CN116885387A - HGO-based organic-inorganic composite solid electrolyte battery diaphragm and preparation method thereof - Google Patents

HGO-based organic-inorganic composite solid electrolyte battery diaphragm and preparation method thereof Download PDF

Info

Publication number
CN116885387A
CN116885387A CN202310954399.6A CN202310954399A CN116885387A CN 116885387 A CN116885387 A CN 116885387A CN 202310954399 A CN202310954399 A CN 202310954399A CN 116885387 A CN116885387 A CN 116885387A
Authority
CN
China
Prior art keywords
solid electrolyte
hgo
organic
lithium
inorganic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310954399.6A
Other languages
Chinese (zh)
Inventor
潘高峰
曹文卓
闫昭
李婷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huzhou Nanmu Nano Technology Co ltd
Original Assignee
Huzhou Nanmu Nano Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huzhou Nanmu Nano Technology Co ltd filed Critical Huzhou Nanmu Nano Technology Co ltd
Priority to CN202310954399.6A priority Critical patent/CN116885387A/en
Publication of CN116885387A publication Critical patent/CN116885387A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Conductive Materials (AREA)

Abstract

The embodiment of the invention relates to an organic-inorganic composite solid electrolyte battery diaphragm based on HGO and a preparation method thereof. The method comprises the following steps: preparing HGO; preparing inorganic solid electrolyte nano-particle/HGO dispersion liquid; preparing an organic solid electrolyte solution; preparing an organic-inorganic composite solid electrolyte solution by using the composite dispersion liquid and the organic solid electrolyte solution; and coating the inorganic composite solid electrolyte solution on a bottom plate, and vacuum drying to obtain the organic-inorganic composite solid electrolyte membrane. By adding porous graphene oxide HGO or HGO and inorganic solid electrolyte nano particles, the crystallinity of the organic solid electrolyte is reduced, a three-dimensional lithium ion transmission channel is constructed, and the high ion conductivity of the organic inorganic solid electrolyte composite membrane is ensured; meanwhile, the HGO can promote lithium ion transmission, and the interaction force between HGO sheets is strong, so that the tensile strength and flexibility of the diaphragm can be enhanced, and the diaphragm has excellent processability.

