CN114628783A - Preparation method and application of high-performance polymer composite solid electrolyte - Google Patents
Preparation method and application of high-performance polymer composite solid electrolyte Download PDFInfo
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Abstract
The invention relates to the technical field of solid electrolytes, and discloses a preparation method and application of a high-performance polymer composite solid electrolyte, which comprises the following steps: (1) carrying out three-step high-temperature aerobic sintering on urea to obtain porous g-C3N4Nanosheets; (2) dissolving a polymer solid electrolyte containing vinyl into an organic solvent to form a mixed solution, then sequentially adding a lithium salt, a photoinitiator and a cross-linking agent, stirring, and then adding the porous g-C in the step (1)3N4Stirring the nanosheets and lithium oxalate; and carrying out ultraviolet crosslinking on the obtained slurry in an inert gas atmosphere to obtain the polymer composite solid electrolyte. The invention adopts a simple ultraviolet crosslinking method to prepare the large-size, high-conductivity and high-safety polymer composite solid electrolyte, reduces the crystallinity and the interface resistance, and improves the ionic conductivity and the mechanical property; the lithium ion battery is suitable for batteries with high current density and capacity, and improves stability, safety and cycle life.
Description
Technical Field
The invention relates to the technical field of solid electrolytes, in particular to a preparation method and application of a high-performance polymer composite solid electrolyte.
Background
Polymer solid electrolytes (SPEs) are solid electrolytes that have good electrochemical stability against metallic lithium, a wide electrochemical window, and high mechanical strength. SPEs also have the advantages of high energy density, no leakage, flame retardance, and flexible geometry compared to liquid electrolytes. Therefore, to develop an all solid-state lithium secondary battery with high safety and high energy density, the use of SPEs instead of a liquid electrolyte is a very promising technical approach.
However, the polymer solid electrolyte still has certain technical defects, such as high crystallinity, low ionic conductivity at normal temperature, narrow electrochemical window, etc., and various methods for reducing the crystallinity of the polymer solid electrolyte to improve the ionic conductivity, such as synthesis of a novel polymer solid electrolyte with a low glass transition temperature, structural crosslinking, introduction of an organic plasticizer or an inorganic filler, etc., are currently studied. Structural crosslinking is considered to be the most reliable method for improving the conductivity and mechanical properties of polymer solid electrolytes, and the structural crosslinking by using an ultraviolet crosslinking method is the simplest and lowest-cost method. By adopting the method, a large-size solid electrolyte membrane can be obtained at room temperature, but the obtained solid electrolyte membrane and the interface between electrodes have higher resistance, so that the interface contact needs to be further improved, the battery performance needs to be improved, and the cycle life needs to be prolonged.
Chinese patent publication No. CN111710817A discloses a solid-state battery, and a method for manufacturing the same, and an application thereof, in which a first polymer monomer, a second polymer monomer, a photoinitiator, and a lithium salt are mixed to prepare an electrolyte slurry, and the electrolyte slurry is cured by ultraviolet irradiation on the surface of a heat-treated composite positive electrode, so that a solid electrolyte membrane is formed on the surface of the heat-treated composite positive electrode. The polymer solid electrolyte prepared by the method has the defects of single material matrix, low conductivity, incapability of meeting charge and discharge under high current density, limited application in high-capacity all-solid batteries, certain flammability and low safety of the solid batteries in practical application.
Disclosure of Invention
The invention aims to provide a preparation method and application of a high-performance polymer composite solid electrolyte, wherein the large-size, high-conductivity and high-safety polymer composite solid electrolyte is prepared by adopting a simple ultraviolet crosslinking method, the defect of high interface resistance is overcome, and the cycle life of a battery is prolonged.
The purpose of the invention is realized by the following technical scheme.
In a first aspect, the present invention provides a method for preparing a high-performance polymer composite solid electrolyte, comprising the steps of:
(1) carrying out three-step high-temperature aerobic sintering on urea, wherein the temperature of the first sintering is 550-; after cooling to room temperature, the temperature of the second sintering is 600-650 ℃, and the speed is 3-6 ℃/min; cooling to room temperature again, wherein the temperature of the third sintering is 600-650 ℃, and the speed is 3-6 ℃/min; cooling, taking out and ball milling to obtain porous g-C3N4Nanosheets; (2) dissolving a polymer solid electrolyte containing vinyl into an organic solvent to form a mixed solution, then sequentially adding a lithium salt, a photoinitiator and a cross-linking agent, stirring, and then adding the porous g-C in the step (1)3N4Stirring the nanosheets and lithium oxalate; and carrying out ultraviolet crosslinking on the obtained slurry in an inert gas atmosphere to obtain the polymer composite solid electrolyte.
g-C3N4The graphite carbon nitride is added to reduce the crystallinity of the polymer solid electrolyte, a lithium ion transmission network is formed in a polymer matrix, the ionic conductivity is effectively improved, and g-C is added3N4The surface has rich nitrogen atoms, and the nitrogen atoms can interact with lithium salt to increase the dissociation degree of the lithium salt. The nano-sheet can form a porous structure by adopting a three-step high-temperature aerobic sintering method, has a high specific surface area and a larger interaction area with a polymer, and polymer chains are not easy to slip relatively under the action of external force, so that the mechanical strength of the polymer solid electrolyte is improved. The surface defects generated by sintering can be used as potential channels for vertical transmission of lithium ions, and the transmission capability of the lithium ions is further improved.
