligent electronic products and intelligent textiles, corresponding flexible energy storage equipment is required to be matched with the wearable intelligent electronic products and the intelligent textiles; the lithium battery has the characteristics of high energy density, power density, environmental friendliness and the like, so that the lithium battery becomes one of the most promising flexible energy storage devices at present. However, the current commercial lithium ion battery has the defects of insufficient energy density and low safety due to the use of organic flammable liquid electrolyte, so that the lithium ion battery is limited to become a flexible energy storage device and cannot be matched with wearable electronic products.
To address the inherent deficiencies of commercial liquid lithium ion batteries, solid electrolytes may be used in place of liquid electrolytes. Compared with liquid electrolyte, the solid electrolyte is nonflammable, has no leakage risk, and can effectively solve the potential safety hazard of the battery. In addition, the solid electrolyte has a wide electrochemical window, so that the solid electrolyte can be matched with lithium metal negative electrode and high-voltage positive electrode materials, and the energy density of the battery is greatly improved. The inorganic ceramic solid electrolyte in the solid electrolyte has high ion conductivity (10 at room temperature) - 4 Scm -1 ) Wide electrochemical window and stable chemical property with lithium metal, and is popular with researchers at home and abroad. However, the inorganic ceramic solid electrolyte is rigid and fragile, and has high interface resistance with the electrodes, so that the requirements of flexible and wearable energy storage devices cannot be met.
For the problems of the inorganic ceramic solid electrolyte, an effective solution is to combine inorganic ceramic nanoparticles with high ionic conductivity with a flexible polymer matrix, i.e., oxide ceramic nanoparticles are used as active fillers and dispersed in the polymer matrix to construct a composite system, so as to exert the complementary advantages of the two. The composite solid electrolyte has high ionic conductivity of the inorganic ceramic solid electrolyte and excellent mechanical flexibility of the polymer, and is an ideal candidate of the solid electrolyte. However, there is a problem that solid-solid contact between the solid electrolyte and the electrodes causes poor interfacial contact, resulting in large interfacial resistance, which affects electrochemical performance of the all-solid battery, which has not yet been solved. Therefore, it is a great challenge how to achieve high ionic conductivity in an all-solid-state positive electrode and to form a small resistive interface with the solid-state electrolyte.
Currently, the preparation of the positive electrode of the lithium ion battery is to directly coat an active material on a rigid current collector (carbon-coated aluminum foil), so that the active material is easy to fall off during the bending process of the electrode, a continuous conductive path is damaged, the capacity of the battery is rapidly attenuated, and the electrochemical performance is degraded. At the same time, the electrochemically inert materials used in the manufacture of the electrodes, including the metal current collectors, the polymeric binder, and the conductive additives, result in a reduction in the energy density of the battery. Binderless electrodes are one of the most efficient designs to achieve the desired electrochemical performance in the cell. For example, self-supporting carbon nanotubes or carbon nanofibers that contain only electroactive materials. Carbon nanotube-based composite electrodes have been passed through a vacuum filtration process (CNTs-LiNi) 0.5 Mn 1.5 O 4 ) Or aerosol spray process (CNTs-Li) 4 Ti 5 O 12 ) And (4) preparation. However, most of these manufacturing methods require a cumbersome process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an electrode-electrolyte integrated composite material, a preparation method and application thereof so as to solve the problems of high interface resistance and low utilization rate of electrode active materials caused by poor interface compatibility between the electrode and the electrolyte.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an electrode-electrolyte integrated composite material comprises the following specific steps:
s1, dissolving a polymer and a conductive lithium salt in an organic solvent to obtain a polymer solution, adding lithium iron phosphate and superconducting carbon black into the polymer solution, stirring and dispersing uniformly to obtain a precursor solution, and performing electrostatic spinning to obtain a three-dimensional fiber structure positive electrode film;
s2, adding the polymer, the conductive lithium salt and the oxide type ceramic nano particles into a solvent, and uniformly stirring and dispersing to obtain a solid electrolyte mixed solution;
s3, then placing the three-dimensional fiber structure positive electrode film on a mold, pouring a layer of solid electrolyte mixed solution on the surface of the three-dimensional fiber structure positive electrode film, demolding after acetonitrile is completely volatilized, and drying in vacuum to obtain the composite electrolyte;
the oxide type ceramic nanoparticles are obtained by carrying out primary ball milling, drying, calcining, forming, sintering and secondary ball milling on metal ion precursor salt containing oxide type ceramic solid electrolyte, wherein the metal ion precursor salt is selected from any one or more of garnet type, NASICON type, perovskite type or anti-perovskite type ceramic precursor salt.
Preferably, the polymer is selected from any one or more of polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC); the conductive lithium salt is selected from lithium halide (LiX, X = F, cl, br, I), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium perchlorate (LiClO) 4 ) Lithium hexafluorophosphate (LiPF) 6 ) Or lithium tetrafluoroborate (LiBF) 4 )。
Preferably, the oxide-type ceramic solid electrolyte is selected from Li 6.75 La 3 Zr 2 T 0.25 O 12 、Li 6.28 Al 0.24 La 3 Zr 2 O 12 、Li 6.75 La 3 Zr 2 T 0.25 O 12 、Li 3x La (2/3)-x TiO 3 Any one of (a); the corresponding metal ion precursor salts are respectively as follows:
Li 6.75 La 3 Zr 2 T 0.25 O 12 ：Li 2 NO 3 、La 2 O 3 、ZrO 2 、Ta 2 O 5 the molar ratio of the four is 3.375:1.5:1.75:0.125;
Li 6.28 Al 0.24 La 3 Zr 2 O 12 ：Li 2 NO 3 、La 2 O 3 、ZrO 2 、Al 2 O 3 the molar ratio of the four is 3.14:1.5:2:0.12;
Li 6.75 La 3 Zr 2 T 0.25 O 12 ：Li 2 NO 3 、La 2 O 3 、ZrO 2 、Ta 2 O 5 the molar ratio of the four is 3.375:1.5:1.75:0.125;
Li 3x La (2/3)-x TiO 3 ：1mmol Li 2 NO 3 、1mmol La 2 O 3 、4mmol TiO 2 the molar ratio of the three is 1:1:4.