Description

HGO-based organic-inorganic composite solid electrolyte battery diaphragm and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery diaphragms, in particular to an organic-inorganic composite solid electrolyte battery diaphragm based on HGO and a preparation method thereof.
Background
With the development and popularization of new energy electric vehicles, the market has raised higher and higher requirements on the energy density and safety of power batteries. The polymer diaphragm in the traditional lithium ion battery has lower mechanical strength, is easy to be pierced by lithium dendrites separated out from the negative electrode, causes the battery to release heat in a short circuit, causes the electrolyte to burn and explode, and has great potential safety hazard. The solid electrolyte has good lithium ion conductivity and excellent mechanical strength, and is hopeful to overcome two problems faced by the traditional lithium ion battery as a new generation battery diaphragm, thereby greatly improving the safety of the lithium ion battery.
The solid electrolyte mainly comprises an inorganic solid electrolyte and an organic solid electrolyte.
The inorganic solid electrolyte has high ionic conductivity at room temperature, strong mechanical strength, poor toughness and poor compatibility with electrodes. To overcome these drawbacks, researchers have focused on developing new inorganic solid electrolyte materials, optimizing the manufacturing process and improving the material properties. For example, the crystal structure of the material is regulated, interface engineering, addition of conductive additives, etc. However, these all complicate the preparation process of the inorganic solid electrolyte and require expensive raw materials and equipment, increasing the cost of battery manufacturing.
The organic solid electrolyte is composed of an organic polymer and a lithium salt, has good flexibility and excellent processability, and is in good contact with the battery electrode interface, however, they have some defects. At high temperatures, organic solid electrolytes tend to crystallize, resulting in a decrease in ionic conductivity. This limits the performance and cycle life of the solid-state battery under high temperature conditions. Organic solid electrolytes generally have low mechanical strength and flexibility. This may lead to cracking or deformation of the battery separator under long-term use or mechanical stress, affecting the stability and life of the battery. In addition, the organic solid electrolyte may have chemical activity to the oxide anode or the metal anode, resulting in an increase in the reactivity of the battery. This may cause side reactions inside the battery, interface problems, and shortening of the life of the battery. Some organic solid state electrolytes have limitations for low or high temperature operation. This may limit the application of solid-state batteries under extreme temperature conditions. To address these issues, researchers have been exploring and developing new organic solid state electrolyte materials and composite systems to improve their performance and stability in order to better meet the needs of solid state battery applications.
Disclosure of Invention
The invention aims to provide an organic-inorganic composite solid electrolyte battery diaphragm based on HGO and a preparation method thereof, wherein the crystallinity of an organic solid electrolyte is reduced by adding porous graphene oxide (HGO) or HGO and inorganic solid electrolyte nano particles, a three-dimensional lithium ion transmission channel is constructed, and the high ion conductivity of the organic-inorganic solid electrolyte composite diaphragm is ensured; meanwhile, the lamellar structure of the HGO enhances the tensile strength and flexibility of the diaphragm, so that the diaphragm has excellent processing performance.
To this end, in a first aspect, an embodiment of the present invention provides a method for preparing an HGO-based organic-inorganic composite solid electrolyte battery separator, the method including:
preparing HGO;
preparing inorganic solid electrolyte nano-particle/HGO dispersion liquid;
preparing an organic solid electrolyte solution;
preparing an organic-inorganic composite solid electrolyte solution by using the dispersion liquid and the organic solid electrolyte solution;
and coating the inorganic composite solid electrolyte solution on a bottom plate, and vacuum drying to obtain the organic-inorganic composite solid electrolyte membrane.
Preferably, the preparing the HGO comprises:
taking a certain amount of graphene oxide GO, dispersing in deionized water, and performing ultrasonic dispersion for 2-4 hours to obtain a uniformly dispersed GO aqueous solution;
adding hydrogen peroxide into the GO aqueous solution, and stirring;
pouring the stirred solution into a hydrothermal reaction kettle for hydrothermal reaction for 8-12 hours at the temperature of 100-150 ℃;
after the reaction kettle is cooled, performing suction filtration by using a nitrocellulose membrane to obtain porous graphene oxide HGO;
and vacuum drying the HGO obtained by suction filtration at room temperature to obtain the dried porous graphene oxide HGO.
Preferably, in the GO aqueous solution, the mass ratio of graphene oxide GO to deionized water is 1:500-1:2000;
the volume ratio of the GO aqueous solution to the hydrogen peroxide is 80:1-120:1, the concentration of the hydrogen peroxide is 30wt%; the stirring time is 20-40min;
the pores of the nitrocellulose membrane are 0.45 μm;
the time of vacuum drying is 12-36 hours.
Preferably, the formulating the inorganic solid electrolyte nanoparticle/HGO dispersion comprises:
adding a certain mass of dispersing agent into a solvent at a stirring speed of 600-1000rpm, and uniformly dispersing to obtain a first dispersion liquid;
adding inorganic solid electrolyte nano particles with a certain mass and HGO with a certain mass into the first dispersion liquid, uniformly stirring, and then performing ultrasonic dispersion to obtain inorganic solid electrolyte nano particles/HGO dispersion liquid; the mass ratio of the inorganic solid electrolyte nano particles to the HGO is 0: 1-2: 1, a step of; when the mass ratio of the inorganic solid electrolyte nano-particles to the HGO is 0:1, the inorganic solid electrolyte nano-particle/HGO dispersion liquid is HGO dispersion liquid;
the solvent comprises: one or more of N, N-Dimethylformamide (DMF), dimethylacetamide (DMAC), acetonitrile, acetone, dimethyl carbonate (DMC), ethylene Carbonate (EC) or N-methylpyrrolidone (NMP);
the dispersant comprises: one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, dodecyl betaine, cetyl ammonium chloride, cetyl ammonium bromide, oleic acid, oleylamine, polyvinylpyrrolidone K30, polyvinyl alcohol, span 80 and tween 80;
the inorganic solid electrolyte nanoparticle includes: one or more of lithium aluminum titanium phosphate LATP, lithium aluminum germanium phosphate LAGP, lithium lanthanum zirconium oxygen LLZO and lithium lanthanum titanium oxygen LLTO, and the granularity D50 is 300nm-500nm;
the total mass of the inorganic solid electrolyte nano-particles and the HGO accounts for 10% -25% of the mass of the inorganic solid electrolyte nano-particles/HGO dispersion;
the addition amount of the dispersing agent is 1wt% of the total mass of the inorganic solid electrolyte nano particles and the HGO;
the stirring time is 1 hour, and the ultrasonic dispersion time is 1 hour.
Preferably, the preparing an organic solid electrolyte solution includes:
weighing a certain mass of solvent, adding a certain mass of polymer into the solvent at a stirring speed of 600-1000rpm, adding a certain mass of lithium salt at the same time, and stirring for 6-8 hours to fully dissolve to obtain an organic solid electrolyte solution;
wherein the solvent comprises: one or more of N, N-Dimethylformamide (DMF), dimethylacetamide (DMAC), acetonitrile, acetone, dimethyl carbonate (DMC), ethylene Carbonate (EC) or N-methylpyrrolidone (NMP);
the polymer comprises: one or more of Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), polyethylene oxide (PEO), polycyanoacrylate (PCA), polyacrylate and polyimide;
the lithium salt includes: lithium perchlorate (LiClO) 4 ) Lithium nitrate (LiNO) 3 ) Lithium fluoride (LiF), lithium bis (oxalato) borate (LiBOB), lithium difluoro (LiDFOB) oxalate borate, lithium bis (fluorosulfonyl) imide (LiLSI), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium (LiCF) triflate (LiQF) 3 SO 3 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluoroarsenate(LiAsF 6 ) Lithium hexafluorophosphate (LiPF) 6 ) At least one of (a) and (b);
in the organic solid electrolyte solution, the mass ratio of the polymer is 5% -15%, and the mass ratio of the lithium salt is 1% -5%.
Preferably, the preparing an organic-inorganic composite solid electrolyte solution from the dispersion liquid and the organic solid electrolyte solution includes:
and adding a certain amount of HGO dispersion liquid into the organic solid electrolyte solution at the stirring speed of 600-1000rpm, and uniformly stirring to obtain the organic-inorganic composite solid electrolyte solution.
Preferably, the base plate is a tetrafluoroethylene base plate.
Preferably, the coating mode comprises at least one of knife coating, roller coating, spin coating and spray coating; the temperature of the vacuum drying is 50-100 ℃, the vacuum degree is-0.1 MPa, and the drying time is 1-2 days.
Preferably, in the organic-inorganic composite solid electrolyte solution, the inorganic solid electrolyte nano particles and HGO account for 5% -20% of the total mass, the polymer accounts for 2.5% -10% of the total mass, the lithium salt accounts for 0.5% -3% of the total mass, and the dispersing agent accounts for 0.005% -0.02% of the total mass.
In a second aspect, the embodiment of the invention provides an organic-inorganic composite solid electrolyte battery separator prepared by the preparation method in the first aspect.
According to the preparation method of the organic-inorganic composite solid electrolyte battery diaphragm based on the HGO, provided by the embodiment of the invention, the crystallinity of the organic solid electrolyte is reduced by adding the porous graphene oxide (HGO) or the HGO and the inorganic solid electrolyte nano particles, a three-dimensional lithium ion transmission channel is constructed, and the high ion conductivity of the organic-inorganic solid electrolyte composite diaphragm is ensured; meanwhile, the HGO surface has a large number of carboxyl, hydroxyl, epoxy and other functional groups, so that lithium ion transmission can be promoted, and the interaction force between HGO sheets is strong, so that the tensile strength and flexibility of the diaphragm can be enhanced, and the diaphragm has excellent processability.
Drawings
FIG. 1 is a flow chart of a method for preparing an organic-inorganic composite solid electrolyte membrane according to embodiment 1 of the present invention;
fig. 2 is a schematic diagram showing the composition of an organic-inorganic composite solid electrolyte separator according to example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
The embodiment of the invention provides an organic-inorganic composite solid electrolyte battery diaphragm based on HGO and a preparation method thereof, wherein the main preparation method comprises the following steps as shown in figure 1:
step 110, preparing HGO;
specific:
step 111, taking a certain amount of graphene oxide GO, dispersing in deionized water, and performing ultrasonic dispersion for 2-4 hours to obtain a uniformly dispersed GO aqueous solution; wherein, the mass ratio of graphene oxide GO to deionized water is 1:500-1:2000.
step 112, adding hydrogen peroxide into the GO aqueous solution, and stirring; wherein, the volume ratio of GO aqueous solution to hydrogen peroxide is 80:1-120:1, a step of; the concentration of the hydrogen peroxide is 30wt%; stirring for 20-40min.
And 113, pouring the stirred solution into a hydrothermal reaction kettle for hydrothermal reaction for 8-12 hours at the temperature of 100-150 ℃.
114, after the reaction kettle is cooled, performing suction filtration by using a nitrocellulose membrane to obtain porous graphene oxide HGO; wherein the pores of the nitrocellulose membrane were 0.45. Mu.m.
Step 115, vacuum drying the HGO obtained by suction filtration at room temperature to obtain dried porous graphene oxide HGO; wherein the vacuum drying time is 12-36 hours.
Step 120, preparing inorganic solid electrolyte nano-particle/HGO dispersion;
specific:
step 121, adding a dispersant with a certain mass into a solvent under the stirring speed of 600-1000rpm, and uniformly dispersing to obtain a first dispersion liquid;
wherein the solvent comprises: one or more of N, N-Dimethylformamide (DMF), dimethylacetamide (DMAC), acetonitrile, acetone, dimethyl carbonate (DMC), ethylene Carbonate (EC) or N-methylpyrrolidone (NMP);
the dispersing agent comprises: one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, dodecyl betaine, cetyl ammonium chloride, cetyl ammonium bromide, oleic acid, oleylamine, polyvinylpyrrolidone K30, polyvinyl alcohol, span 80 and tween 80.
The addition amount of the dispersing agent is 1wt% of the total mass of the inorganic solid electrolyte nano particles and the HGO in the next step.
Step 122, adding inorganic solid electrolyte nano particles with a certain mass and HGO with a certain mass into the first dispersion liquid, stirring uniformly, and then performing ultrasonic dispersion to obtain inorganic solid electrolyte nano particles/HGO dispersion liquid;
wherein the inorganic solid electrolyte nanoparticle comprises: one or more of lithium aluminum titanium phosphate LATP, lithium aluminum germanium phosphate LAGP, lithium lanthanum zirconium oxygen LLZO and lithium lanthanum titanium oxygen LLTO, and the granularity D50 is 300nm-500nm;
the total mass of the inorganic solid electrolyte nano-particles and the HGO accounts for 10% -25% of the mass of the inorganic solid electrolyte nano-particles/HGO dispersion;
the mass ratio of the inorganic solid electrolyte nano-particles to the HGO is 0: 1-2: 1, a step of; when the mass ratio of the inorganic solid electrolyte nano-particles to the HGO is 0:1, the inorganic solid electrolyte nanoparticle/HGO dispersion is an HGO dispersion.
The stirring time was 1 hour, and the ultrasonic dispersion time was 1 hour.
Step 130, preparing an organic solid electrolyte solution;
weighing a certain mass of solvent, adding a certain mass of polymer into the solvent at a stirring speed of 600-1000rpm, adding a certain mass of lithium salt at the same time, and stirring for 6-8 hours to fully dissolve to obtain an organic solid electrolyte solution;
wherein the solvent comprises: one or more of N, N-Dimethylformamide (DMF), dimethylacetamide (DMAC), acetonitrile, acetone, dimethyl carbonate (DMC), ethylene Carbonate (EC) or N-methylpyrrolidone (NMP);
the polymer comprises: one or more of Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), polyethylene oxide (PEO), polycyanoacrylate (PCA), polyacrylate and polyimide;
the lithium salt includes: lithium perchlorate (LiClO) 4 ) Lithium nitrate (LiNO) 3 ) Lithium fluoride (LiF), lithium bis (oxalato) borate (LiBOB), lithium difluoro (LiDFOB) oxalate borate, lithium bis (fluorosulfonyl) imide (LiLSI), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium (LiCF) triflate (LiQF) 3 SO 3 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium hexafluorophosphate (LiPF) 6 ) At least one of (a) and (b);
in the organic solid electrolyte solution, the mass ratio of the polymer is 5% -15%, and the mass ratio of the lithium salt is 1% -5%.
Step 140, preparing an organic-inorganic composite solid electrolyte solution by using the dispersion liquid and the organic solid electrolyte solution;
and adding a certain amount of HGO dispersion liquid into the organic solid electrolyte solution at the stirring speed of 600-1000rpm, and uniformly stirring to obtain the organic-inorganic composite solid electrolyte solution.
And 150, coating the inorganic composite solid electrolyte solution on a bottom plate, and vacuum drying to obtain the organic-inorganic composite solid electrolyte membrane.
Wherein the bottom plate is concretely a tetrafluoroethylene bottom plate.
The coating mode comprises at least one of knife coating, roller coating, spin coating and spray coating; the temperature of the vacuum drying is 50-100 ℃, the vacuum degree is-0.1 MPa, and the drying time is 1-2 days.
According to the method, through adding the porous graphene oxide HGO or HGO and the inorganic solid electrolyte nano particles, the crystallinity of the organic solid electrolyte is reduced, a three-dimensional lithium ion transmission channel is constructed, and the high ion conductivity of the organic inorganic solid electrolyte composite membrane is ensured. Meanwhile, the surface of the porous graphene oxide HGO of the lamellar structure of the porous graphene oxide HGO is provided with a large number of carboxyl, hydroxyl, epoxy groups and other functional groups, so that lithium ion transmission can be promoted, the interaction force between HGO lamellar layers is strong, the tensile strength and flexibility of the diaphragm are enhanced, and the diaphragm has excellent processing performance.