In the three-step high-temperature aerobic sintering method, the first sintering is to convert urea into graphite carbon nitride, the temperature rising speed is slow, the urea can be converted more thoroughly, and g-C is obtained after cooling to room temperature3N4And (3) powder. Second sintering to achieve g-C3N4Is porousThe dissolving and heating speed is faster, so that the obtained g-C3N4Small grains of the particle section are gradually hollowed, and hollow structures formed in the sintering process are connected together along the radial direction of larger grains to form a partial porous structure. The partially hollowed structure is shrunk or collapsed after being cooled to room temperature again, and the third sintering process is carried out again to carry out the unoriented hollowing, so that the internal structure of the particle is more porous. g-C can be prepared by adopting a three-step high-temperature sintering method3N4The method has the advantages that a more uniform and abundant porous structure is formed, the specific surface area is improved, certain surface defects are formed, the dissociation degree and the lithium ion transmission capability of lithium salt can be increased, and the formation of a CEI film is accelerated.
The lithium oxalate can form a flexible, stable and rapid lithium ion Conductive (CEI) film on the surface of the positive active particles, so that the thermal stability and the high-voltage performance are improved, the generation of non-conductive side reaction products and cracks of the high-voltage layered ternary positive particles in the circulating process can be effectively inhibited, the interface resistance between the polymer solid electrolyte and the positive plate is reduced, and the cycle life of the battery is prolonged.
The structure of the polymer solid electrolyte is crosslinked by using an ultraviolet crosslinking method, and under the irradiation of ultraviolet light, the photoinitiator generates an alkyl oxygen free radical which is added with double bonds in the polymer solid electrolyte to generate crosslinking, so that a high molecular chain is extended. In order to prevent the main chain of the polymer solid electrolyte from being broken in the cross-linking process and improve the cross-linking efficiency, the cross-linking agent is added to quickly generate free radical reaction with the polymer solid electrolyte, and the occurrence probability of main chain breaking reaction is greatly reduced. Finally, the crystallinity of the polymer solid electrolyte is reduced, and the ionic conductivity and the mechanical property are improved.
Preferably, in the step (1), the time for the first sintering is 2-4 h; the time of the second sintering is 1-2 h; the time for the third sintering is 1-2 h; the ball milling time is 10-30 min.
Preferably, in the step (2), the lithium oxalate salt is lithium bis (oxalato) borate, lithium difluoro (oxalato) phosphate or lithium tetrafluoro (oxalato) phosphate.
Preferably, in the step (2), the polymer solid electrolyte is polyethylene glycol diacrylate; the molar ratio of vinyl groups to lithium ions of the polyethylene glycol diacrylate is 10-25: 1; the lithium oxalate salt is lithium bis (oxalate) borate. The molar ratio of the vinyl group of the polyethylene glycol diacrylate to the lithium ion is controlled, if the content of the lithium salt is too low, the conductivity of the polymer solid electrolyte is too low, and if the content of the lithium salt is too high, the solubility is poor, and the material cost is high.
The lithium bis (oxalato) borate contains boron, so that the surface stability of the layered ternary active material of the positive electrode can be improved in the charging and discharging processes, the thickness of a CEI (CeI) film on the surface of the positive electrode is reduced, the increase of the internal resistance of the solid battery is reduced, the polarization loss in the circulating process is reduced, and the circulating life is prolonged.
Preferably, the lithium salt in step (2) is LiTFSI; the organic solvent is acetonitrile; the photoinitiator is 2, 2-dimethoxy-2-acetophenone; the cross-linking agent is pentaerythritol tetra-3-mercaptopropionate.
Preferably, in the step (2), the mass fraction of the polyethylene glycol diacrylate in the mixed solution is 30-60%; the molar ratio of mercaptan in pentaerythritol tetra-3-mercaptopropionate to vinyl in polyethylene glycol diacrylate is 0.5-1.0: 1.0-2.0; the mass ratio of the 2, 2-dimethoxy-2-acetophenone to the pentaerythritol tetra-3-mercaptopropionate is 1-3: 50-60 parts of; porous g-C in the step (1)3N4The molar ratio of the nanosheets, the lithium bis (oxalato) borate to the LiTFSI is 0.1-0.3: 0.2-0.5: 1.0-1.3; the inert gas is nitrogen.
Preferably, in the step (2), the ultraviolet light crosslinking is carried out at a wavelength of 365nm and an intensity of 5-9mW/cm2The ultraviolet lamp is exposed for 5-8 times, each exposure time is 5-10s, and each exposure interval is 10 min.