preferably, when the oxide type ceramic nano-particles are prepared, lithium nitrate is added as a compensation agent, and the dosage of the lithium nitrate is 15 percent of the total weight of the metal ion precursor salt;
the primary ball milling or the secondary ball milling uses isopropanol as a ball milling medium, zirconia balls are adopted, the ball milling speed is 300rpm, and the ball milling time is 12 hours;
the drying process conditions are as follows: drying at 80 ℃ for 12 hours; the calcination process conditions are as follows: calcining at 900 ℃ for 12 hours; the molding process conditions are as follows: pressing the mixture into pellets under the pressure of 15 MPa; the sintering process conditions are as follows: heating to 1100 ℃ at 1 ℃/min under air atmosphere, and sintering for 1-32 hours under heat preservation.
Preferably, in step S1, the mass ratio of the polymer, the conductive lithium salt and the organic solvent is 1 to 5:1:100 to 250; the organic solvent is acetonitrile or N, N-dimethylformamide, and the dissolving temperature is 25-50 ℃.
Further preferably, the mass ratio of the polymer, the conductive lithium salt and the organic solvent is 2 to 3:1: 115-125 ℃ and the dissolving temperature is room temperature or 40 ℃.
Preferably, in step S1, the mass ratio of the lithium iron phosphate, the superconducting carbon black, and the polymer solution is 3 to 12:0.2 to 3:100 to 300 ℃ and the stirring temperature is 25 to 50 ℃.
Further preferably, the mass ratio of the lithium iron phosphate to the superconducting carbon black to the polymer solution is 5-6: 1:118 to 129 ℃ and the stirring temperature is room temperature or 40 ℃.
Preferably, in step S1, the process conditions of electrostatic spinning are as follows: the electrostatic voltage is 8-15 kV, the spinning distance is 8-15 cm, the flow rate of spinning solution is 0.5-1.0 mL/h, the total amount of spinning is 3-15 mL, and the rotating speed of a spinning rotary drum is 200-400 rpm.
Further preferably, the electrostatic spinning process conditions are as follows: the static voltage is 13kV, the spinning distance is 10cm, the flow rate of the spinning solution is 0.8mL/h, and the rotating speed of the rotary drum is 250rpm.
Preferably, in step S1, the thickness of the three-dimensional fiber structure positive electrode film is controlled to be 10 to 50 μm.
Preferably, in step S2, the mass ratio of the polymer, the conductive lithium salt, the oxide-type ceramic nanoparticles, and the solvent is 2 to 4:1:0.1 to 1.5:25 to 70 percent; the stirring time is 24 to 48 hours; the solvent is any one of N, N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, deionized water, acetone or absolute ethyl alcohol.
Further preferably, the mass volume ratio of the polymer, the conductive lithium salt, the oxide type ceramic nanoparticles and the solvent is 2.45g:0.8g:0.3611g:50mL.
Preferably, in step S3, the dosage per unit area of the solid electrolyte mixed solution poured on the surface of the three-dimensional fiber structure positive electrode film is 0.2-1 mL/cm -2 。
Preferably, in step S3, the vacuum drying process conditions are as follows: vacuum drying at 40-60 deg.c for 12-48 hr; further preferably, the drying is carried out under vacuum at 50 ℃ for 24 hours.
An electrode-electrolyte integrated composite material is obtained by the preparation method.
The electrode-electrolyte integrated composite material is applied to the preparation of a flexible all-solid-state lithium battery.
The invention has the beneficial effects that:
firstly, liFePO is used 4 Dissolving conductive carbon black (Super P), a polymer and conductive lithium salt in a solvent according to a certain proportion to prepare a composite spinning precursor solution; then carrying out electrostatic spinning on the composite spinning precursor solution to obtain a three-dimensional nanofiber anode; finally, compounding the three-dimensional nanofiber positive electrode and a polymer-inorganic filler-conductive lithium salt system in a pouring mode to obtain the electrode-electrolyte integrated composite with the three-dimensional structureAnd (3) a film.
The composite material prepared by the invention has good mechanical flexibility, has good electrochemical performance when being used as a material of a solid-state lithium battery, can meet the requirement of a flexible battery, can be used as an electrode and an electrolyte material of the solid-state lithium battery, can be applied to the energy storage field represented by the flexible all-solid-state lithium battery, and has good safety. Compared with the traditional coating mode, the active material with the same unit mass has higher specific capacity and lower interface resistance, and the application potential in the aspect of preparing the lithium metal solid-state battery with low cost and high performance is proved.
The invention disperses active substance-conductive carbon black material in polymer solution, collects on carbon-coated aluminum foil through electrostatic spinning method, prepares three-dimensional net-shaped anode framework, and uses as flexible electrode-electrolyte integrated fiber framework.
The Super P has good conductivity, and the three-dimensional continuous frame of the electrospun nanofiber membrane enables the Super P to easily form a long-range continuous conductive grid, so that a good effect can be achieved at a low addition amount, and the Super P has good electrical property and is uniformly distributed in LiFePO 4 And polymer composite fibers, the conductivity of the electrode can be effectively improved, and the overall electrochemical performance of the full battery is further improved. The invention disperses oxide type inorganic ceramic filler in PEO-LiTFSI conductive polymer solution, and liquid phase assembly is carried out on a positive electrode nano fiber membrane by a solution casting method to be integrated with the positive electrode nano fiber membrane, thereby obtaining integrated LiFePO 4 A positive electrode-LLZTO composite electrolyte nano-fiber composite membrane (In-LFP-LLZTO). The integrated electrode electrolyte structure enables the electrolyte to have a net-shaped long-distance continuous ion transmission path in the positive electrode frame, so that the rapid migration of lithium ions can be realized, the rate capability of the solid-state battery is improved, and the rapid charge and discharge are realized; and the separation between inorganic ceramic and organic polymer can be avoided, and the mechanical flexibility of the integrated composite solid electrolyte-electrode and the energy density of the whole battery are further improved. Construction of three-dimensional active substance-conductive carbon black nanofiber conductive frameworks in polymer matrices by optimizing the dispersion of active substance-conductive carbon black in the polymerThe method not only can keep the uniform dispersion of the active substance-conductive carbon black particles to a certain degree, but also can provide more contact surfaces and active sites for the good contact of the electrolyte and the electrode, fully utilizes the 3D frame structure, improves the mass load and the electron/ion transmission performance of the positive active substance, and reduces the interface resistance between the electrode and the electrolyte.