The invention is further illustrated by the drawings and the specific examples, which are to be understood as being for the purpose of more detailed description only and are not to be construed as limiting the invention in any way, i.e. not intended to limit the scope of the invention.
Example 1
The embodiment provides a method for preparing a LATP/HGO/LiTFSI@PVDF organic-inorganic composite solid electrolyte battery diaphragm, which comprises the following specific steps:
step 1: preparing porous graphene oxide HGO.
Dispersing 0.1g of graphene oxide GO in 100ml of deionized water, and performing ultrasonic dispersion for 2 hours to obtain uniformly dispersed GO aqueous solution; adding 1ml hydrogen peroxide H with concentration of 30wt% 2 O 2 Stirring for 30 minutes; pouring the solution into a 150ml hydrothermal reaction kettle, and carrying out hydrothermal reaction for 8 hours at the temperature of 100 ℃; after the reaction kettle is cooled, a nitrocellulose membrane with a gap size of 0.45 mu m is used for suction filtration to obtain porous graphene oxide HGO; and (3) vacuum drying the HGO obtained by suction filtration for 24 hours at room temperature to obtain the required dried porous graphene oxide HGO.
Step 2: preparing inorganic solid electrolyte nano-particle/porous graphene oxide HGO composite dispersion liquid A.
180g of N, N-Dimethylformamide (DMF) is weighed, 0.2g of dispersing agent polyvinyl alcohol PEG-400 is added under the stirring speed of 1000rpm, the dispersion is uniform, 10g of inorganic solid electrolyte nano particles LATP and 10g of porous graphene oxide HGO are added into the solution, and after 1000prm stirring is carried out for 1 hour, the LATP/HGO composite dispersion A is obtained by ultrasonic dispersion for 1 hour.
Step 3: an organic solid electrolyte solution B was prepared.
150g of N, N-Dimethylformamide (DMF) and 26g of dimethyl carbonate (DMC) were weighed, 20g of polyvinylidene fluoride (PVDF) was added at a stirring rate of 1000rpm, and simultaneously 4g of lithium bistrifluoromethane-sulfonyl imide (LiTFSI) was added, and the mixture was stirred for 6 to 8 hours to be sufficiently dissolved to obtain an organic solid electrolyte solution B.
Step 4: preparing organic-inorganic composite solid electrolyte solution.
100g of LATP/HGO composite dispersion A was added to 100g of the organic solid electrolyte solution B at a stirring rate of 1000rpm, and stirred uniformly to obtain an organic-inorganic composite solid electrolyte solution C.
Step 5: coating and forming a film.
And coating the organic-inorganic composite solid electrolyte solution C on a tetrafluoroethylene bottom plate by adopting a knife coating method, and drying in a vacuum drying oven together, wherein the vacuum degree is-0.1 MPa, and drying at 80 ℃ for 2 days to obtain the LATP/HGO/LiTFSI@PVDF organic-inorganic composite solid electrolyte battery diaphragm.
Fig. 2 is a schematic diagram showing the composition of an organic-inorganic composite solid electrolyte separator according to example 1 of the present invention.
Example 2
The embodiment provides a method for preparing a diaphragm of an HGO/LiTFSI@PVDF organic-inorganic composite solid electrolyte battery, which comprises the following specific steps:
step 1: preparing porous graphene oxide HGO.
Dispersing 0.1g of graphene oxide GO in 100ml of deionized water, and performing ultrasonic dispersion for 2 hours to obtain uniformly dispersed GO aqueous solution; adding 1ml hydrogen peroxide H with concentration of 30wt% 2 O 2 Stirring for 30 minutes; pouring the solution into a 150ml hydrothermal reaction kettle, and carrying out hydrothermal reaction for 8 hours at the temperature of 100 ℃; after the reaction kettle is cooled, a nitrocellulose membrane with a gap size of 0.45 mu m is used for suction filtration to obtain porous graphene oxide HGO; and (3) vacuum drying the HGO obtained by suction filtration for 24 hours at room temperature to obtain the required dried porous graphene oxide HGO.
Step 2: preparing a porous graphene oxide HGO dispersion liquid A.
180g of DMF was weighed, 0.2g of the dispersing agent polyvinyl alcohol PEG-400 was added under a stirring rate of 1000rpm, and dispersed uniformly, and then 20g of HGO was taken, added to the above solution, and after stirring for 1 hour at 1000prm, ultrasonic dispersion was carried out for 1 hour, to obtain HGO dispersion A.
Step 3: an organic solid electrolyte solution B was prepared.
150g of N, N-Dimethylformamide (DMF) and 26g of dimethyl carbonate (DMC) were weighed, 20g of PVDF was added at a stirring rate of 1000rpm, and at the same time 4g of lithium salt LiTFSI was added, and stirred for 8 hours to be sufficiently dissolved to obtain an organic solid electrolyte solution B.
Step 4: preparing organic-inorganic composite solid electrolyte solution C.
100g of the dispersion A was added to 100g of the solution B at a stirring rate of 1000rpm, and stirred uniformly to obtain an organic-inorganic composite solid electrolyte solution C.
Step 5: coating and forming a film.
And (3) coating the organic-inorganic composite solid electrolyte solution C on a tetrafluoroethylene bottom plate by adopting a knife coating method, and drying in a vacuum drying oven at the vacuum degree of-0.1 MPa for 2 days at the temperature of 80 ℃ to obtain the HGO/LiTFSI@PVDF organic-inorganic composite solid electrolyte battery diaphragm.
Comparative example 1