Ultraviolet light under the wavelength is long-wave ultraviolet light which basically has no harm to human bodies, and short-wave ultraviolet light and medium-wave ultraviolet light can penetrate through and enter skin tissues of human bodies, so that potential safety hazards exist; the skin and eyes of a human body can be damaged due to too high illumination intensity, the reaction time is too long due to too low intensity, and the preparation efficiency is reduced; the exposure time is too short, the photoinitiator and the like are not fully activated, the crosslinking reaction is not complete, the exposure time is too long, the aging of reactants and the breakage of molecular chains can be caused, and the crosslinking efficiency is reduced; the PEGDA and PETMP crosslinking reaction is not complete due to too short interval time, and the preparation time is prolonged and the cost is increased due to too long interval time.
Preferably, in the step (2), the thickness of the polymer composite solid electrolyte is 50 to 500 μm. In the thickness range, on the premise of not significantly influencing the energy density of the solid battery, higher conductivity is kept, and the performance of the solid battery is favorably exerted.
In a second aspect, the invention also provides a battery comprising the polymer composite solid electrolyte, wherein the battery is an all-solid battery prepared by respectively pressing positive and negative pole pieces on two sides of the polymer composite solid electrolyte.
The battery obtained by using the polymer composite solid electrolyte can reduce the interface resistance between the solid electrolyte layer and the anode, form a flexible, stable and rapid CEI film, and improve the stability and safety. And the polymer composite solid electrolyte has high ionic conductivity and mechanical property, and can prolong the cycle life of the battery.
Preferably, the capacity of the battery is not less than 5 Ah. The polymer composite solid electrolyte has the characteristics of large size, high ionic conductivity and the like, and is suitable for batteries with high current density and capacity.
Compared with the prior art, the invention has the following beneficial effects:
(1) porous g-C prepared by three-step high-temperature aerobic sintering method3N4The nano sheet can improve the specific surface area, reduce the crystallinity of the polymer solid electrolyte, effectively improve the ion conductivity, increase the dissociation degree and the lithium ion transmission capability of lithium salt and contribute to accelerating the formation of a CEI film;
(2) the lithium oxalate can form a flexible, stable and rapid CEI film on the surface of the positive active particles, so that the thermal stability and high-voltage performance are improved, and the interface resistance between the polymer solid electrolyte and the positive plate is reduced;
(3) the large-size, high-conductivity and high-safety polymer composite solid electrolyte is prepared by adopting a simple ultraviolet crosslinking method, the crystallinity of the polymer solid electrolyte is reduced, and the ionic conductivity and the mechanical property are improved;
(4) the battery obtained by using the polymer composite solid electrolyte can reduce the interface resistance between the solid electrolyte layer and the anode, improve the stability and the safety, is suitable for batteries with high current density and capacity, and prolongs the cycle life of the battery.
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
general examples
1. Preparation of polymer composite solid electrolyte
(1) Carrying out three-step high-temperature aerobic sintering on urea, wherein the first sintering is carried out at the temperature of 550-600 ℃ for 2-4h at the speed of 1-3 ℃/min; after cooling to room temperature, the second sintering is sintering at 600-650 ℃ for 1-2h at the speed of 3-6 ℃/min; cooling to room temperature again, and sintering for the third time at 600-650 deg.C for 1-2h at 3-6 deg.C/min; cooling, taking out and ball milling for 10-30min to obtain porous g-C3N4Nanosheets;
(2) dissolving polyethylene glycol diacrylate (PEGDA) in acetonitrile to form a mixed solution, wherein the mass fraction of the PEGDA is 30-60%; then adding LiTFSI, 2-dimethoxy-2-acetophenone (DMPA) and pentaerythritol tetra-3-mercaptopropionate (PETMP) in sequence, and stirring, wherein the molar ratio of vinyl to lithium ions of PEGDA is 10-25: 1, the mass ratio of DMPA to PETMP is 1-3: 50-60, the mol ratio of mercaptan in PETMP and vinyl of PEGDA is 0.5-1.0: 1.0-2.0; then adding the porous g-C in the step (1)3N4Stirring nanosheet and lithium bis (oxalato) borate (LiBOB), and preparing porous g-C3N4The molar ratio of the nanosheets, the lithium bis (oxalato) borate to the LiTFSI is 0.1-0.3: 0.2-0.5: 1.0-1.3; performing ultraviolet crosslinking on the obtained slurry in nitrogen atmosphere at a wavelength of 365nm and an intensity of 5-9mW/cm2Exposing the substrate for 5-8 times by using an ultraviolet lamp, wherein each exposure time is 5-10s, and each exposure interval is 10min, so as to obtain the polymer composite solid electrolyte with the thickness of 50-500 mu m.
The acetonitrile can be replaced by absolute ethyl alcohol, isopropanol, acetone, N-dimethylformamide or N-methylpyrrolidone; the lithium bis (oxalato) borate may be replaced by lithium difluorooxalato phosphate, lithium difluorobis (oxalato) phosphate or lithium tetrafluorooxalato phosphate.
2. Preparation of all-solid-state battery
Positive plate: adding the layered ternary active material, the carbon nano fiber, the PVDF and the LLZO inorganic solid electrolyte particles into a high-energy vibration ball mill according to the mass ratio of 65:3:5:3, ball-milling for 30 minutes at normal temperature, transferring the mixed powder into a mold, and pressing into a positive plate under 300 standard atmospheric pressures, wherein the thickness of the positive plate is 200 microns.