The preparation method is simple, large-scale production can be realized, the obtained composite material constructs a continuous contact interface between the electrode and the electrolyte, the ultralow resistance of the electrode and the electrolyte interface is realized, and the LFP anode nano-fiber is tightly contacted with the PEO-LLZTO composite electrolyte to form a continuous ion transmission interface. The finally obtained composite material has good mechanical flexibility, and the all-solid-state lithium battery based on the electrode-electrolyte integrated composite material also shows high reversible capacity and long-term cycling stability, and can meet the requirements of flexible batteries.
Briefly, the present invention has the following features:
(1) The preparation method is simple, the reaction conditions are easy to control and realize, and the large-scale production can be realized;
(2) Compared with the anode obtained by the traditional coating method, the electrode-electrolyte integrated composite membrane has a 3D interconnected ion transmission network, and can accelerate Li + Migration in a solid state electrolyte; a continuous contact interface between the electrode and the electrolyte is constructed, and the ultralow resistance of the electrode and the electrolyte interface is realized.
(3) The three-dimensional structure and the larger specific surface area of the three-dimensional nanofiber positive electrode framework can promote a polymer-inorganic filler-conductive lithium salt system to permeate into the three-dimensional positive electrode framework to form a continuous and compact electrode-electrolyte contact interface, so that Li is improved + A transmission rate at the interface;
(4) The obtained electrode-electrolyte integrated composite membrane with the three-dimensional structure can be applied to a flexible all-solid-state lithium battery, and has good electrochemical performance, mechanical flexibility and high safety;
(5) This fabrication method can be considered as a method for preparing a novel electrode, an electrode-electrolyte integrated preparation method, which can be commonly used to incorporate active materials into electrodes, making it an advanced technology for exploring general battery materials.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of three-dimensional LFP positive nanofiber prepared in example 1;
FIG. 2 is a photograph of EDX-Mapping of the three-dimensional LFP positive electrode nanofibers prepared in example 1;
fig. 3 is an SEM photograph of a cross-section of the three-dimensional LFP cathode nanofiber membrane prepared in example 2;
FIG. 4 is an EDX-Mapping photograph of a cross-section of the three-dimensional LFP positive electrode nanofiber membrane prepared in example 2;
FIG. 5 is a surface SEM photograph of an LFP positive electrode-LLZTO composite electrolyte integrated composite membrane (In-LFP-LLZTO) prepared In example 3;
FIG. 6 is a SEM photograph showing a cross-section of an LFP positive electrode-LLZTO composite electrolyte integrated composite membrane (In-LFP-LLZTO) obtained In example 3;
FIG. 7 is a photograph of cross-sectional EDS-Mapping of the LFP positive electrode-LLZTO composite electrolyte integrated composite membrane (In-LFP-LLZTO) obtained In example 3;
FIG. 8 is the Electrochemical Impedance Spectroscopy (EIS) curve before and after the ring of the In-LFP-LLZTO/Li full cell assembled by the LFP positive electrode-LLTO composite electrolyte integrated composite membrane prepared In example 4;
FIG. 9 shows the long-term cycle performance of the In-LFP-LLZTO/Li all-solid-state battery assembled by the LFP positive electrode-LLTO composite electrolyte integrated composite membrane prepared In example 5.
Fig. 10 is a schematic view of lighting an LED strip of an In-LFP-LLZTO/Li all-solid-state soft package battery assembled by the LFP positive electrode-LLTO composite electrolyte integrated composite film prepared In example 5.
Detailed Description
The present invention will be further illustrated by the following examples, which are intended to be merely illustrative and not limitative.
Example 1
A novel electrode-electrolyte integrated composite membrane with an integrated structure and a preparation method thereof are disclosed, the method comprises the following steps:
(1) Preparation of oxide-type ceramic nanoparticles:
3.375mmol of Li 2 NO 3 ，1.5mmol La 2 O 3 ，1.75mmol ZrO 2 ，0.125mmol Ta 2 O 5 Precursor salt, placed in a ball mill pot, taking into account lithium volatilization and Li during high temperature reaction 6.75 La 3 Zr 2 T 0.25 O 12 (LLZTO) decomposition with the addition of 15% by weight of Li, based on the total weight of the precursor salts 2 NO 3 . And (3) carrying out mixed ball milling for 12h by taking isopropanol as a ball milling medium, and adopting zirconia grinding balls, wherein the ball milling rotating speed is 300rpm. And drying the mixture subjected to ball milling in an oven at 80 ℃ for 12h. Then, calcining for 12h at 900 ℃, pressing and molding under the pressure of 15MPa, heating to 1100 ℃ at the speed of 1 ℃/min under the air atmosphere, preserving heat and sintering for 6 h, and then ball-milling for 12h to obtain cubic-phase oxide ceramic nanoparticles.
