CN112670673A - Ion-conducting organic-inorganic composite modified diaphragm and preparation method and application thereof - Google Patents
Ion-conducting organic-inorganic composite modified diaphragm and preparation method and application thereof Download PDFInfo
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- CN112670673A CN112670673A CN202011553978.2A CN202011553978A CN112670673A CN 112670673 A CN112670673 A CN 112670673A CN 202011553978 A CN202011553978 A CN 202011553978A CN 112670673 A CN112670673 A CN 112670673A
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- 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
Abstract
The invention belongs to the technical field of lithium ion batteries, and discloses an ion-conducting organic-inorganic composite modified diaphragm, wherein PVDF-HFP contained in the diaphragm has ion conductivity, and-F functional groups in a chemical structure can react with metal lithium to generate LiF, so that a solid electrolyte interface layer is stabilized, and meanwhile, the interface contact with the metal lithium is improved due to good flexibility and the lithium-philic effect of polar groups, and the wettability and the storability of the diaphragm with an electrolyte are improved; NaTi2(PO4)3As the inorganic particles are compounded with PVDF-HFP, the crystallinity of the PVDF-HFP can be obviously reducedIonic conductivity is mentioned. The composite layer with high ionic conductivity reduces space charge effect and inhibits dendritic crystal formation and growth. Meanwhile, the uniformly distributed particles further enable the lithium ions to flow more uniformly, and the lithium metal negative electrode can be protected.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an ion-conducting organic-inorganic composite modified diaphragm and a preparation method and application thereof.
Background
With the rapid development in the fields of portable electronic equipment, electric automobiles, new energy storage and the like, higher requirements are put forward on the energy density, the cycle stability and the safety of energy storage equipment. However, the conventional lithium ion secondary battery is limited in theoretical capacity and has not been able to meet the demand for technical development. Therefore, it is of great interest to develop new battery systems with high energy density, high power density and long cycle life. The lithium metal negative electrode material has high specific capacity (3860mAh g)-1) Low reduction potential (-3.04V compared to standard hydrogen electrode) and small density (0.543g cm)-3) And is considered to be the most potential next generation high energy density battery cathode material. However, the problems of low coulombic efficiency, short cycle life, poor safety, etc., caused by uncontrolled dendrite growth and infinite volume expansion during the deposition/dissolution of lithium, have severely hindered the use of lithium metal in high energy density batteries.
The control of lithium nucleation and growth during charging and discharging is the key to solving the above problems. Currently, researchers have adopted many strategies to inhibit lithium dendrite growth, mainly: (1) developing a solid electrolyte; (2) improving the electrolyte; (3) designing a novel structure metal lithium cathode; (4) constructing an artificial solid electrolyte interface layer; (5) and (3) modifying the diaphragm. Wherein, the diaphragm modification technology has the outstanding advantages of simple operation, low cost and the like. Therefore, the reasonable selection of the diaphragm modified material and the adoption of the efficient and low-cost modified diaphragm mode become the key of the commercialization of the metal lithium battery.
Disclosure of Invention
The invention aims to overcome the defects of the prior art related to less membrane modification technology and provide a novel ion-conducting organic-inorganic composite modified membrane.
The second purpose of the invention is to provide a preparation method of the ion-conducting organic-inorganic composite modified diaphragm.
The third purpose of the invention is to provide the application of the ion-conducting organic-inorganic composite modified membrane.
The purpose of the invention is realized by the following technical scheme:
an ion-conducting organic-inorganic composite modified diaphragm comprises a porous diaphragm substrate and slurry coated on the porous diaphragm substrate; the slurry is prepared by the following method: the lithium ion conductive inorganic particle, the lithium ion conductive polymer and the lithium salt are dispersed in the solvent.
Preferably, the lithium ion conductive inorganic particles are garnet-type solid electrolytes, perovskite-type Li3xLa2/3–xTiO3Solid electrolyte, NASICON type Li1+xAlxTi2–x(PO4)3，Li1+xAlxGe2–x(PO4)3Solid electrolyte, anti-perovskite Li3–2xMxHalO solid electrolyte, LiPON solid electrolyte and sulfide solid electrolyte.
Preferably, the polymer capable of conducting lithium ions is at least one of polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polypropylene oxide, polyvinylpyrrolidone, polyvinylidene chloride, polypropylene carbonate and polyvinylidene fluoride-hexafluoropropylene.
Preferably, the lithium salt is at least one of lithium perchlorate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonate) imide and lithium tris (trifluoromethanesulfonate) methide.
Preferably, the porous separator substrate is one or both of a polyethylene separator and a polypropylene separator.
As a preferred embodiment, the inorganic particle capable of conducting lithium ions is NaTi2(PO4)3(ii) a The polymer capable of conducting lithium ions is PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene); the chemical structure of the organic PVDF-HFP in the composite layer can interact with lithium ions to conduct the lithium ions. PVDF-HFP has a chemical structure with a functional group of-F, and can react with lithium to generateForming LiF and stabilizing the solid electrolyte interface layer. The PVDF-HFP polymer has good flexibility, improves interface contact between electrodes, and improves wettability and retainability to electrolyte. Inorganic NaTi in the composite layer2(PO4)3Can be used as a lithium ion conductor to improve the ionic conductivity of the composite layer. NaTi2(PO4)3As the inorganic particles compounded with PVDF-HFP, the crystallinity of PVDF-HFP can be significantly reduced, and ion conductivity is mentioned. The composite layer with high ionic conductivity reduces space charge effect and inhibits dendritic crystal formation. Meanwhile, the uniformly distributed particles further enable the lithium ions to flow more uniformly.
The invention also provides a preparation method of the ion-conducting organic-inorganic composite modified diaphragm, which comprises the steps of coating the slurry on a porous diaphragm substrate, immersing the porous diaphragm substrate in absolute ethyl alcohol, and drying the porous diaphragm substrate to obtain the ion-conducting organic-inorganic composite modified diaphragm.
Preferably, in the preparation method, the drying is carried out at 60-80 ℃.
As a specific embodiment, the preparation method comprises the following steps:
mixing Ti (OC)4H9)4Dissolving in anhydrous ethanol, and adding CH under magnetic stirring3COONa·3H2O and concentrated hydrochloric acid. H is to be3PO4(concentration 85 wt%) was dissolved in absolute ethanol and added dropwise to the above solution. And then stirring for 3h at 55 ℃, and evaporating the absolute ethanol solvent to dryness to obtain NTP precursor particles. Grinding NTP precursor particles into powder in a mortar, calcining in Ar atmosphere to obtain NTP powder, and carrying out high-energy ball milling on the NTP powder for 3 hours for later use.
And adding 20-90 wt% of NTP powder into DMF for ultrasonic dispersion. Then, PVDF-HFP and LiClO were mixed4(mass ratio 3: 1) is added into the mixed solution, and the mixture is stirred, dissolved and dispersed uniformly. And then coating the uniform slurry on a PP diaphragm or a PE diaphragm by adopting a 100-micrometer scraper to prepare a composite diaphragm, and then soaking the composite diaphragm into absolute ethyl alcohol for phase inversion. And finally, drying the composite diaphragm to obtain the composite diaphragm, cutting the composite diaphragm into a wafer, and putting the wafer into a glove box for later use.
The invention also provides application of the ion-conducting organic-inorganic composite modified diaphragm, which is to cover the diaphragm on a lithium metal cathode. Preferably, the thickness of the cover is 1 to 10 μm.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides an ion-conducting organic-inorganic composite modified diaphragm, wherein PVDF-HFP contained in the diaphragm has ion conductivity, a-F functional group in a chemical structure can react with metal lithium to generate LiF, so that a solid electrolyte interface layer is stabilized, meanwhile, the interface contact with the metal lithium is improved due to good flexibility and the lithium affinity effect of polar groups, and the wettability and the storage property with an electrolyte are improved; NaTi2(PO4)3As the inorganic particles compounded with PVDF-HFP, the crystallinity of PVDF-HFP can be significantly reduced, and ion conductivity is mentioned. The composite layer with high ionic conductivity reduces space charge effect and inhibits dendritic crystal formation and growth. Meanwhile, the uniformly distributed particles further enable the lithium ions to flow more uniformly, and the lithium metal negative electrode can be protected.
Drawings
FIG. 1 is NaTi2(PO4)3XRD contrast patterns of PP and PP @ PHNTP-90;
FIG. 2 shows NaTi2(PO4)3And SEM scan of PP @ PHNTP-90;
FIG. 3 shows that the Cu-Li asymmetric battery of PP and PP @ PHNTP-90 is at 0.5mA cm-2,1mAh cm-2Coulombic efficiency plots under test conditions;
FIG. 4 shows that the Li-Li symmetrical battery of PP and PP @ PHNTP-90 is at 1mA cm-2,1mAh cm-2The cycling performance under the test conditions was tested.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The test methods used in the following examples and experimental examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are commercially available reagents and materials; the equipment used, unless otherwise specified, is conventional laboratory equipment.
Example 1
The embodiment of the invention provides an ion-conducting organic-inorganic composite layer modified diaphragm, which is prepared by the following steps:
1.7204g of Ti (OC) were first introduced4H9)4Dissolved in 20mL of absolute ethanol and 0.3404g of CH were added under magnetic stirring3COONa·3H2O and 2mL of concentrated hydrochloric acid were added to the above solution to obtain solution A. 0.8566g H will be mixed3PO4(concentration 85 wt.%) was dissolved in 15mL of absolute ethanol and added dropwise to solution A. Then stirring for 3h at 55 ℃, and evaporating the absolute ethyl alcohol to dryness to obtain NaTi2(PO4)3And (3) precursor particles. Grinding the precursor particles into fine powder in a mortar, and calcining for 5 hours at 750 ℃ in Ar atmosphere to obtain NaTi2(PO4)3And (3) powder. Then adding NaTi2(PO4)3And performing high-energy ball milling on the powder for 3 hours for later use.
90 wt% NTP powder is added into 5mL DMF for ultrasonic dispersion for 1 h. Then, PVDF-HFP and LiClO were mixed4(mass ratio 3: 1) and stirring at 60 ℃ for 12h to obtain a uniform mixed solution. Thereafter, the uniform slurry was coated on a PP separator (Celgard 2500) using a 100 μm doctor blade, and the composite separator was immersed in anhydrous ethanol to perform phase inversion. Finally, the composite membrane was vacuum dried at 70 ℃ for 24 h. The obtained composite membrane was designated as PP @ PHNTP-90.
The prepared PP @ PHNTP-90 is used as a diaphragm, a lithium foil or a copper foil is used as an electrode, and 1M LiPF6DMC EMC (volume ratio 1:1:1) was used as an electrolyte to assemble a button cell for lithium deposition testing and charge-discharge cycle testing. Meanwhile, a PP diaphragm is used as a comparison sample to carry out corresponding deposition test and charge-discharge cycle test.
The experimental result shows that compared with a PP diaphragm, NaTi is loaded on the surface of PP @ PHNTP-902(PO4)3. NaTi can be seen by SEM picture2(PO4)3The particle diameter was about 100-300nm and the thickness of the composite coating was about 5 μm (FIG. 2). In subsequent coulombic efficiency tests, the asymmetric cells assembled with PP @ PHNTP-90 separator exhibited higher coulombic efficiency (fig. 3). Li-Li symmetrical battery assembled by PP @ PHNTP-90 diaphragms has current density of 1mA cm-2The deposition capacity is 1mAh cm-2The cycle was stabilized for 350h (fig. 4). The coulomb efficiency and the cycle stability of the battery assembled by the PP @ PHNTP-90 diaphragm are obviously superior to those of the battery assembled by the PP diaphragm.
Example 2
The embodiment of the invention provides an ion-conducting organic-inorganic composite layer modified diaphragm, which is prepared by the following steps:
1.7204g of Ti (OC) were first introduced4H9)4Dissolved in 20mL of absolute ethanol and 0.3404g of CH were added under magnetic stirring3COONa·3H2O and 2mL of concentrated hydrochloric acid were added to the above solution to obtain solution A. 0.8566g H will be mixed3PO4(concentration 85 wt.%) was dissolved in 15mL of absolute ethanol and added dropwise to solution A. Then stirring for 3h at 55 ℃, and evaporating the absolute ethyl alcohol solvent to dryness to obtain NaTi2(PO4)3And (3) precursor particles. Grinding the precursor particles into powder in a mortar, and calcining for 5 hours at 750 ℃ in Ar atmosphere to obtain NaTi2(PO4)3And (3) powder. Then adding NaTi2(PO4)3And performing high-energy ball milling on the powder for 3 hours.
20 wt% of NTP powder is added into 5mL of DMF for ultrasonic dispersion for 1 h. Then, PVDF-HFP and LiClO were mixed4(mass ratio 3: 1) and stirring at 60 ℃ for 12h to obtain a uniform mixed solution. Thereafter, the uniform slurry was coated on a PP separator (Celgard 2500) using a 100 μm doctor blade, and the composite separator was immersed in anhydrous ethanol to perform phase inversion. Finally, the composite membrane was vacuum dried at 70 ℃ for 24 h. The obtained composite membrane was designated as PP @ PHNTP-20.
Example 3
1.7204g of Ti (OC) were first introduced4H9)4Dissolved in 20mL ofIn aqueous ethanol, 0.3404g of CH were added under magnetic stirring3COONa·3H2O and 2mL of concentrated hydrochloric acid were added to the above solution to obtain solution A. 0.8566g H will be mixed3PO4(concentration 85 wt.%) was dissolved in 15mL of absolute ethanol and added dropwise to solution A. Then stirring for 3h at 55 ℃, and evaporating the absolute ethyl alcohol solvent to dryness to obtain NaTi2(PO4)3And (3) precursor particles. Grinding the precursor particles into powder in a mortar, and calcining for 5 hours at 750 ℃ in Ar atmosphere to obtain NaTi2(PO4)3And (3) powder. Then adding NaTi2(PO4)3And performing high-energy ball milling on the powder for 3 hours.
90 wt% NTP powder is added into 5mL DMF for ultrasonic dispersion for 1 h. Then, PVDF-HFP and LiClO were mixed4(mass ratio 3: 1) and stirring at 60 ℃ for 12h to obtain a uniform mixed solution. And then, coating the uniform slurry on a PE diaphragm by using a 100-micrometer scraper, and then soaking the composite diaphragm into absolute ethyl alcohol for phase inversion. Finally, the composite membrane was vacuum dried at 70 ℃ for 24 h. The obtained composite membrane was designated as PE @ PHNTP-90.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (9)
1. An ion-conducting organic-inorganic composite modified diaphragm is characterized by comprising a porous diaphragm substrate and slurry coated on the porous diaphragm substrate; the slurry is prepared by the following method: the lithium ion conductive inorganic particle, the lithium ion conductive polymer and the lithium salt are dispersed in the solvent.
2. The ion-conducting organic-inorganic composite modified separator according to claim 1, wherein the lithium ion-conducting inorganic particles are garnet-type solid electrolytes, perovskite-type Li3xLa2/3–xTiO3Solid electrolyte, NASICON type Li1+xAlxTi2–x(PO4)3，Li1+xAlxGe2–x(PO4)3Solid electrolyte, anti-perovskite Li3–2xMxHalO solid electrolyte, LiPON solid electrolyte and sulfide solid electrolyte.
3. The ion-conducting organic-inorganic composite modified membrane according to claim 1, wherein the polymer capable of conducting lithium ions is at least one of polyethylene oxide, polyacrylonitrile, polyvinylidene fluoride, polymethyl methacrylate, polypropylene oxide, polyvinylpyrrolidone, polyvinylidene chloride, polypropylene carbonate, polyvinylidene fluoride-hexafluoropropylene.
4. The ion conducting organic-inorganic composite modified separator according to claim 1, wherein the lithium salt is at least one of lithium perchlorate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bis (oxalato) borate, lithium trifluoromethylsulfonate, lithium bis (trifluoromethylsulfonate) imide, and lithium tris (trifluoromethylsulfonate) methide.
5. The ion-conducting organic-inorganic composite modified membrane according to claim 1, wherein the porous membrane substrate is one or both of a polyethylene membrane and a polypropylene membrane.
6. The method for preparing the ion-conducting organic-inorganic composite modified membrane as claimed in any one of claims 1 to 5, wherein the ion-conducting organic-inorganic composite modified membrane is obtained by coating the slurry on a porous membrane substrate, immersing the porous membrane substrate in absolute ethyl alcohol and drying the porous membrane substrate.
7. The method for preparing the ion-conducting organic-inorganic composite modified membrane according to claim 6, wherein the drying is performed at 60 to 80 ℃.
8. The use of the ion-conducting organic-inorganic composite modified separator as claimed in any one of claims 1 to 5, wherein the separator is coated on a lithium metal negative electrode.
9. The use of the ion-conducting organic-inorganic composite modified membrane according to claim 8, wherein the coating thickness is 1 to 10 μm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024052076A1 (en) | 2022-09-08 | 2024-03-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for producing an electrode, electrode, alkaline battery, and uses of the alkaline battery |
| CN117855582A (en) * | 2024-03-08 | 2024-04-09 | 河南师范大学 | Flexible composite solid electrolyte and preparation and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1969407A (en) * | 2004-07-07 | 2007-05-23 | 株式会社Lg化学 | New organic/inorganic composite porous film and electrochemical device prepared thereby |
| WO2015152478A1 (en) * | 2013-04-05 | 2015-10-08 | 주식회사 엘지화학 | Secondary battery having improved life span performance |
| US20170194663A1 (en) * | 2016-01-04 | 2017-07-06 | Aruna Zhamu | Solid state electrolyte for lithium secondary battery |
| WO2018038524A1 (en) * | 2016-08-26 | 2018-03-01 | 삼성에스디아이 주식회사 | Separation film for lithium metal battery, lithium metal battery comprising same |
| CN108695547A (en) * | 2018-04-28 | 2018-10-23 | 浙江锋锂新能源科技有限公司 | A kind of Organic-inorganic composite dielectric film and the battery with the dielectric film |
| CN109286039A (en) * | 2018-10-22 | 2019-01-29 | 浙江锋锂新能源科技有限公司 | A kind of solid state battery dielectric film and preparation method thereof and the solid state battery with the dielectric film |
-
2020
- 2020-12-24 CN CN202011553978.2A patent/CN112670673A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1969407A (en) * | 2004-07-07 | 2007-05-23 | 株式会社Lg化学 | New organic/inorganic composite porous film and electrochemical device prepared thereby |
| WO2015152478A1 (en) * | 2013-04-05 | 2015-10-08 | 주식회사 엘지화학 | Secondary battery having improved life span performance |
| US20170194663A1 (en) * | 2016-01-04 | 2017-07-06 | Aruna Zhamu | Solid state electrolyte for lithium secondary battery |
| WO2018038524A1 (en) * | 2016-08-26 | 2018-03-01 | 삼성에스디아이 주식회사 | Separation film for lithium metal battery, lithium metal battery comprising same |
| CN108695547A (en) * | 2018-04-28 | 2018-10-23 | 浙江锋锂新能源科技有限公司 | A kind of Organic-inorganic composite dielectric film and the battery with the dielectric film |
| CN109286039A (en) * | 2018-10-22 | 2019-01-29 | 浙江锋锂新能源科技有限公司 | A kind of solid state battery dielectric film and preparation method thereof and the solid state battery with the dielectric film |
Non-Patent Citations (1)
| Title |
|---|
| 黄志峰: "NASICON型磷酸钛盐的制备及储锂_钠性能研究", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024052076A1 (en) | 2022-09-08 | 2024-03-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for producing an electrode, electrode, alkaline battery, and uses of the alkaline battery |
| DE102022209362A1 (en) | 2022-09-08 | 2024-03-14 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Method for producing an electrode, electrode, alkaline battery and uses of the alkaline battery |
| CN117855582A (en) * | 2024-03-08 | 2024-04-09 | 河南师范大学 | Flexible composite solid electrolyte and preparation and application thereof |
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Application publication date: 20210416 |