And (3) negative plate: the lithium indium alloy (lithium atom percentage is 60%) is adopted, and the thickness of the negative plate is 150 mu m.
And respectively pressing the positive and negative pole pieces on two sides of the polymer composite solid electrolyte under 200 standard atmospheric pressures to prepare the all-solid battery, wherein the battery is of a large-size square structure, the length of the battery is 80mm, the width of the battery is 60mm, and the capacity of the battery is more than or equal to 5 Ah.
Example 1
1. Preparation of polymer composite solid electrolyte
(1) Carrying out three-step high-temperature aerobic sintering on urea, wherein the first sintering is carried out at 600 ℃ for 4h at the speed of 2 ℃/min; after cooling to room temperature, the second sintering is sintering at 650 ℃ for 2h at a speed of 5 ℃/min; cooling to room temperature again, and sintering at 650 deg.C for 2 hr at 5 deg.C/min for the third time; cooling, taking out and ball milling for 30min to obtain porous g-C3N4Nanosheets;
(2) dissolving polyethylene glycol diacrylate (PEGDA) in acetonitrile to form a mixed solution, wherein the mass fraction of the PEGDA is 30%; then adding LiTFSI, 2-dimethoxy-2-acetophenone (DMPA) and pentaerythritol tetra-3-mercaptopropionate (PETMP) in sequence, and stirring, wherein the molar ratio of vinyl to lithium ions of PEGDA is 15: 1, the mass ratio of DMPA to PETMP is 2: 50, the molar ratio of thiol in PETMP to vinyl in PEGDA is 1.0: 1.0; then adding the porous g-C in the step (1)3N4Stirring the nanosheet and lithium bis (oxalato) borate (LiBOB) for 2h, wherein the g-C is porous3N4The molar ratio of the nanosheets, lithium bis (oxalato) borate to LiTFSI is 0.1: 0.2: 1.1; transferring the obtained slurry into a polytetrafluoroethylene plate, performing ultraviolet crosslinking in nitrogen atmosphere, and performing ultraviolet crosslinking at 365nm and 5mW/cm intensity2The ultraviolet lamp was exposed 5 times, each exposure time was 5 seconds, and each exposure interval was 10min, to obtain a polymer composite solid electrolyte having a thickness of 150 μm.
2. Preparing a positive plate of the all-solid battery: adding the layered ternary active material, the carbon nano fiber, the PVDF and the LLZO inorganic solid electrolyte particles into a high-energy vibration ball mill according to the mass ratio of 65:3:5:3, ball-milling for 30 minutes at normal temperature, transferring the mixed powder into a mold, and pressing into a positive plate under 300 standard atmospheric pressures, wherein the thickness of the positive plate is 200 microns.
And (3) negative plate: the lithium indium alloy (lithium atom percentage is 60%) is adopted, and the thickness of the negative plate is 150 mu m.
And respectively pressing the positive and negative pole pieces on two sides of the polymer composite solid electrolyte under 200 standard atmospheric pressures to prepare the all-solid battery, wherein the battery is of a large-size square structure, the length of the battery is 80mm, and the width of the battery is 60 mm.
Example 2
1. Preparation of polymer composite solid electrolyte
(1) Carrying out three-step high-temperature aerobic sintering on urea, wherein the first sintering is carried out at 550 ℃ for 2h at the speed of 3 ℃/min; after cooling to room temperature, the second sintering is sintering at 600 ℃ for 2h at the speed of 5 ℃/min; cooling to room temperature again, and sintering at 650 deg.C for 2 hr at 6 deg.C/min for the third time; cooling, taking out and ball milling for 30min to obtain porous g-C3N4Nanosheets;
(2) dissolving polyethylene glycol diacrylate (PEGDA) in acetonitrile to form a mixed solution, wherein the mass fraction of the PEGDA is 30%; then adding LiTFSI, 2-dimethoxy-2-acetophenone (DMPA) and pentaerythritol tetra-3-mercaptopropionate (PETMP) in sequence, and stirring, wherein the molar ratio of vinyl to lithium ions of PEGDA is 20: 1, the mass ratio of DMPA to PETMP is 2: 50, the molar ratio of thiol in PETMP to vinyl in PEGDA is 1.0: 1.0; then adding the porous powder into the step (1)g-C3N4Stirring the nanosheet and lithium bis (oxalato) borate (LiBOB) for 2h, wherein the g-C is porous3N4The molar ratio of the nanosheets, lithium bis (oxalato) borate to LiTFSI is 0.1: 0.2: 1.1; transferring the obtained slurry into a polytetrafluoroethylene plate, performing ultraviolet crosslinking in nitrogen atmosphere, and performing ultraviolet crosslinking at 365nm wavelength and 5mW/cm intensity2The ultraviolet lamp was exposed 5 times, each exposure time was 5 seconds, and each exposure interval was 10min, to obtain a polymer composite solid electrolyte having a thickness of 150 μm.