(2) Preparing three-dimensional LFP anode nano-fibers:
0.08g of polyethylene oxide (PEO) and 0.04g of lithium bistrifluoromethanesulfonylimide (LiTFSI) were dissolved in 4.6g of acetonitrile, and stirred at room temperature to obtain a PEO polymer solution; adding 0.24g of lithium iron phosphate (LFP) and 0.04g of superconducting carbon black (Super P) into a PEO polymer solution, and stirring and dispersing uniformly at room temperature to obtain an LFP positive electrode composite solution electrostatic spinning precursor solution; spinning the precursor solution into a nanofiber membrane (collecting nanofiber membrane electrospinning on a carbon-coated aluminum foil) under the spinning conditions that the electrostatic voltage is 13kV, the spinning distance is 10cm, the flow rate of a spinning solution is 0.8mL/h, the total spinning amount is 3mL and the rotating drum speed is 250rpm, then carrying out vacuum drying for 24h at 60 ℃, taking out and placing in a glove box filled with argon for later use, and obtaining the three-dimensional LFP positive electrode nanofiber. A Scanning Electron Microscope (SEM) photograph of the three-dimensional LFP positive electrode nanofibers is shown in fig. 1. An X-ray energy spectrum (EDS-Mapping) of the three-dimensional LFP positive nanofiber is shown in fig. 2 (element distribution maps of C, O, and P elements on the LFP positive composite nanofiber, respectively).
(3) Preparing an electrode-electrolyte integrated composite membrane:
respectively drying 2.45g of PEO, 0.3611g of LLZTO nano-particles and 0.8g of LiTFSI under vacuum at 50 ℃, 100 ℃ and 100 ℃ for 24 hours, then dissolving the three into 50mL of acetonitrile, and fully stirring (the stirring time is 24 hours) to form a uniformly mixed composite solid electrolyte solution;
II, placing the three-dimensional LFP positive electrode nano-fiber membrane obtained in the step (2) on a polytetrafluoroethylene mold, and pouring a layer of the LLZTO composite solid electrolyte solution obtained in the step I on the surface of the polytetrafluoroethylene mold; the unit area dosage of the solid electrolyte mixed solution poured on the surface of the three-dimensional fiber structure positive electrode film (with the thickness of 10 mu m) is 0.2mL/cm -2 ；
III, after the organic solvent acetonitrile is completely volatilized, separating the LFP positive electrode-LLZTO composite electrolyte integrated composite membrane (In-LFP-LLZTO) from the mold, and vacuum drying at 50 ℃ for 24H to remove the residual acetonitrile and the adsorbed H 2 O。
Example 2
A novel electrode-electrolyte integrated composite membrane with an integrated structure and a preparation method thereof are disclosed, the method comprises the following steps:
(1) Preparation of oxide-type ceramic nanoparticles:
3.14mmol of Li 2 NO 3 ，1.5mmol La 2 O 3 ，2mmol ZrO 2 ，0.12mmol Al 2 O 3 Precursor salt, placed in a ball mill pot, taking into account lithium volatilization and Li during high temperature reaction 6.28 Al 0.24 La 3 Zr 2 O 12 (LALZO) decomposition, an additional addition of Li in an amount of 15% by weight of the total precursor salt 2 NO 3 . And (3) carrying out mixed ball milling for 12h by taking isopropanol as a ball milling medium, and adopting zirconia grinding balls, wherein the ball milling rotating speed is 300rpm. And drying the mixture subjected to ball milling in an oven at 80 ℃ for 12h. Then calcining at 900 ℃ for 12h, pressing and forming under the pressure of 15MPa, heating to 1100 ℃ at the speed of 1 ℃/min under the air atmosphere, preserving heat and sintering for 12h, and then ball-milling for 12h to obtain the oxide type LALZO ceramic nanoparticles.
(2) Preparing three-dimensional LFP anode nano-fibers:
dissolving 0.12g of Polytetrafluoroethylene (PVDF) and 0.04g of lithium bistrifluoromethanesulfonimide (LiTFSI) in 4.6g of N, N-dimethylformamide, and stirring at room temperature to obtain a PVDF polymer solution; adding 0.20g of lithium iron phosphate (LFP) and 0.04g of superconducting carbon black (Super P) into a PVDF polymer solution, and stirring and dispersing uniformly at room temperature to obtain an electrostatic spinning precursor solution of an LFP positive electrode composite solution; spinning the precursor solution into a nanofiber membrane (collecting nanofiber membrane electrospinning on a carbon-coated aluminum foil) under the spinning conditions that the electrostatic voltage is 13kV, the spinning distance is 10cm, the flow rate of a spinning solution is 0.8mL/h, the total spinning amount is 15mL and the rotating drum speed is 250rpm, then carrying out vacuum drying for 24h at 60 ℃, taking out and placing in a glove box filled with argon for later use, and obtaining the three-dimensional LFP positive electrode nanofiber. A cross-sectional Scanning Electron Microscope (SEM) photograph of the three-dimensional LFP positive electrode nanofiber is shown in fig. 3. An X-ray energy spectrum (EDS-Mapping) of the cross section of the three-dimensional LFP positive electrode nanofiber is shown in fig. 4 (element distribution maps of C, O, F, P, fe elements respectively corresponding to the inside of the three-dimensional structure of the LFP positive electrode composite nanofiber).
(3) Preparing an electrode-electrolyte integrated composite membrane:
respectively drying 2.45g of PVDF, 0.3611g of LALZO nanoparticles and 0.8g of LiTFSI under vacuum at 50 ℃, 100 ℃ and 100 ℃ for 24h, then dissolving the three into 50mL of acetonitrile, and fully stirring (stirring time is 48 hours) to form a uniformly mixed composite solid electrolyte solution;
II, placing the three-dimensional LFP positive electrode nanofiber membrane obtained in the step (2) on a polytetrafluoroethylene mold, and pouring a layer of LALZO composite solid electrolyte solution obtained in the step I on the surface of the three-dimensional LFP positive electrode nanofiber membrane; the unit area dosage of pouring the solid electrolyte mixed solution on the surface of the three-dimensional fiber structure positive electrode film (with the thickness of 50 mu m) is 1mL/cm -2 ；
III, after the organic solvent acetonitrile is completely volatilized, separating the LFP anode-LALZO composite electrolyte integrated composite membrane (In-LFP-LALZO) from the mould, and carrying out vacuum drying for 24H at 50 ℃ to remove the residual acetonitrile and the adsorbed H 2 O。
Example 3
A novel electrode-electrolyte integrated composite membrane with an integrated structure and a preparation method thereof are disclosed, the method comprises the following steps:
(1) Preparation of oxide type ceramic nanoparticles:
3.375mmol of Li 2 NO 3 ，1.5mmol La 2 O 3 ，1.75mmol ZrO 2 ，0.125mmol Ta 2 O 5 Precursor salt, placed in a ball mill pot, taking into account lithium volatilization and Li during high temperature reaction 6.75 La 3 Zr 2 T 0.25 O 12 (LLZTO) decomposition with the addition of 15% by weight of Li, based on the total weight of the precursor salts 2 NO 3 . And (3) carrying out mixed ball milling for 12 hours by taking isopropanol as a ball milling medium, and adopting zirconia grinding balls, wherein the ball milling rotating speed is 300rpm. And drying the mixture subjected to ball milling in an oven at 80 ℃ for 12h. Then, calcining for 12h at 900 ℃, pressing and molding under the pressure of 15MPa, heating to 1100 ℃ at the speed of 1 ℃/min under the air atmosphere, preserving heat and sintering for 4h, and then ball-milling for 12h to obtain cubic-phase oxide ceramic nanoparticles.