The comparative example provides a method for preparing a LATP/GO/LiTFSI@PVDF organic-inorganic composite solid electrolyte battery diaphragm, which comprises the following specific steps:
step 1: preparation of Graphene Oxide (GO) by hummers method
A 250mL reaction bottle is assembled in ice water bath, 46mL of concentrated sulfuric acid is added, a solid mixture of 2g of graphite powder and 1g of sodium nitrate is added under stirring, 6g of potassium permanganate is added in multiple times, the reaction temperature is controlled to be not more than 20 ℃, and the stirring reaction is carried out for 2 hours; then heating to about 35 ℃ and continuing stirring for 30 minutes; then 92ml of deionized water is slowly added, the temperature is increased to 98 ℃, the reaction is continued for 20 minutes, the solution is brown yellow, and red smoke is emitted; adding 10g of hydrogen peroxide with concentration of 30wt% to reduce residual oxidant to make the solution become bright yellow; filtering while the solution is hot, and washing the solution with 5% HCl solution and deionized water in sequence until no sulfate radical is detected in the filtrate. And finally, placing the filter cake in a vacuum drying oven at 60 ℃ for full drying to obtain graphene oxide GO.
Step 2: an inorganic solid electrolyte nanoparticle/graphene oxide (LATP/GO) dispersion a was formulated.
180g of DMF is weighed by the composite dispersion liquid A, 0.2g of dispersing agent polyvinyl alcohol PEG-400 is added under the stirring speed of 1000rpm, the dispersion is uniform, then 10g of inorganic solid electrolyte nano particles LATP and 10g of graphene oxide GO are added into the solution, after 1000prm stirring is carried out for 1 hour, the LATP/GO dispersion liquid A is obtained by ultrasonic dispersion for 1 hour.
Step 3: preparing organic solid electrolyte solution B
150g of N, N-Dimethylformamide (DMF) and 26g of dimethyl carbonate (DMC) were weighed, 20g of PVDF was added at a stirring rate of 1000rpm, and at the same time 4g of LiTFSI was added, and stirring was carried out for 6 to 8 hours to sufficiently dissolve to obtain an organic solid electrolyte solution B.
Step 4: preparing organic-inorganic composite solid electrolyte solution C.
100g of LATP/GO dispersion A is added into 100g of organic solid electrolyte solution B at a stirring speed of 1000rpm, and the mixture is stirred uniformly to obtain organic-inorganic composite solid electrolyte solution C.
Step 5: coating and forming a film.
And coating the organic-inorganic composite solid electrolyte solution C on a tetrafluoroethylene bottom plate by adopting a knife coating method, putting the diaphragm and the tetrafluoroethylene bottom plate together into a vacuum drying oven for drying, and drying at the vacuum degree of-0.1 MPa and 80 ℃ for 2 days to obtain the LATP/GO/LiTFSI@PVDF organic-inorganic composite solid electrolyte battery diaphragm.
Comparative example 2
The comparative example provides a method for preparing a LATP/LiTFSI@PVDF organic-inorganic composite solid electrolyte battery diaphragm, which comprises the following specific steps:
step 1: preparing inorganic solid electrolyte nano particle dispersion liquid A.
180g of DMF is weighed, 0.2g of dispersing agent polyvinyl alcohol PEG-400 is added under the stirring speed of 1000rpm, the dispersion is uniform, then 20g of inorganic solid electrolyte LATP is taken, the solution is added, and after stirring for 1 hour at 1000prm, the ultrasonic dispersion is carried out for 1 hour, thus obtaining LATP dispersion A.
Step 2: an organic solid electrolyte solution B was prepared.
150g of N, N-Dimethylformamide (DMF) and 26g of dimethyl carbonate (DMC) were weighed, 20g of PVDF was added at a stirring rate of 1000rpm, and at the same time 4g of LiTFSI was added, and stirring was carried out for 6 to 8 hours to sufficiently dissolve to obtain an organic solid electrolyte solution B.
Step 3: preparing organic-inorganic composite solid electrolyte solution C.
100g of LATP dispersion A was added to 100g of the organic solid electrolyte solution B at a stirring rate of 1000rpm, and stirred uniformly to obtain an organic-inorganic composite solid electrolyte solution C.
Step 4: coating and forming a film.
And (3) coating the organic-inorganic composite solid electrolyte solution C on a tetrafluoroethylene bottom plate by adopting a knife coating method, putting the diaphragm and the tetrafluoroethylene bottom plate together into a vacuum drying oven for drying, and drying at the vacuum degree of-0.1 MPa and the temperature of 80 ℃ for 2 days to obtain the LATP/LiTFSI@PVDF organic-inorganic composite solid electrolyte battery diaphragm.
In order to verify the properties of the separator obtained by the method for preparing the organic-inorganic composite solid electrolyte battery separator by using the porous graphene oxide, tensile strength and ionic conductivity of the organic-inorganic composite solid electrolyte separators prepared in examples 1 and 2 and comparative examples 1 and 2 are tested.
According to national standard GB 13022-1991, a universal tensile tester is adopted to measure the tensile strength of the prepared organic-inorganic composite solid electrolyte membrane.
The ion conductivity of the organic-inorganic composite solid electrolyte separator was measured by Electrochemical Impedance Spectroscopy (EIS). Stainless steel is used as a blocking electrode, the frequency range of EIS test is 5 MHz-1 Hz, the test temperature range is-20-80 ℃, and the perturbation voltage is 10mV.
The test results are shown in table 1 below.
TABLE 1
It can be seen that the separators of examples 1 and 2 of the present invention have better tensile strength and also have higher ionic conductivity.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (10)