2. Preparing a positive plate of the all-solid battery: adding the layered ternary active material, the carbon nano fiber, the PVDF and the LLZO inorganic solid electrolyte particles into a high-energy vibration ball mill according to the mass ratio of 65:3:5:3, ball-milling for 30 minutes at normal temperature, transferring the mixed powder into a mold, and pressing into a positive plate under 300 standard atmospheric pressures, wherein the thickness of the positive plate is 200 microns.
And (3) negative plate: the lithium indium alloy (lithium atom percentage is 60%) is adopted, and the thickness of the negative plate is 150 mu m.
And respectively pressing the positive and negative pole pieces on two sides of the polymer composite solid electrolyte under 200 standard atmospheric pressures to prepare the all-solid battery, wherein the battery is of a large-size square structure, the length of the battery is 80mm, and the width of the battery is 60 mm.
Example 3
1. Preparation of polymer composite solid electrolyte
(1) Carrying out three-step high-temperature aerobic sintering on urea, wherein the first sintering is carried out at 600 ℃ for 4h at the speed of 2 ℃/min; after cooling to room temperature, the second sintering is sintering at 650 ℃ for 2h at a speed of 5 ℃/min; cooling to room temperature again, and sintering at 650 deg.C for 2 hr at 5 deg.C/min for the third time; cooling, taking out and ball milling for 30min to obtain porous g-C3N4A nanosheet;
(2) dissolving polyethylene glycol diacrylate (PEGDA) in acetonitrile to form a mixed solution, wherein the mass fraction of the PEGDA is 30%; then adding LiTFSI, 2-dimethoxy-2-acetophenone (DMPA) and pentaerythritol tetra-3-mercaptopropionate (PETMP) in sequence, and stirring, wherein the molar ratio of vinyl to lithium ions of PEGDA is 15: 1, the mass ratio of DMPA to PETMP is 1.5: 55, PThe molar ratio of thiol to vinyl groups of PEGDA in ETMP is 1.0: 1.0; then adding the porous g-C in the step (1)3N4Stirring the nanosheet and lithium bis (oxalato) borate (LiBOB) for 2h, wherein the g-C is porous3N4The molar ratio of the nanosheets, lithium bis (oxalato) borate to LiTFSI is 0.1: 0.3: 1.0; transferring the obtained slurry into a polytetrafluoroethylene plate, performing ultraviolet crosslinking in nitrogen atmosphere, and performing ultraviolet crosslinking at 365nm and 5mW/cm intensity2The ultraviolet lamp was exposed 5 times, each exposure time was 5 seconds, and each exposure interval was 10min, to obtain a polymer composite solid electrolyte having a thickness of 150 μm.
2. Preparing a positive plate of the all-solid battery: adding the layered ternary active material, the carbon nano fiber, the PVDF and the LLZO inorganic solid electrolyte particles into a high-energy vibration ball mill according to the mass ratio of 65:3:5:3, ball-milling for 30 minutes at normal temperature, transferring the mixed powder into a mold, and pressing into a positive plate under 300 standard atmospheric pressures, wherein the thickness of the positive plate is 200 microns.
And (3) negative plate: the lithium indium alloy (lithium atom percentage is 60%) is adopted, and the thickness of the negative plate is 150 mu m.
And respectively pressing the positive and negative pole pieces on two sides of the polymer composite solid electrolyte under 200 standard atmospheric pressures to prepare the all-solid battery, wherein the battery is of a large-size square structure, the length of the battery is 80mm, and the width of the battery is 60 mm.
Example 4
1. Preparation of polymer composite solid electrolyte
(1) Carrying out three-step high-temperature aerobic sintering on urea, wherein the first sintering is sintering at 600 ℃ for 2h at the speed of 5 ℃/min; after cooling to room temperature, the second sintering is sintering at 650 ℃ for 2h at a speed of 5 ℃/min; cooling to room temperature again, and sintering at 650 deg.C for 1 hr at 6 deg.C/min for the third time; cooling, taking out and ball milling for 20min to obtain porous g-C3N4Nanosheets;
(2) dissolving polyethylene glycol diacrylate (PEGDA) in acetonitrile to form a mixed solution, wherein the mass fraction of the PEGDA is 30%; then sequentially adding LiTFSI, 2-dimethoxy-2-acetophenone (DMPA) and pentaerythritol tetra-3-mercaptopropionate (PETMP) and stirring, wherein,the molar ratio of vinyl groups to lithium ions of PEGDA was 20: 1, the mass ratio of DMPA to PETMP is 2: 50, the molar ratio of thiol in PETMP to vinyl in PEGDA is 1.0: 1.0; then adding the porous g-C in the step (1)3N4Stirring the nanosheet and lithium bis (oxalato) borate (LiBOB) for 2h, wherein the g-C is porous3N4The molar ratio of the nanosheets, lithium bis (oxalato) borate to LiTFSI is 0.2: 0.5: 1.1; transferring the obtained slurry into a polytetrafluoroethylene plate, performing ultraviolet crosslinking in nitrogen atmosphere, and performing ultraviolet crosslinking at 365nm and 5mW/cm intensity2The polymer composite solid electrolyte with the thickness of 250 μm is obtained by exposing the polymer composite solid electrolyte on an ultraviolet lamp for 5 times, wherein each exposure time is 5s, and each exposure interval is 10 min.