(2) Preparing three-dimensional LFP anode nano-fibers:
dissolving 0.08g of Polytetrafluoroethylene (PVDF), 0.04g of polyethylene oxide (PEO) and 0.04g of lithium bistrifluoromethanesulfonylimide (LiTFSI) in 5g of N, N-dimethylformamide, and stirring at 40 ℃ to obtain a mixed polymer solution; adding 0.20g of lithium iron phosphate (LFP) and 0.04g of superconducting carbon black (Super P) into the mixed polymer solution, and stirring and dispersing uniformly at 40 ℃ to obtain an LFP positive electrode composite solution electrostatic spinning precursor solution; spinning the precursor solution into a nanofiber membrane (collecting nanofiber membrane electrospinning on a carbon-coated aluminum foil) under the spinning conditions that the electrostatic voltage is 13kV, the spinning distance is 10cm, the flow rate of a spinning solution is 0.8mL/h, the total spinning amount is 10mL and the rotating speed of a rotary drum is 250rpm, then carrying out vacuum drying for 24h at 60 ℃, taking out the nanofiber membrane and placing the nanofiber membrane into a glove box filled with argon for later use, thus obtaining the three-dimensional LFP positive electrode nanofiber.
(3) Preparing an electrode-electrolyte integrated composite membrane:
respectively drying 2.45g of PEO, 0.3611g of LLZTO nano-particles and 0.8g of LiTFSI under vacuum at 50 ℃, 100 ℃ and 100 ℃ for 24h, then dissolving the three into 50mL of acetonitrile, and fully stirring (the stirring time is 30 hours) to form a uniformly mixed composite solid electrolyte solution;
II, placing the three-dimensional LFP positive electrode nano-fiber membrane obtained in the step (2) on a polytetrafluoroethylene mold, and pouring a layer of the LLZTO composite solid electrolyte solution obtained in the step I on the surface of the polytetrafluoroethylene mold; the unit area dosage of pouring the solid electrolyte mixed solution on the surface of the three-dimensional fiber structure positive electrode film (with the thickness of 10 mu m) is 1mL/cm -2 ；
III, after the organic solvent acetonitrile is completely volatilized, separating the LFP anode-LLZTO composite electrolyte integrated composite membrane (In-LFP-LLZTO) from the mold, and drying In vacuum for 24H at 50 ℃ to remove residual acetonitrile and adsorbed H 2 And (O). The SEM image of the surface of the In-LFP-LALZO composite membrane is shown In figure 5. The SEM image of the cross section of the In-LFP-LLZTO composite membrane is shown In figure 6. The EDS-Mapping element distribution diagram of the cross section of the obtained In-LFP-LLZTO composite membrane is shown In figure 7 (respectively corresponding to the element distribution diagrams of C, P, zr, ta and O elements In the LFP anode-LALZO composite electrolyte integrated composite membrane structure).
Example 4
A novel electrode-electrolyte integrated composite membrane with an integrated structure and a preparation method thereof are disclosed, the method comprises the following steps:
(1) Preparation of oxide type ceramic nanoparticles:
1mmol of Li 2 NO 3 ，1mmol La 2 O 3 ，4mmol TiO 2 Precursor salt, placed in a ball mill pot, taking into account lithium volatilization and Li during high temperature reaction 3x La (2/3)-x TiO 3 (LLTO) decomposition with the addition of 15% by weight of Li based on the total weight of the precursor salts 2 NO 3 . And (3) carrying out mixed ball milling for 12h by taking isopropanol as a ball milling medium, and adopting zirconia grinding balls, wherein the ball milling rotating speed is 300rpm. And drying the mixture subjected to ball milling in an oven at 80 ℃ for 12h. Then, calcining for 12h at 900 ℃, pressing and molding under the pressure of 15MPa, heating to 1100 ℃ at the speed of 1 ℃/min under the air atmosphere, preserving heat and sintering for 24h, and then ball-milling for 12h to obtain the oxide type LLTO ceramic nano-particles.
(2) Preparing three-dimensional LFP anode nano-fibers:
dissolving 0.12g of Polyacrylonitrile (PAN) and 0.04g of lithium bistrifluoromethanesulfonylimide (LiTFSI) in 5g of N, N-dimethylformamide, and stirring at room temperature to obtain a PAN polymer solution; adding 0.20g of lithium iron phosphate (LFP) and 0.04g of superconducting carbon black (Super P) into the PAN polymer solution, and stirring and dispersing uniformly at room temperature to obtain an LFP positive electrode composite solution electrostatic spinning precursor solution; spinning the precursor solution into a nanofiber membrane (collecting nanofiber membrane electrospinning on a carbon-coated aluminum foil) under the spinning conditions that the electrostatic voltage is 13kV, the spinning distance is 10cm, the flow rate of a spinning solution is 0.8mL/h, the total spinning amount is 12mL and the rotating speed of a rotary drum is 250rpm, then carrying out vacuum drying for 24h at 60 ℃, taking out the nanofiber membrane and placing the nanofiber membrane into a glove box filled with argon for later use, thus obtaining the three-dimensional LFP positive electrode nanofiber.