1. A method for preparing an organic-inorganic composite solid electrolyte battery separator based on HGO, which is characterized by comprising the following steps:
preparing HGO;
preparing inorganic solid electrolyte nano-particle/HGO dispersion liquid;
preparing an organic solid electrolyte solution;
preparing an organic-inorganic composite solid electrolyte solution by using the dispersion liquid and the organic solid electrolyte solution;
and coating the inorganic composite solid electrolyte solution on a bottom plate, and vacuum drying to obtain the organic-inorganic composite solid electrolyte membrane.
2. The method of preparing HGO according to claim 1, wherein said preparing HGO comprises:
taking a certain amount of graphene oxide GO, dispersing in deionized water, and performing ultrasonic dispersion for 2-4 hours to obtain a uniformly dispersed GO aqueous solution;
adding hydrogen peroxide into the GO aqueous solution, and stirring;
pouring the stirred solution into a hydrothermal reaction kettle for hydrothermal reaction for 8-12 hours at the temperature of 100-150 ℃;
after the reaction kettle is cooled, performing suction filtration by using a nitrocellulose membrane to obtain porous graphene oxide HGO;
and vacuum drying the HGO obtained by suction filtration at room temperature to obtain the dried porous graphene oxide HGO.
3. The preparation method of claim 2, wherein in the GO aqueous solution, the mass ratio of graphene oxide GO to deionized water is 1:500-1:2000;
the volume ratio of the GO aqueous solution to the hydrogen peroxide is 80:1-120:1, a step of; the concentration of the hydrogen peroxide is 30wt%; the stirring time is 20-40min;
the pores of the nitrocellulose membrane are 0.45 μm;
the time of vacuum drying is 12-36 hours.
4. The method of preparing according to claim 1, wherein said formulating an inorganic solid electrolyte nanoparticle/HGO dispersion comprises:
adding a certain mass of dispersing agent into a solvent at a stirring speed of 600-1000rpm, and uniformly dispersing to obtain a first dispersion liquid;
adding inorganic solid electrolyte nano particles with a certain mass and HGO with a certain mass into the first dispersion liquid, uniformly stirring, and then performing ultrasonic dispersion to obtain inorganic solid electrolyte nano particles/HGO dispersion liquid; the mass ratio of the inorganic solid electrolyte nano particles to the HGO is 0: 1-2: 1, a step of; when the mass ratio of the inorganic solid electrolyte nano-particles to the HGO is 0:1, the inorganic solid electrolyte nano-particle/HGO dispersion liquid is HGO dispersion liquid;
the solvent comprises: one or more of N, N-Dimethylformamide (DMF), dimethylacetamide (DMAC), acetonitrile, acetone, dimethyl carbonate (DMC), ethylene Carbonate (EC) or N-methylpyrrolidone (NMP);
the dispersant comprises: one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, dodecyl betaine, cetyl ammonium chloride, cetyl ammonium bromide, oleic acid, oleylamine, polyvinylpyrrolidone K30, polyvinyl alcohol, span 80 and tween 80;
the inorganic solid electrolyte nanoparticle includes: one or more of lithium aluminum titanium phosphate LATP, lithium aluminum germanium phosphate LAGP, lithium lanthanum zirconium oxygen LLZO and lithium lanthanum titanium oxygen LLTO, and the granularity D50 is 300nm-500nm;
the total mass of the inorganic solid electrolyte nano-particles and the HGO accounts for 10% -25% of the mass of the inorganic solid electrolyte nano-particles/HGO dispersion;
the addition amount of the dispersing agent is 1wt% of the total mass of the inorganic solid electrolyte nano particles and the HGO;
the stirring time is 1 hour, and the ultrasonic dispersion time is 1 hour.
5. The method of preparing according to claim 1, wherein said formulating an organic solid electrolyte solution comprises:
weighing a certain mass of solvent, adding a certain mass of polymer into the solvent at a stirring speed of 600-1000rpm, adding a certain mass of lithium salt at the same time, and stirring for 6-8 hours to fully dissolve to obtain an organic solid electrolyte solution;
wherein the solvent comprises: one or more of N, N-Dimethylformamide (DMF), dimethylacetamide (DMAC), acetonitrile, acetone, dimethyl carbonate (DMC), ethylene Carbonate (EC) or N-methylpyrrolidone (NMP);
the polymer comprises: one or more of Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), polyethylene oxide (PEO), polycyanoacrylate (PCA), polyacrylate and polyimide;
the lithium salt includes: lithium perchlorate (LiClO) 4 ) Lithium nitrate (LiNO) 3 ) Lithium fluoride (LiF), lithium bis (oxalato) borate (LiBOB), lithium difluoro (LiDFOB) oxalate borate, lithium bis (fluorosulfonyl) imide (LiLSI), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium (LiCF) triflate (LiQF) 3 SO 3 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium hexafluorophosphate (LiPF) 6 ) At least one of (a) and (b);
in the organic solid electrolyte solution, the mass ratio of the polymer is 5% -15%, and the mass ratio of the lithium salt is 1% -5%.
6. The method of preparing according to claim 1, wherein the preparing an organic-inorganic composite solid electrolyte solution from the dispersion liquid and the organic solid electrolyte solution comprises:
and adding a certain amount of HGO dispersion liquid into the organic solid electrolyte solution at the stirring speed of 600-1000rpm, and uniformly stirring to obtain the organic-inorganic composite solid electrolyte solution.
7. The method of claim 1, wherein the substrate is a tetrafluoroethylene substrate.
8. The method of claim 1, wherein the coating comprises at least one of knife coating, roller coating, spin coating, and spray coating; the temperature of the vacuum drying is 50-100 ℃, the vacuum degree is-0.1 MPa, and the drying time is 1-2 days.
9. The preparation method according to claim 1, wherein in the organic-inorganic composite solid electrolyte solution, the inorganic solid electrolyte nano particles and HGO account for 5% -20% of the total mass, the polymer accounts for 2.5% -10% of the total mass, the lithium salt accounts for 0.5% -3% of the total mass, and the dispersant accounts for 0.005% -0.02% of the total mass.
10. An organic-inorganic composite solid electrolyte battery separator prepared by the preparation method of any one of claims 1 to 9.
CN202310954399.6A 2023-07-31 2023-07-31 HGO-based organic-inorganic composite solid electrolyte battery diaphragm and preparation method thereof Pending CN116885387A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310954399.6A CN116885387A (en) 2023-07-31 2023-07-31 HGO-based organic-inorganic composite solid electrolyte battery diaphragm and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310954399.6A CN116885387A (en) 2023-07-31 2023-07-31 HGO-based organic-inorganic composite solid electrolyte battery diaphragm and preparation method thereof