2. Preparing a positive plate of the all-solid battery: adding the layered ternary active material, the carbon nano fiber, the PVDF and the LLZO inorganic solid electrolyte particles into a high-energy vibration ball mill according to the mass ratio of 65:3:5:3, ball-milling for 30 minutes at normal temperature, transferring the mixed powder into a mold, and pressing into a positive plate under 300 standard atmospheric pressures, wherein the thickness of the positive plate is 200 microns.
And (3) negative plate: the lithium indium alloy (lithium atom percentage is 60%) is adopted, and the thickness of the negative plate is 150 mu m.
And respectively pressing the positive and negative pole pieces on two sides of the polymer composite solid electrolyte under 200 standard atmospheric pressures to prepare the all-solid battery, wherein the battery is of a large-size square structure, the length of the battery is 80mm, and the width of the battery is 60 mm.
Example 5
1. Preparation of polymer composite solid electrolyte
(1) Carrying out three-step high-temperature aerobic sintering on urea, wherein the first sintering is carried out at 600 ℃ for 4h at the speed of 3 ℃/min; after cooling to room temperature, the second sintering is sintering at 650 ℃ for 2h at the speed of 5 ℃/min; cooling to room temperature again, and sintering at 650 deg.C for 2 hr at 5 deg.C/min for the third time; cooling, taking out and ball milling for 20min to obtain porous g-C3N4Nanosheets;
(2) dissolving polyethylene glycol diacrylate (PEGDA) in acetonitrile to form a mixed solution, wherein the mass fraction of the PEGDA is 40%; then sequentially adding LiTFSI and 2, 2-bisMethoxy-2-acetophenone (DMPA) and pentaerythritol tetra-3-mercaptopropionate (PETMP) are stirred, wherein the molar ratio of vinyl to lithium ions of PEGDA is 15: 1, the mass ratio of DMPA to PETMP is 2: 50, the molar ratio of thiol in PETMP to vinyl in PEGDA is 0.8: 1.2; then adding the porous g-C in the step (1)3N4Stirring the nanosheet and lithium bis (oxalato) borate (LiBOB) for 2h, wherein the g-C is porous3N4The molar ratio of the nanosheets, lithium bis (oxalato) borate to LiTFSI is 0.5: 0.2: 1.3; transferring the obtained slurry into a polytetrafluoroethylene plate, performing ultraviolet crosslinking in nitrogen atmosphere, and performing ultraviolet crosslinking at 365nm wavelength and 8mW/cm intensity2The ultraviolet lamp was exposed 8 times, each exposure time was 10s, and each exposure interval was 10min, to obtain a polymer composite solid electrolyte having a thickness of 50 μm.
2. Preparing a positive plate of the all-solid battery: the layered ternary active material, the carbon nanofiber, the PVDF and the LLZO inorganic solid electrolyte particles are put into a high-energy vibration ball mill according to the mass ratio of 65:3:5:3, ball-milled for 30 minutes at normal temperature, the mixed powder is transferred into a mold, and is pressed into a positive plate under 300 standard atmospheric pressures, wherein the thickness of the positive plate is 200 microns.
And (3) negative plate: the lithium indium alloy (lithium atom percentage is 60%) is adopted, and the thickness of the negative plate is 150 mu m.
And respectively pressing the positive and negative pole pieces on two sides of the polymer composite solid electrolyte under 200 standard atmospheric pressures to prepare the all-solid battery, wherein the battery is of a large-size square structure, the length of the battery is 80mm, and the width of the battery is 60 mm.
Example 6
1. Preparation of polymer composite solid electrolyte
(1) Carrying out three-step high-temperature aerobic sintering on urea, wherein the first sintering is carried out at 600 ℃ for 4h at the speed of 2 ℃/min; after cooling to room temperature, the second sintering is sintering at 650 ℃ for 2h at a speed of 5 ℃/min; cooling to room temperature again, and sintering at 600 deg.C for 1 hr at 4 deg.C/min for the third time; cooling, taking out and ball milling for 30min to obtain porous g-C3N4Nanosheets;
(2) dissolving polyethylene glycol diacrylate (PEGDA) in acetonitrileForming a mixed solution, wherein the mass fraction of the PEGDA is 30%; then adding LiTFSI, 2-dimethoxy-2-acetophenone (DMPA) and pentaerythritol tetra-3-mercaptopropionate (PETMP) in sequence, and stirring, wherein the molar ratio of vinyl to lithium ions of PEGDA is 15: 1, the mass ratio of DMPA to PETMP is 3: 55, the molar ratio of thiol in PETMP to vinyl in PEGDA is 0.5: 2.0; then adding the porous g-C in the step (1)3N4Stirring the nanosheet and lithium bis (oxalato) borate (LiBOB) for 2h, wherein the g-C is porous3N4The molar ratio of the nanosheets, lithium bis (oxalato) borate to LiTFSI is 0.1: 0.2: 1.1; transferring the obtained slurry into a polytetrafluoroethylene plate, performing ultraviolet crosslinking in nitrogen atmosphere, and performing ultraviolet crosslinking at 365nm and 5mW/cm intensity2The ultraviolet lamp was exposed 6 times, each exposure time was 6 seconds, and each exposure interval was 10min, to obtain a polymer composite solid electrolyte having a thickness of 500 μm.
