CN111916716A - PVDF-TiO2Preparation method of composite membrane and application of composite membrane in inhibiting growth of lithium dendrite - Google Patents
PVDF-TiO2Preparation method of composite membrane and application of composite membrane in inhibiting growth of lithium dendrite Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000012528 membrane Substances 0.000 title claims abstract description 32
- 210000001787 dendrite Anatomy 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 12
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002033 PVDF binder Substances 0.000 claims abstract description 22
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011241 protective layer Substances 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000000807 solvent casting Methods 0.000 abstract description 3
- 238000009827 uniform distribution Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000006183 anode active material Substances 0.000 abstract 1
- 238000010923 batch production Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 7
- 239000011268 mixed slurry Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229920009405 Polyvinylidenefluoride (PVDF) Film Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive 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
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses PVDF-TiO2The preparation method of the composite membrane adopts polyvinylidene fluoride (PVDF) as a matrix and adds nano titanium dioxide (TiO)2) Dissolving the lithium ion battery anode active material in N-methylpyrrolidone (NMP) and ethanol, preparing a film by a solvent casting method, and taking the prepared composite film as a protective layer on the surface of a metal lithium anode for inhibiting the growth of lithium dendrite; the prepared composite membrane has good mechanical property, uniform distribution and stable structure, can prevent the electrolyte from generating side reaction with lithium, prevents the lithium dendrite from puncturing the diaphragm, and further improves the cycle performance of the lithium battery and the safety and stability of the battery. In the whole preparation process, the operation is simple, the cost is low, the equipment and technology investment is small, and the method is suitable for batch production.
Description
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to PVDF-TiO2A method for preparing a composite membrane and its use for inhibiting the growth of lithium dendrites.
Background
With the development of social science and technology, human beings have huge demands for energy sources at present, such as: electronic products, electric vehicles, power grid energy storage and the like, which have higher requirements on the energy density of energy storage materials. Lithium metal is researched and used as a negative electrode of a next-generation lithium ion battery due to high theoretical capacity and low electrochemical potential, however, when the lithium metal is used as the negative electrode of the battery, a great challenge exists, namely dendritic crystal growth in a lithium deposition process, which not only can cause the attenuation of reversible capacity after the battery is cycled, but also lithium dendritic crystals can cause short circuit of the battery and even fire and explosion if penetrating through a diaphragm, and the safety of people is seriously endangered. The current methods for inhibiting the growth of lithium dendrites in lithium metal batteries mainly follow several aspects: (1) starting from the non-uniform deposition of lithium. In 2019, Zhai et al synthesized graphene doped with atomic dispersed metal to regulate nucleation of lithium metal and guide deposition of lithium metal, loaded with monoatomic metal on nitrogen-doped graphene, and constructed a coordination mode of M-Nx-C (M, N, C are respectively expressed as metal, nitrogen and carbon atoms), so that not only can the Li adsorption energy of a metal atom site surrounding domain region be improved under a medium adsorption energy gradient, but also the atomic structure stability of the whole material can be improved. (Zhai et al, Advanced Energy Materials, 2019, 9(18): 1804019). (2) Starting from an SEI film on the surface of lithium metal. In 2018, Assegie et al inhibited the growth of lithium dendrites and increased the cycle efficiency of lithium metal batteries by coating a layer of polyethylene oxide (PEO) on the surface of lithium metal, and the PEO coating promoted the formation of SEI film by coating on the surface of lithium metal and adjusting the side reaction of lithium with electrolyte, increasing the cycle efficiency of lithium metal batteries (Assegie et al, nanoscales, 2018, 10 (13): 6125-. (3) Starting from the alloying of lithium. In 2018, Ye et Al prepared a lithium-philic binary lithium-aluminum alloy layer by an in-situ electrochemical method, and led metal lithium to nucleate and grow uniformly without forming dendrites, and further, the formed Li-Al alloy layer can be used as a Li reservoir to compensate for irreversible Li loss, so that the battery is stable for a long time and shows good cycle performance in a lithium symmetric battery (Ye et Al, angelwalgate Chemie-International Edition, 2019, 58(4): 1094-.