(3) Preparing an electrode-electrolyte integrated composite membrane:
respectively drying 2.45g of PEO, 0.3611g of LLTO nano-particles and 0.8g of LiTFSI under vacuum at 50 ℃, 100 ℃ and 100 ℃ for 24h, then dissolving the three into 50mL of acetonitrile, and fully stirring (the stirring time is 35 hours) to form a uniformly mixed composite solid electrolyte solution;
II, placing the three-dimensional LFP positive electrode nano-fiber membrane obtained in the step (2) on a polytetrafluoroethylene mold, and pouring a layer of the LLTO composite solid electrolyte solution obtained in the step I on the surface of the three-dimensional LFP positive electrode nano-fiber membrane; the unit area dosage of the solid electrolyte mixed solution poured on the surface of the three-dimensional fiber structure positive electrode film (with the thickness of 50 mu m) is 0.2mL/cm -2 ；
III, after the organic solvent acetonitrile is completely volatilized, separating the LFP positive electrode-LLTO composite electrolyte integrated composite membrane (In-LFP-LLTO) from the mold, and vacuum drying at 50 ℃ for 24H to remove the residual acetonitrile and the adsorbed H 2 O。
The Electrochemical Impedance Spectra (EIS) of the In-LFP-LLTO/Li all-solid-state battery of the LFP positive electrode-LLTO composite electrolyte integrated composite membrane (In-LFP-LLTO) prepared In the embodiment before and after the battery cycle is shown In FIG. 8.
Example 5
A novel electrode-electrolyte integrated composite membrane with an integrated structure and a preparation method thereof are disclosed, the method comprises the following steps:
(1) Preparation of oxide type ceramic nanoparticles:
1mmol of Li 2 NO 3 ，1mmol La 2 O 3 ，4mmol TiO 2 Precursor salt, placed in a ball mill pot, taking into account lithium volatilization and Li during high temperature reaction 3x La (2/3)-x TiO 3 (LLTO) decomposition with the addition of 15% by weight of Li based on the total weight of the precursor salts 2 NO 3 . And (3) carrying out mixed ball milling for 12h by taking isopropanol as a ball milling medium, and adopting zirconia grinding balls, wherein the ball milling rotating speed is 300rpm. And drying the mixture subjected to ball milling in an oven at 80 ℃ for 12h. Then, calcining for 12h at 900 ℃, pressing and molding under the pressure of 15MPa, heating to 1100 ℃ at the speed of 1 ℃/min under the air atmosphere, preserving heat and sintering for 2h, and then ball-milling for 12h to obtain the oxide type LLTO ceramic nano-particles.
(2) Preparing three-dimensional LFP anode nano-fibers:
0.12g of polyethylene oxide (PEO) and 0.04g of lithium bistrifluoromethanesulfonylimide (LiTFSI) were dissolved in 5g of acetonitrile, and stirred at room temperature to obtain a PEO polymer solution; adding 0.24g of lithium iron phosphate (LFP) and 0.02g of superconducting carbon black (Super P) into a PEO polymer solution, and stirring and dispersing uniformly at room temperature to obtain an electrostatic spinning precursor solution of an LFP positive electrode composite solution; spinning the precursor solution into a nanofiber membrane (collecting nanofiber membrane electrospinning on a carbon-coated aluminum foil) under the spinning conditions that the electrostatic voltage is 13kV, the spinning distance is 10cm, the flow rate of a spinning solution is 0.8mL/h, the total spinning amount is 12mL and the rotating speed of a rotary drum is 250rpm, then carrying out vacuum drying for 24h at 60 ℃, taking out the nanofiber membrane and placing the nanofiber membrane into a glove box filled with argon for later use, thus obtaining the three-dimensional LFP positive electrode nanofiber.
(3) Preparing an electrode-electrolyte integrated composite membrane:
respectively drying 2.45g of PMMA, 0.3611g of LLTO nano-particles and 0.8g of LiTFSI under vacuum at 50 ℃, 100 ℃ and 100 ℃ for 24h, then dissolving the PMMA, the LLTO nano-particles and the LiTFSI in 50mL of acetonitrile, and fully stirring (the stirring time is 35 hours) to form a uniformly mixed composite solid electrolyte solution;
II, placing the three-dimensional LFP positive electrode nano-fiber membrane obtained in the step (2) on a polytetrafluoroethylene mold, and pouring a layer of the LLTO composite solid electrolyte solution obtained in the step I on the surface of the three-dimensional LFP positive electrode nano-fiber membrane; in thatThe unit area dosage of the solid electrolyte mixed solution poured on the surface of the three-dimensional fiber structure positive electrode film (with the thickness of 30 mu m) is 0.7mL/cm -2 ；
III, after the organic solvent acetonitrile is completely volatilized, separating the LFP positive electrode-LLTO composite electrolyte integrated composite membrane (In-LFP-LLTO) from the mold, and vacuum drying at 50 ℃ for 24H to remove the residual acetonitrile and the adsorbed H 2 O。
The long-term cycle performance of the In-LFP-LLTO/Li all-solid-state battery with the LFP positive electrode-LLTO composite electrolyte integrated composite membrane (In-LFP-LLTO) prepared In the embodiment is shown In figure 9. The schematic lighting diagram of the LED lamp strip of the In-LFP-LLTO/Li all-solid-state soft package battery assembled by the prepared LFP anode-LLTO composite electrolyte integrated composite membrane is shown In figure 10.
Results of the experiment
A Scanning Electron Microscope (SEM) photograph of the three-dimensional LFP cathode nanofiber prepared in example 1 is shown in fig. 1. Both the LFP positive electrode particles and the Super P are more uniformly dispersed on the nanofibers and the fiber structure remains intact. This avoids the aggregation of LFP positive electrode particles in the positive electrode film, and is Li + Provides a continuous and rapid transmission path, and is beneficial to improving the utilization rate of the active substances of the cathode material. In addition, the pores exist in the three-dimensional LFP positive electrode nanofiber framework, which is beneficial to the complete penetration of the subsequent composite electrolyte solution into the three-dimensional positive electrode network to form a compact electrode/electrolyte interface, so that the conduction rate of ions at the interface can be increased, and the interface resistance of the two can be reduced.
An X-ray energy spectrum (EDS-Mapping) of the three-dimensional LFP cathode nanofiber prepared in example 1 is shown in fig. 2. C. The O and P elements are uniformly distributed on the composite three-dimensional network fiber. So that the LFP anode nano composite fiber is interwoven into a three-dimensional network structure, and has more active sites contacted with the electrolyte. Forming a continuous and rapid ion and electron transport path.
The cross-sectional SEM image of the three-dimensional LFP positive electrode nanofiber composite membrane prepared in example 2 is shown in fig. 3. The surface and the inside of the composite fiber membrane both present a three-dimensional fiber network structure, the LFP positive electrode is interwoven into the three-dimensional network structure, and in the nanofiber framework, the microscale gap channel can provide enough electrolyte storage space, so that the ion and electron transfer process is enhanced.
The cross-sectional X-ray energy spectrum (EDS-Mapping) of the three-dimensional LFP cathode nanofiber prepared in example 2 is shown in fig. 4. C. The elements O and P are uniformly distributed on the surface and the internal fibers of the composite three-dimensional network fiber membrane. Forming homogeneous three-dimensional LFP active sites. Thereby facilitating the formation of continuous and rapid ion and electron transport paths. The unique structure of the LFP positive nanofiber ensures better charge and discharge performance under higher mass loading. The nanofibers prepared by the electrospinning method have a high specific surface area, so that the current density per unit area is uniform, which can enhance the kinetics of the redox reaction and alleviate the polarization of the battery.
The SEM image of the surface of the obtained In-LFP-LLZTO composite membrane prepared In example 3 is shown In FIG. 5. The SEM image of the cross section of the In-LFP-LLZTO composite membrane is shown In FIG. 6. The EDS-Mapping element distribution diagram of the cross section of the obtained In-LFP-LLZTO composite membrane is shown In figure 7. The LFP positive electrode nanofibers and the LLZTO composite electrolyte are intimately fused together. The composite electrolyte solution enters the inside of the nanofiber membrane through gaps among fibers, and the anode and the electrolyte are combined into a whole, so that a continuous lithium ion transmission channel is formed between the electrode and the electrolyte.
Fig. 8 shows Electrochemical Impedance Spectra (EIS) before and after battery cycle of the In-LFP-LLTO/Li all-solid-state battery of the LFP positive electrode-LLTO composite electrolyte integrated composite membrane (In-LFP-LLTO) prepared In example 4. The interface resistance before and after the In-LFP-LLTO/Li battery is far lower than that of LiFePO assembled by the anode obtained by the traditional coating method 4 The interface resistance of the LLTO Li battery shows that the constructed continuous and compact electrode/electrolyte interface enhances the compatibility between the positive electrode and the electrolyte, thereby effectively reducing the interface resistance, and proving that LiFePO 4 The interface adaptability and stability between the anode nano-fiber and the LLTO composite electrolyte.
The long-term cycle performance of the In-LFP-LLTO/Li all-solid-state battery of the LFP cathode-LLTO composite electrolyte integrated composite membrane (In-LFP-LLTO) prepared In example 5 is shown In FIG. 9. All-solid-state battery on-cycleAfter 50 circles of the ring, the ring still has 130.1mAh g -1 The average coulombic efficiency of the battery is higher than 99.76 percent, and the charging and discharging specific capacity in the circulating process is higher than that of LiFePO assembled by the traditional coating method 4 The LLTO Li battery has excellent cycle stability due to the charge-discharge specific capacity. These results indicate that In-LFP-LLTO has a higher capacity retention rate and better electrode structural integrity after long cycling.
Fig. 10 shows a schematic lighting diagram of an LED strip of an In-LFP-LLTO/Li all-solid-state soft-package battery assembled by the LFP positive electrode-LLTO composite electrolyte integrated composite film prepared In example 5. The LED lamp illumination test can intuitively show the working state of the soft package flexible all-solid-state battery under the bending deformation. The result shows that flexible all-solid-state soft package battery can be continuously and stably supplied power for a string of LED lamp strips under different bending conditions. (including tiling, bending and restoring conditions that still illuminate the LED strip).
The above embodiments prepare different types of electrode-electrolyte integrated composite membranes, including integrated composite membranes integrated by three-dimensional LFP positive electrode nanofibers formed by electrospinning garnet-type and perovskite-type ceramic composite electrolytes with different polymers, so that the method of preparing the positive electrode nanofibers by electrospinning the polymers, positive active substances and conductive carbon materials so as to integrate the positive electrode nanofibers with different ceramic composite electrolytes is suitable for preparing various types of electrode-electrolyte integrated composite membranes.
Although the present invention has been described with reference to the specific embodiments, it is not intended to limit the scope of the present invention, and various modifications and variations can be made by those skilled in the art without inventive changes based on the technical solution of the present invention.
Claims (10)
1. A preparation method of an electrode-electrolyte integrated composite material comprises the following specific steps:
s1, dissolving a polymer and a conductive lithium salt in an organic solvent to obtain a polymer solution, adding lithium iron phosphate and superconducting carbon black into the polymer solution, stirring and dispersing uniformly to obtain a precursor solution, and performing electrostatic spinning to obtain a three-dimensional fiber structure positive electrode film;
s2, adding the polymer, the conductive lithium salt and the oxide type ceramic nano particles into a solvent, and uniformly stirring and dispersing to obtain a solid electrolyte mixed solution;
s3, then placing the three-dimensional fiber structure positive electrode film on a mold, pouring a layer of solid electrolyte mixed solution on the surface of the three-dimensional fiber structure positive electrode film, demolding after acetonitrile is completely volatilized, and drying in vacuum to obtain the composite electrolyte;
the oxide type ceramic nanoparticles are obtained by carrying out primary ball milling, drying, calcining, forming, sintering and secondary ball milling on metal ion precursor salt containing oxide type ceramic solid electrolyte, wherein the metal ion precursor salt is selected from any one or more of garnet type, NASICON type, perovskite type or anti-perovskite type ceramic precursor salt.
2. The preparation method according to claim 1, wherein the polymer is selected from any one or more of polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, polyvinylidene fluoride and polyvinyl chloride; the conductive lithium salt is selected from lithium halide, lithium bis (trifluoromethylsulfonyl) imide, lithium perchlorate, lithium hexafluorophosphate or lithium tetrafluoroborate.
3. The production method according to claim 1, wherein the oxide-type ceramic solid electrolyte is selected from Li 6.75 La 3 Zr 2 T 0.25 O 12 、Li 6.28 Al 0.24 La 3 Zr 2 O 12 、Li 6.75 La 3 Zr 2 T 0.25 O 12 、Li 3x La (2/3)-x TiO 3 Any one of (a); the corresponding metal ion precursor salts are respectively as follows:
Li 6.75 La 3 Zr 2 T 0.25 O 12 ：Li 2 NO 3 、La 2 O 3 、ZrO 2 、Ta 2 O 5 the molar ratio of the four is 3.375:1.5:1.75:0.125;
Li 6.28 Al 0.24 La 3 Zr 2 O 12 ：Li 2 NO 3 、La 2 O 3 、ZrO 2 、Al 2 O 3 the molar ratio of the four is 3.14:1.5:2:0.12;
Li 6.75 La 3 Zr 2 T 0.25 O 12 ：Li 2 NO 3 、La 2 O 3 、ZrO 2 、Ta 2 O 5 the molar ratio of the four is 3.375:1.5:1.75:0.125;
Li 3x La (2/3)-x TiO 3 ：1mmol Li 2 NO 3 ，1mmol La 2 O 3 ，4mmol TiO 2 the molar ratio of the three is 1:1:4.
4. the preparation method according to claim 1, wherein, in the preparation of the oxide type ceramic nanoparticles, lithium nitrate is added as a compensating agent in an amount of 15% by weight based on the total weight of the metal ion precursor salt;
the isopropanol is used as a ball milling medium for primary ball milling or secondary ball milling, zirconia grinding balls are adopted, the ball milling speed is 300rpm, and the ball milling time is 12 hours;
the drying process conditions are as follows: drying at 80 ℃ for 12 hours; the calcination process conditions are as follows: calcining at 900 ℃ for 12 hours; the molding process conditions are as follows: pressing the mixture into pellets under 15 MPa; the sintering process conditions are as follows: heating to 1100 ℃ at 1 ℃/min under air atmosphere, and sintering for 1-32 hours under heat preservation.
5. The preparation method according to claim 1, wherein in the step S1, the mass ratio of the polymer, the conductive lithium salt and the organic solvent is 1 to 5:1:100 to 250; the organic solvent is acetonitrile or N, N-dimethylformamide, and the dissolving temperature is 25-50 ℃.
6. The preparation method according to claim 1, wherein in step S1, the mass ratio of the lithium iron phosphate, the superconducting carbon black and the polymer solution is 3 to 9:0.2 to 3:100 to 300 ℃ and the stirring temperature is 25 to 50 ℃.
7. The method according to claim 1, wherein in step S1, the process conditions of the electrospinning are as follows: the electrostatic voltage is 8-15 kV, the spinning distance is 8-15 cm, the flow rate of the spinning solution is 0.5-1.0 mL/h, the total amount of the spinning is 3-15 mL, and the rotating speed of the spinning drum is 200-400 rpm.
8. The preparation method according to claim 1, wherein in step S2, the mass ratio of the polymer, the conductive lithium salt, the oxide-type ceramic nanoparticles, and the solvent is 2 to 4:1:0.1 to 1.5:25 to 70 percent; the stirring time is 24 to 48 hours; the solvent is selected from any one of N, N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, deionized water, acetone or absolute ethyl alcohol.
9. An electrode-electrolyte integrated composite material obtained by the production method according to any one of claims 1 to 8.
10. Use of an electrode-electrolyte integrated composite material according to claim 9 for the preparation of a flexible all solid-state lithium battery.
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| CN116705989A (en) * | 2023-07-31 | 2023-09-05 | 山东硅纳新材料科技有限公司 | Flexible polymer electrolyte silicon integrated electrode and preparation method and application thereof |
| CN117117293A (en) * | 2023-08-14 | 2023-11-24 | 合源锂创(苏州)新能源科技有限公司 | Electrode-electrolyte integrated assembly with three-dimensional structure and preparation process thereof |
| CN117423896A (en) * | 2023-12-19 | 2024-01-19 | 江苏蓝固新能源科技有限公司 | Composite solid electrolyte, preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116705989A (en) * | 2023-07-31 | 2023-09-05 | 山东硅纳新材料科技有限公司 | Flexible polymer electrolyte silicon integrated electrode and preparation method and application thereof |
| CN116705989B (en) * | 2023-07-31 | 2023-10-24 | 山东硅纳新材料科技有限公司 | Flexible polymer electrolyte silicon integrated electrode and preparation method and application thereof |
| CN117117293A (en) * | 2023-08-14 | 2023-11-24 | 合源锂创(苏州)新能源科技有限公司 | Electrode-electrolyte integrated assembly with three-dimensional structure and preparation process thereof |
| CN117423896A (en) * | 2023-12-19 | 2024-01-19 | 江苏蓝固新能源科技有限公司 | Composite solid electrolyte, preparation method and application thereof |
| CN117423896B (en) * | 2023-12-19 | 2024-04-05 | 江苏蓝固新能源科技有限公司 | Composite solid electrolyte, preparation method and application thereof |
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