2. Preparing a positive plate of the all-solid battery: the layered ternary active material, the carbon nanofiber, the PVDF and the LLZO inorganic solid electrolyte particles are put into a high-energy vibration ball mill according to the mass ratio of 65:3:5:3, ball-milled for 30 minutes at normal temperature, the mixed powder is transferred into a mold, and is pressed into a positive plate under 300 standard atmospheric pressures, wherein the thickness of the positive plate is 200 microns.
And (3) negative plate: the lithium indium alloy (lithium atom percentage is 60%) is adopted, and the thickness of the negative plate is 150 mu m.
And respectively pressing the positive and negative pole pieces on two sides of the polymer composite solid electrolyte under 200 standard atmospheric pressures to prepare the all-solid battery, wherein the battery is of a large-size square structure, the length of the battery is 80mm, and the width of the battery is 60 mm.
Comparative example 1
The difference from example 1 is that:
in the preparation of the polymer composite solid electrolyte, the step (1) is changed into:
sintering urea at 600 ℃ for 4h at the speed of 2 ℃/min; cooling to room temperature and ball milling for 30min to obtain g-C3N4Nanosheets.
Comparative example 2
The difference from example 1 is that:
the preparation of the polymer composite solid electrolyte is not added with porous g-C3N4Nanosheet, removal step (1).
Comparative example 3
The difference from example 1 is that:
in the preparation of the polymer composite solid electrolyte, the step (1) is changed into two-step high-temperature aerobic sintering, and the specific steps are as follows: sintering urea for the first time at 600 ℃ for 4h at the speed of 2 ℃/min; after cooling to room temperature, the second sintering is sintering at 650 ℃ for 4h at a speed of 5 ℃/min; cooling, taking out and ball milling for 30min to obtain porous g-C3N4Nanosheets.
Comparative example 4
The difference from example 1 is that:
lithium bis (oxalato) borate (LiBOB) was not added in the preparation of the polymer composite solid electrolyte.
Comparative example 5
The difference from example 1 is that:
pentaerythritol tetra-3-mercaptopropionate (PETMP) was not added in the preparation of the polymer composite solid electrolyte.
Comparative example 6
The difference from example 1 is that:
polyethylene glycol diacrylate (PEGDA) is not added in the preparation of the polymer composite solid electrolyte, namely the step (2) is changed into the following steps: sequentially adding LiTFSI, 2-dimethoxy-2-acetophenone (DMPA) and pentaerythritol tetra-3-mercaptopropionate (PETMP) into an acetonitrile solution, and stirring, wherein the mass ratio of DMPA to PETMP is 2: 50, the molar ratio of mercaptan to lithium ion in PETMP is 1.0: 0.07; then adding the porous g-C in the step (1)3N4Stirring the nanosheet and lithium bis (oxalato) borate (LiBOB) for 2h, wherein the g-C is porous3N4The molar ratio of the nanosheets, lithium bis (oxalato) borate to LiTFSI is 0.1: 0.2: 1.1; transferring the obtained slurry into a polytetrafluoroethylene plate, performing ultraviolet crosslinking in nitrogen atmosphere, and performing ultraviolet crosslinking at 365nm and 5mW/cm intensity2The ultraviolet lamp was exposed 5 times, each exposure time was 5 seconds, and each exposure interval was 10min, to obtain a polymer composite solid electrolyte having a thickness of 150 μm.
TABLE 1 evaluation results of the Performance of solid State batteries of different groups
| Group of | Tensile Strength (MPa) | Ionic conductivity (. about.10)-4S/cm) | Cycle life (week) |
| Example 1 | 3.45 | 0.42 | 433 |
| Example 2 | 3.32 | 0.39 | 430 |
| Example 3 | 3.38 | 0.32 | 421 |
| Example 4 | 3.42 | 0.38 | 423 |
| Example 5 | 3.3 | 0.34 | 428 |
| Example 6 | 3.36 | 0.39 | 430 |
| Comparative example 1 | 3.21 | 0.34 | 407 |
| Comparative example 2 | 2.76 | 0.24 | 352 |
| Comparative example 3 | 2.91 | 0.30 | 385 |
| Comparative example 4 | 3.29 | 0.37 | 312 |
| Comparative example 5 | 2.01 | 0.29 | 334 |
| Comparative example 6 | 1.95 | 0.24 | 320 |
The specific results are shown in table 1, and it can be seen by combining examples 1 to 6 and comparative examples 1 to 6 that within the technical range required by the present invention, the polymer composite solid electrolyte has good mechanical properties and electrical conductivity, and is suitable for large-current density and large-size solid batteries, and the cycle life of all-solid batteries is good. Combining example 1 and comparative examples 1-2, porous g-C was added to the polymer solid electrolyte3N4The two-dimensional nanosheet can remarkably improve the mechanical property and lithium ion transmission conductivity of the polymer composite solid electrolyte, and the improvement effect is more obvious after porous treatment. By combining the embodiment 1 and the comparative example 3, the effect of using the two-step high-temperature aerobic sintering method is poor, mainly because the two-step method does not have the processes of re-sintering and cooling, a compact porous structure cannot be formed in the internal structure of the nanosheet, the specific surface area is reduced, and the mechanical property and the electric conductivity of the polymer composite solid electrolyte are further reduced.
By combining example 1 and comparative example 3, the stability of the interface between the polymer solid electrolyte and the positive electrode can be improved by adding lithium bis (oxalato) borate (LiBOB), thereby prolonging the cycle life of the solid battery. With the combination of example 1 and comparative examples 4-5, no pentaerythritol tetra-3-mercaptopropionate (PETMP) or polyethylene glycol diacrylate (PEGDA) was added, and an effective crosslinked structure could not be formed, and only after the crosslinking treatment of the two combined structures, the mechanical properties and conductivity of the polymer solid electrolyte were improved, mainly because the crosslinking could reduce the crystallinity of the polymer electrolyte, provide more lithium ion transport channels, increase the mechanical strength of the polymer solid electrolyte, and greatly prolong the cycle life of the all-solid battery. The results show that the method provided by the invention can effectively improve the comprehensive performance of the polymer solid electrolyte and the cycle life of the solid battery.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The preparation method of the high-performance polymer composite solid electrolyte is characterized by comprising the following steps of:
(1) carrying out three-step high-temperature aerobic sintering on urea, wherein the temperature of the first sintering is 550-600 ℃, and the speed is 1-3 ℃/min; after cooling to room temperature, the temperature of the second sintering is 600-650 ℃, and the speed is 3-6 ℃/min; cooling to room temperature again, wherein the temperature of the third sintering is 600-650 ℃, and the speed is 3-6 ℃/min; cooling, taking out and ball milling to obtain porous g-C3N4Nanosheets;
(2) dissolving a polymer solid electrolyte containing vinyl into an organic solvent to form a mixed solution, then sequentially adding a lithium salt, a photoinitiator and a cross-linking agent, stirring, and then adding the porous g-C in the step (1)3N4Stirring the nanosheet and lithium oxalate; and carrying out ultraviolet crosslinking on the obtained slurry in an inert gas atmosphere to obtain the polymer composite solid electrolyte.
2. The method for preparing a high-performance polymer composite solid electrolyte according to claim 1, wherein in the step (1), the time for the first sintering is 2-4 h; the time of the second sintering is 1-2 h; the time for the third sintering is 1-2 h; the ball milling time is 10-30 min.
3. The method for preparing a high-performance polymer composite solid electrolyte according to claim 1, wherein in the step (2), the organic solvent is acetonitrile, absolute ethyl alcohol, isopropyl alcohol, acetone, N-dimethylformamide or N-methylpyrrolidone; the lithium oxalate salt is lithium bis (oxalato) borate, lithium difluoro (oxalato) phosphate or lithium tetrafluoro (oxalato) phosphate.
4. The method for preparing a high-performance polymer composite solid electrolyte according to claim 3, wherein in the step (2), the polymer solid electrolyte is polyethylene glycol diacrylate; the molar ratio of vinyl groups to lithium ions of the polyethylene glycol diacrylate is 10-25: 1; the lithium oxalate salt is lithium bis (oxalate) borate.
5. The method for preparing a high-performance polymer composite solid electrolyte as claimed in claim 4, wherein the lithium salt in the step (2) is LiTFSI; the organic solvent is acetonitrile; the photoinitiator is 2, 2-dimethoxy-2-acetophenone; the cross-linking agent is pentaerythritol tetra-3-mercaptopropionate.
6. The method for preparing a high-performance polymer composite solid electrolyte according to claim 5, wherein, in the step (2),
the mass fraction of the polyethylene glycol diacrylate in the mixed solution is 30-60%;
the molar ratio of mercaptan in pentaerythritol tetra-3-mercaptopropionate to vinyl in polyethylene glycol diacrylate is 0.5-1.0: 1.0-2.0;
the mass ratio of the 2, 2-dimethoxy-2-acetophenone to the pentaerythritol tetra-3-mercaptopropionate is 1-3: 50-60 parts of;
porous g-C in the step (1)3N4The molar ratio of the nanosheet to the lithium bis (oxalato) borate to the LiTFSI is 0.1-0.3: 0.2-0.5: 1.0-1.3;
the inert gas is nitrogen.
7. The method for preparing a high-performance polymer composite solid electrolyte as claimed in claim 1 or 6, wherein in the step (2), the UV crosslinking is performed at a wavelength of 365nm and an intensity of 5-9mW/cm2The ultraviolet lamp is exposed for 5-8 times, each exposure time is 5-10s, and each exposure interval is 10 min.
8. The method for preparing a high-performance polymer composite solid electrolyte according to claim 7, wherein in the step (2), the thickness of the polymer composite solid electrolyte is 50 to 500 μm.
9. A battery comprising the polymer composite solid electrolyte according to any one of claims 1 to 8, wherein the battery is an all-solid battery prepared by pressing positive and negative electrode sheets on both sides of the polymer composite solid electrolyte, respectively.
10. The battery according to claim 9, wherein the battery has a capacity of 5Ah or more.
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