Polyvinylidene fluoride (PVDF) is mainly applied to three fields of petrochemical industry, electronics and electrics and fluorocarbon coatings, has good chemical stability and electrical insulation, is widely used in lithium batteries due to the fact that porous membranes, gels, diaphragms and the like made of PVDF are widely used at present, and needs to be improved to meet requirements under different conditions in practical application although single PVDF has good advantages. In 2019, Fan et Al designed a composite polymer electrolyte by a two-step process, where the composite polymer electrolyte was modified with Al on a conventional cellulose membrane2O3A layer of/PVD-HFP and coated on both sides with in-situ polymerized PMMA. The PMMA layer is hard enough to make it difficult for dendrites to penetrate, even if dendrites enter the outer layer, Al2O3the/PVDF-HFP layer must also consume lithium dendrites to prevent further growth. The complex structure of the design can ensure the mechanical property and the electrochemical property on one hand, and can also avoid the safety problems of short circuit and the like (Fan et al, Acs Applied Energy matrices, 2019, 2(7): 5292-.
Titanium dioxide (TiO)2) Because of its high chemical stability, strong adhesion and less binding energy with lithium, it is often used as an excellent lithium storage material using TiO2To enhance the electrochemical performance of high specific capacity electrode materials. In 2020, Fu et al used a simple air calcination strategy to prepare cake TiO with rich pores2Nanoparticles, which were then further coated on one side of a commercial Celgard separator, TiO2The nanoscale mesoporous channels on the particle surface can effectively prevent the growth of lithium dendrites, resulting in dense and uniform Li deposition with high coulombic efficiency. (Fu et al, ChemElectrochem, 2020, 7 (9): 2159-2164).
The invention uses titanium dioxide (TiO)2) Improved polyvinylidene fluoride (PVDF) film prepared by solvent casting method and used in lithium metal battery due to excellent mechanical property and TiO of PVDF2The lithium affinity of the lithium ion battery can well protect the lithium metal anode in the charge-discharge cycle of the battery, thereby improving the safety of the battery.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the PVDF-TiO with low cost, simple preparation process and environmental protection2The invention also provides a preparation method of the composite membrane, and simultaneously provides an application of the composite membrane in inhibiting the growth of lithium dendrites.
The technical scheme of the invention is as follows:
PVDF-TiO2The preparation method of the composite membrane comprises the following steps:
1) weighing a certain amount of polyvinylidene fluoride (PVDF) and nano titanium dioxide, dissolving the PVDF and nano titanium dioxide in a mixed solution of N-methyl pyrrolidone (NMP) and ethanol, and magnetically stirring for 8-12h to obtain milky mixture slurry;
2) slowly pouring the milky mixture slurry onto a glass plate, and rotating the glass plate obliquely to enable the mixture slurry to be uniformly attached to the glass plate and form a mixture film;
3) putting the mixture film and a glass plate into a vacuum drying oven at 55-65 ℃, and drying for 10-15h to obtain the PVDF-TiO2A composite membrane.
Preferably, in the step (1), the PVDF-TiO2In composite membranes, PVDF and TiO2The mass ratio of (A) to (B) is 1: 0.1-0.2;
preferably, in the step (1), the volume ratio of N-methylpyrrolidone (NMP) to ethanol is 1: (0.8-1.5), preferably 1: 1.
the invention also provides the PVDF-TiO2The composite film is used as a protective layer on the surface of a metal lithium anode, and can effectively inhibit the growth of lithium dendrites; the composite membrane has good mechanical property, uniform distribution, stable structure and good effect of inhibiting lithium dendrite, and has a current density of 500mAg-1Under the condition, the lithium metal electrode can be used for 700 hours in a charging and discharging cycle.
The invention has the advantages that: TiO prepared by the invention2The PVDF composite membrane is prepared by a solvent casting method, and is used as a protective layer of the surface of a metallic lithium anodeTiO2Can induce lithium to be uniformly deposited and can inhibit the growth of lithium dendrites;
the composite membrane prepared by the invention has good mechanical property, uniform distribution and stable structure, can prevent the electrolyte and lithium from generating side reaction, prevents the lithium dendrite from piercing the diaphragm, and further improves the cycle performance of the lithium battery and the safety and stability of the battery.
Drawings
FIG. 1 shows PVDF-TiO prepared by the present invention2XRD pattern of the composite film;
FIG. 2 shows PVDF-TiO prepared by the present invention2SEM picture of composite membrane;
FIG. 3 shows PVDF-TiO prepared by the present invention2The composite film is used as a protective film on the surface of a metal lithium anode.
Detailed Description
The solvents and synthetic starting materials described in examples 1-3 below were all chemically pure.
Example 1
PVDF-TiO2The preparation method of the composite membrane comprises the following steps:
weighing 2 g of polyvinylidene fluoride (PVDF) and 0.15g of nano titanium dioxide (TiO)2) Dissolving in 10 mL of N-methylpyrrolidone (NMP), adding 10 mL of ethanol, and magnetically stirring for 10 hours to obtain milky mixture slurry; slowly pouring the milky mixed slurry on a glass plate, and uniformly attaching the mixed slurry on the glass plate by obliquely rotating the glass plate to form a mixed film; putting the mixture film and a glass plate into a vacuum drying oven at 60 ℃ and drying for 12h to obtain the PVDF-TiO2A composite membrane.
The obtained composite film material was subjected to X-ray powder diffraction, and the result showed TiO2The corresponding diffraction peak of (fig. 1); observing the morphology of the film by using a scanning electron microscope SEM (figure 2); the composite film obtained above was cut into a circular sheet having a diameter of 19 mm, placed on the surface of a metallic lithium anode in a battery, and the cycling performance of a lithium symmetrical battery thereof was tested (fig. 3), and the results showed that the cycling performance of a symmetrical battery with respect to bare lithium was exhibited(comparative example), the cycle performance of the lithium symmetric battery having the composite film to protect the surface of the metallic lithium anode was greatly improved, and the battery was able to stably cycle for 700 hours.
Example 2
PVDF-TiO2The preparation method of the composite membrane comprises the following steps:
1.0 g of polyvinylidene fluoride (PVDF) and 0.10 g of nano-titanium dioxide (TiO) were weighed out2) Dissolving in 10 mL of N-methylpyrrolidone (NMP), adding 8 mL of ethanol, and magnetically stirring for 12h to obtain milky mixture slurry; slowly pouring the milky mixed slurry on a glass plate, and uniformly attaching the mixed slurry on the glass plate by obliquely rotating the glass plate to form a mixed film; putting the mixture film and a glass plate into a vacuum drying oven at 65 ℃ and drying for 10 hours to obtain the PVDF-TiO2A composite membrane.
Example 3
PVDF-TiO2The preparation method of the composite membrane comprises the following steps:
1.0 g of polyvinylidene fluoride (PVDF) and 0.20 g of nano-titanium dioxide (TiO) were weighed out2) Dissolving in 10 mL of N-methylpyrrolidone (NMP), adding 15mL of ethanol, and magnetically stirring for 8 hours to obtain milky mixture slurry; slowly pouring the milky mixed slurry on a glass plate, and uniformly attaching the mixed slurry on the glass plate by obliquely rotating the glass plate to form a mixed film; putting the mixture film and a glass plate into a vacuum drying oven at 55 ℃ and drying for 15h to obtain the PVDF-TiO2A composite membrane.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. PVDF-TiO2Of composite membranesThe preparation method is characterized by comprising the following steps:
1) weighing a certain amount of polyvinylidene fluoride (PVDF) and nano titanium dioxide, dissolving the PVDF and nano titanium dioxide in a mixed solution of N-methyl pyrrolidone (NMP) and ethanol, and magnetically stirring for 8-12h to obtain milky mixture slurry;
2) slowly pouring the milky mixture slurry onto a glass plate, and rotating the glass plate obliquely to enable the mixture slurry to be uniformly attached to the glass plate and form a mixture film;
3) putting the mixture film and a glass plate into a vacuum drying oven at 55-65 ℃, and drying for 10-15h to obtain the PVDF-TiO2A composite membrane.
2. PVDF-TiO according to claim 12The preparation method of the composite membrane is characterized in that in the step (1), the PVDF-TiO2In composite membranes, PVDF and TiO2The mass ratio of (A) to (B) is 1: 0.1-0.2.
3. PVDF-TiO according to claim 12The preparation method of the composite membrane is characterized in that in the step (1), the volume ratio of the N-methylpyrrolidone to the ethanol is 1: (0.8-1.5).
4. PVDF-TiO according to claim 12The preparation method of the composite membrane is characterized in that the volume ratio of the N-methyl pyrrolidone to the ethanol is 1: 1.
5. PVDF-TiO according to any one of claims 1 to 42The preparation method of the composite membrane is characterized in that the PVDF-TiO prepared by the method2The composite film can be applied to a protective layer on the surface of a lithium metal anode.
6. PVDF-TiO according to claim 52The preparation method of the composite membrane is characterized in that the PVDF-TiO prepared by the method2Composite film as surface of metallic lithium anodeAnd a protective layer for inhibiting the growth of lithium dendrites.
7. PVDF-TiO according to claim 52The preparation method of the composite membrane is characterized in that the PVDF-TiO prepared by the method2Composite film with current density of 500mAg-1Under the condition, the lithium metal electrode is used for 700 hours in a charging and discharging cycle.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112490410A (en) * | 2020-11-26 | 2021-03-12 | 宁波大学 | PEO-TiO for inhibiting growth of lithium dendrite2Composite film material and preparation method thereof |
| CN113161546A (en) * | 2021-03-01 | 2021-07-23 | 电子科技大学 | Has PVDF/TiO2Metal lithium cathode of composite protective film and preparation method thereof |
| CN114904054A (en) * | 2022-07-18 | 2022-08-16 | 北京大学口腔医学院 | High-osteogenic-activity charged composite membrane material and preparation method and application thereof |
| CN114976490A (en) * | 2022-06-27 | 2022-08-30 | 山东大学 | A laminated titanium dioxide modified diaphragm and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251377A (en) * | 2015-09-15 | 2016-01-20 | 上海应用技术学院 | Preparation method for polyvinylidene fluoride microfiltration membrane |
| CN106905648A (en) * | 2015-12-22 | 2017-06-30 | 史晓强 | TiO2Nanometer particle-modified PVDF/PMMA laminated films |
| CN109888347A (en) * | 2019-04-03 | 2019-06-14 | 山东星火科学技术研究院 | Preparation method of inorganic nanoparticles modified sulfonated polyetheretherketone membrane |
| CN110075725A (en) * | 2019-06-04 | 2019-08-02 | 武汉轻工大学 | A kind of preparation method of modified polyvinilidene fluoride film |
-
2020
- 2020-07-08 CN CN202010650286.3A patent/CN111916716A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251377A (en) * | 2015-09-15 | 2016-01-20 | 上海应用技术学院 | Preparation method for polyvinylidene fluoride microfiltration membrane |
| CN106905648A (en) * | 2015-12-22 | 2017-06-30 | 史晓强 | TiO2Nanometer particle-modified PVDF/PMMA laminated films |
| CN109888347A (en) * | 2019-04-03 | 2019-06-14 | 山东星火科学技术研究院 | Preparation method of inorganic nanoparticles modified sulfonated polyetheretherketone membrane |
| CN110075725A (en) * | 2019-06-04 | 2019-08-02 | 武汉轻工大学 | A kind of preparation method of modified polyvinilidene fluoride film |
Non-Patent Citations (1)
| Title |
|---|
| 吴梅芬: "锂电池金属锂电极表面修饰及应用研究", 《万方》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112490410A (en) * | 2020-11-26 | 2021-03-12 | 宁波大学 | PEO-TiO for inhibiting growth of lithium dendrite2Composite film material and preparation method thereof |
| CN113161546A (en) * | 2021-03-01 | 2021-07-23 | 电子科技大学 | Has PVDF/TiO2Metal lithium cathode of composite protective film and preparation method thereof |
| CN114976490A (en) * | 2022-06-27 | 2022-08-30 | 山东大学 | A laminated titanium dioxide modified diaphragm and its preparation method and application |
| CN114904054A (en) * | 2022-07-18 | 2022-08-16 | 北京大学口腔医学院 | High-osteogenic-activity charged composite membrane material and preparation method and application thereof |
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Application publication date: 20201110 |