Publications (1)

Publication Number Publication Date
CN116885387A true CN116885387A (en) 2023-10-13

Family

ID=88254904

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310954399.6A Pending CN116885387A (en) 2023-07-31 2023-07-31 HGO-based organic-inorganic composite solid electrolyte battery diaphragm and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116885387A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117275795A (en) * 2023-11-23 2023-12-22 琥崧科技集团股份有限公司 Graphene composite material conductive paste and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117275795A (en) * 2023-11-23 2023-12-22 琥崧科技集团股份有限公司 Graphene composite material conductive paste and preparation method thereof
CN117275795B (en) * 2023-11-23 2024-01-26 琥崧科技集团股份有限公司 Graphene composite material conductive paste and preparation method thereof

Similar Documents

Publication Publication Date Title
CN108232288B (en) Sulfur-containing polymer electrolyte, solid lithium battery formed by sulfur-containing polymer electrolyte and preparation of solid lithium battery
CN103280571B (en) A kind of anode material for lithium-ion batteries and preparation method thereof
CN107666011B (en) Non-aqueous electrolyte and non-aqueous electrolyte secondary battery
KR20150050458A (en) Manufacturing method of cathode active material, and cathode active material for lithium secondary battery manufactured thereby
CN114024025B (en) Copolymerization solid electrolyte, preparation method thereof and solid polymer lithium battery
CN116885387A (en) HGO-based organic-inorganic composite solid electrolyte battery diaphragm and preparation method thereof
CN111786024B (en) Titanium oxygen cluster based solid polymer electrolyte and preparation method and application thereof
CN113540560A (en) Electrolyte and preparation method and application thereof
CN110828891B (en) Sulfur-containing polymer solid electrolyte and preparation method and application thereof
CN101197436A (en) Positive plate of lithium ion secondary battery, and battery including the same
CN112490495A (en) Inorganic-organic composite solid electrolyte, preparation method and solid lithium battery
CN113346132B (en) Fluorinated polyethylene oxide solid electrolyte material and preparation method and application thereof
CN115347181A (en) Preparation method of manganese dioxide/quinone polymer composite material and zinc ion storage application thereof
CN114573484A (en) Organic electrode material, intermediate thereof, positive plate and battery
CN101359748B (en) Lithium-ion secondary cell and manufacturing method therefor
CN113991175B (en) Polycarbonate-based solid electrolyte and preparation method and application thereof
CN111092265A (en) Preparation method of positive electrode support type all-solid-state lithium ion battery
CN118136847B (en) Self-supporting electrode, preparation method, application and battery
CN106469806B (en) A kind of positive electrode active materials and preparation method thereof, positive plate and lithium ion battery
CN117913357B (en) Preparation method of LATP ceramic particle reinforced quasi-solid polymer electrolyte
CN114759260B (en) Electrolyte for improving high-temperature performance of battery and lithium ion battery
CN115275170B (en) Preparation method of cerium dioxide modified lithium iron manganese phosphate electrode material
CN112397771B (en) Solid electrolyte membrane, preparation method thereof and application thereof in solid lithium-sulfur battery
CN118213610A (en) Preparation method of low-temperature composite quasi-solid electrolyte and application of solid lithium battery
CN116345061A (en) Ultrathin glass fiber diaphragm for lithium/sodium metal battery and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination